1 s2.0 S2772656822000239 Main

Carbon Capture Science & Technology 4 (2022) 100052
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Carbon Capture Science & Technology

journal homepage: www.elsevier.com/locate/ccst
Full Length Article
Recent Progress in Integrated CO2 Capture and Conversion Process Using

Dual Function Materials: A State-of-the-Art Review
Jian Chen a,†, Yongqing Xu b,†, Peizhi Liao c, Haiming Wang b,∗, Hui Zhou b,∗
a
School of Automotive Engineering, Changshu Institute of Technology, Changshu, 215500, China
b
Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Beijing Key Laboratory of CO2 Utilization and Reduction Technology, Department
of Energy and Power Engineering, Tsinghua University, Beijing, 100084, China
c
Key Laboratory of Smart Manufacturing in Energy Chemical Processes, Ministry of Education, East China University of Science and Technology, Shanghai, 200237,
China
a r t i c l e i n f o a b s t r a c t
Keywords: CO2 , despite its role as the primary greenhouse gas, is well-accepted as the most affordable and abundant non-
CO2 capture toxic C1 source. Integrated CO2 capture and conversion (ICCC) is an emerging and promising process capable of
In-situ CO2 conversion reducing CO2 emissions and in-situ producing value-added products such as CH4 and syngas. This article reviews
Dual function materials
the recent research progress on the ICCC process, with an emphasis on the development of dual function materials
Thermodynamic
(DFMs). The ICCC process with the combination of different CO2 catalytic conversions is first discussed from a
Mechanism
thermodynamic point of view. The influence of operation parameters on the performance of DFMs is also sum-
marized in detail. Then, the development of DFMs categorized by the catalytic component (i.e., Ni, Ru, etc.) is
reviewed, including their performance and potential reaction mechanisms. Finally, the challenges and prospects
of the ICCC process are highlighted.
Introduction Institute, 2021). According to the IEA, approximately 20% of anthro-

pogenic CO2 emissions can be reduced by applying CCS (IEA, 2019,
Since the industrial revolution and excessive consumption of fossil 2021). The CCS is mainly composed of three steps: the capture, trans-
fuels, a large amount of anthropogenic CO2 has been emitted into the at- port, and storage of CO2 . The CO2 capture is the first step and is usu-
mosphere. As a result, the atmospheric CO2 concentration has increased ally implemented to concentrate CO2 from the exhaust gases of power
to 416 ppm in 2021, which is nearly 1.45 times as high as that in 1850 stations, cement plants, and other industries (Bains et al., 2017). How-
(Gul and Tezcan Un, 2022; Mountourakis et al., 2021). The increase in ever, compared to the latter two steps, the CO2 capture is the most
the atmospheric CO2 concentration has raised global concerns as CO2 is energy-intensive, accounting for about 60−70% of the total cost for CCS
the major component in greenhouse gases responsible for global warm- (Bhown and Freeman, 2011). Therefore, significant efforts have been de-
ing (Bhattacharyya et al., 2021). In this context, the Paris Agreement voted to developing CO2 capture technologies with high technical and
was adopted in December 2015 to hold the global average tempera- economic feasibility (Gao et al., 2022; Guo et al., 2021). In terms of the
ture increase to well below 2°C and pursue efforts to limit it to 1.5°C details on the recent research progresses on these CO2 capture technolo-
above pre-industrial levels (McCollum et al., 2018; Rogelj et al., 2016; gies (e.g., post-combustion CO2 capture, pre-combustion CO2 capture,
Tollefson and Weiss, 2015). To achieve this target, the International oxy-fuel combustion, and chemical looping combustion), we refer read-
Energy Agency (IEA) recommended that the global energy-related CO2 ers to relevant review papers (Bui et al., 2018; Chen et al., 2020; Dunstan
emissions in 2060 should be eliminated to approximately 25% of that et al., 2021; Gao, W. et al., 2020; Sun et al., 2018; Yan et al., 2019). Af-
in 2014 (IEA, 2017). Recently, China also pledged to have CO2 emis- ter the capture step, the concentrated CO2 stream is compressed, trans-
sions peak before 2030 and to achieve carbon neutrality before 2060 ported, and stored in deep geological features permanently (Kim et al.,
(Liu et al., 2021). Hence, it is necessary and urgent to find solutions to 2017).
cut CO2 emissions effectively. Despite its role as a major greenhouse gas, CO2 is also re-
Carbon capture and storage (CCS) is a promising approach to mit- garded as an ideal C1 source because of its high abundance, low
igate excessive CO2 emissions in the short-to-mid term (Hong, 2022; cost, nontoxicity, and renewability (Cunningham and Jessop, 2019;
∗
Corresponding authors.
E-mail addresses: wang2020@tsinghua.edu.cn (H. Wang), huizhou@tsinghua.edu.cn (H. Zhou).
†
These authors contributed equally.
https://doi.org/10.1016/j.ccst.2022.100052
Received 11 May 2022; Received in revised form 25 May 2022; Accepted 25 May 2022
2772-6568/© 2022 The Author(s). Published by Elsevier Ltd on behalf of Institution of Chemical Engineers (IChemE). This is an open access article under the CC
BY license (http://creativecommons.org/licenses/by/4.0/)
J. Chen, Y. Xu, P. Liao et al. Carbon Capture Science & Technology 4 (2022) 100052
Ikreedeegh and Tahir, 2021; Zhang, R.-Z. et al., 2020). Hence, carbon that a reducing atmosphere is used for sorbent regeneration in the ICCC,
capture and utilization (CCU), where the captured CO2 is featured by rather than a CO2 -rich atmosphere commonly recommended in the con-
utilization rather than geological storage, has received growing atten- ventional CO2 capture process using sorbents (Chen et al., 2019). As a
tion worldwide. The CO2 utilization can be classified into direct and result, the regeneration temperature of sorbents can be significantly de-
indirect uses. Direct use involves the utilization of CO2 at its pure state creased, thus saving great energy and even making it highly possible to
or suspended in a solution, mainly including enhanced oil recovery, food operate isothermally in the ICCC. For example, when calcium looping
preservation, carbonated drinks, and fire extinguishers (Alper and Yuk- process is integrated with dry reforming of methane (i.e., ICCC-DRM)
sel Orhan, 2017; Kamkeng et al., 2021). In contrast, indirect CO2 uti- using Ni-based DFMs, the regeneration temperature of CaO-based sor-
lization, also named as CO2 conversion, converts CO2 into value-added bents was decreased from 940 to 720 °C (Kim et al., 2018). Moreover,
chemicals and fuels through different chemical processes, which is more the energy consumption in the ICCC-DRM process was 22% lower than
attractive than direct CO2 utilization as it is capable of solving environ- that of conventional dry reforming of methane for CO2 utilization (Tian
mental problems and energy crises simultaneously (Anwar et al., 2020). et al., 2019).
Thus tremendous research has been conducted on CO2 conversion (Das Herein, we critically review the recent research progress on the ICCC
et al., 2020; Jiang et al., 2019; Zhang, W. et al., 2021), with an em- process, focusing on the development of DFMs. It is well-known that the
phasis on thermocatalysis (De et al., 2020; Liang, J. et al., 2021; Wang operating parameters such as reaction temperature and atmosphere play
et al., 2021), photocatalysis (Gao, Y. et al., 2020; Kong et al., 2020; a crucial role in the performance of DFMs (mainly referring to their CO2
Ran et al., 2018), electrocatalysis (Liang, F. et al., 2021; Zhang et al., capture, decarbonation, and catalytic performance). Hence, the ICCC
2018), and other emerging CO2 catalytic conversion processes such as with the production of different products is first analyzed from a ther-
thermo-photocatalysis and application of external magnetic fields (Ma modynamic point of view, and the influence of operation parameters
et al., 2020; Zhang, Y. et al., 2020). Moreover, CO2 conversion can also on DFMs’ performance is discussed in detail. Then, the development
be regarded as an alternative approach for renewable energy storage, of DFMs categorized by the catalytic component is reviewed, including
when renewable electricity or H2 produced from water electrolysis by their performance and reaction mechanisms. Finally, the challenges and
using renewable electricity is involved in the process. For instance, the prospects of the ICCC process are discussed.
concept of Power-to-Gas (PtG, or P2G) has been developed in recent
years, in which renewable electricity is used to produce H2 via water Fundamental understandings of the ICCC process
electrolysis, and the H2 is then used to react with CO2 to produce CH4
(Mazza et al., 2018; Thema et al., 2019). As a result, the energy from A typical ICCC process starts from a CO2 capture stage, where DFMs
electricity is stored in CH4 through PtG technology. are applied to capture the CO2 from the flue gases or ambient air un-
Although value-added chemicals and fuels such as CH4 , syngas, and til saturation, as shown in Fig. 1. After that, the carbonated DFMs are
methanol, can be produced through carbon capture and conversion exposed to a reducing atmosphere, such as H2 , and CH4 , to launch an
(CCC), the high cost associated with CO2 compression and transporta- in-situ CO2 conversion stage. In such a stage, the absorbed CO2 is con-
tion remains a significant challenge for the CCC process. To make the verted into different products (e.g., CH4 , CO, or syngas, according to
CCC process more economically viable and realize its application on Eqs. 1–4), and the DFMs are regenerated at the same time. To the best
large scales, a novel integrated CO2 capture and conversion (ICCC) is of our knowledge, ICCC-methanation (ICCC-Met), ICCC-reverse water
proposed and has been a hot research topic (Omodolor et al., 2020; gas shift (ICCC-RWGS), and ICCC-dry reforming (ICCC-DR) have been
Sun, S. et al., 2021b; Tsiotsias et al., 2020). Thus far, various kinds of investigated mostly (Shao et al., 2021b; Sun, S. et al., 2021b; Zhang, W.
the ICCC processes have been developed by combinations of different et al., 2021) since the concept of ICCC process using DFMs was proposed
CO2 capture and CO2 conversion approaches, such as the ionic liquids- in 2015 (Duyar et al., 2015). Note that the operation conditions such as
based hybrid process (Lian et al., 2021), the solvent-based CO2 cap- temperatures, gas hourly space velocity (GHSV), and atmospheres differ
ture and electrolysis process (Daniel et al., 2022), the high-temperature a lot in each ICCC process, which is mainly due to the difference in ther-
electrochemistry-based CO2 transport membranes (Zhang, P. et al., modynamics and kinetics of each reaction route. Therefore, to give read-
2021), the hybrid CO2 capture and photocatalytic conversion process ers a better comprehensive idea of the ICCC process, each ICCC process
by using a novel hybrid sorbent/photocatalyst (Liu et al., 2015), and (i.e., ICCC-Met, ICCC-RWGS, and ICCC-DR) is discussed in this section
the hybrid CO2 capture (based on solid CO2 sorbent) and thermocat- from a thermodynamic point of view. Then, the influence of operation
alytic conversion process (Sun, S. et al., 2021b). This review focuses parameters on the performance of each ICCC process is summarized in
on the hybrid CO2 capture and thermocatalytic conversion process. In detail.
such a process, CO2 capture and conversion are integrated by using dual
function materials (DFMs). The DFMs consist of a sorbent and a catalytic CO2 + 4H2 → CH4 + 2H2 O ∆H298K 0 = −164 kJ/mol (1)
component for CO2 capture and conversion, respectively. The sorbent
component is usually composed of alkali metal oxides or carbonates, CO2 + H2 → CO + H2 O ∆H298K 0 = +41 kJ/mol (2)
whereas the catalytic component is usually composed of metal-based
catalysts such as Ru, Rh, and Ni. First, CO2 is captured from the ex- CO2 + CH4 → 2CO + 2H2 ∆H298K 0 = +247 kJ/mol (3)
haust gases (e.g., flue gas from coal-fired power plants with a CO2 con-
centration of 15 vol.% (Chen et al., 2021)) by the sorbent component 2CO2 + C2 H6 → 4CO + 3H2 ∆H298K 0 = +149 kJ/mol (4)
in the DFMs. Once the CO2 capture step is finished, a reducing agent
(e.g., H2 , CH4, or other alkanes) is introduced to convert the adsorbed The design of reactors and optimization of process parameters are al-
CO2 to different value-added products by the catalytic component in ways dependent on the targeted reaction products and the DFM has been
the DFMs and to regenerate the sorbent component simultaneously. In used. Generally, sorbents such as K2 O, Na2 O, MgO, and CaO are applied
other words, CO2 is concentrated from the CO2 -lean exhaust gases and at different temperatures for CO2 capture, as illustrated in Fig. 2a, which
subsequently converted into different value-added products by using is determined by the reaction kinetics and thermodynamics. Besides,
DFMs through the ICCC. On one hand, energy-intensive CO2 compres- the products such as CH4 , CO, and syngas are also achieved at different
sion and transportation steps are avoided in the ICCC process. On the temperatures based on thermodynamics, as shown in Fig. 2b, which is
other hand, the conversion of CO2 and regeneration of sorbents are con- simulated by the Gibbs free energy minimization method. However, the
ducted simultaneously in one reactor. Hence, the ICCC process is more actual reaction path of the in-situ CO2 conversions is also determined
economically feasible than the conventional CCC process. Besides, note by the kinetics and the types of catalyst.
2
Fig. 1. Schematic diagram of the ICCC process.
Fig. 2. (a) The CO2 uptake capacity of the typical sorbents in ICCC processes (Sun, S. et al., 2021b); (b) Thermodynamic equilibrium of the products with a feed of
gas mixture of H2 and CO2 (H2 /CO2 = 4) under ambient pressure (Shao et al., 2021b).
ICCC-Met process fects of reaction system parameters on the performance of the ICCC-Met
process.
The ICCC-Met process comprises a CO2 capture stage and a metha-
nation stage. An exothermic methanation reaction, as shown in Eq. 1, 2CO → CO2 + C ∆H298K 0 =+172 kJ/mol (5)
also known as the Sabatier reaction, occurs in the methanation stage,
where the CO2 absorbed is converted into CH4 . The ICCC-Met is an The CO2 capture and conversion processes are highly recommended
exothermic process, which does not require additional heat input and to be operated under isothermal conditions, thus avoiding CO2 de-
is critical for industrial applications. From a thermodynamic perspec- carbonation by temperature swing for the consideration of energy-
tive, the methanation reaction is more favorable at lower temperatures, consuming. Besides, in situ CO2 conversion by the catalytic sites, ac-
and it is thermodynamically spontaneous (Δ𝐺𝑚 0 < 0) when the reaction
companied by the regeneration of the carbonation sites, significantly
temperature is below 350 °C, as illustrated in Fig. 2b. However, with simplifies the overall CO2 conversion process and enhances the process
a decrease in the reaction temperatures, the rate of methanation re- efficiency.
action drops drastically, which is controlled and limited by the reac- The reaction temperature is a critical factor in the ICCC-Met pro-
tion kinetics. Moreover, the selectivity of the CH4 is highly sensitive cess, which is highly dependent on the type of CO2 sorbents used in
to the reaction temperature because the side reactions such as RWGS the DFMs. For the Na2 O- and K2 O-based DFMs, the ICCC-Met process
(Eq. 2), dry reforming of methane (DRM) (Eq. 3), and Boudouard reac- always runs at 300−400 °C because the decomposition temperatures of
tion (Eq. 5), may occur when the reaction temperature is above 400 °C. Na2 CO3 and K2 CO3 (decomposed to K2 O, Na2 O, and CO2 ) were reported
Tables 1 and 2 list some typical ICCC-Met systems and summarize the ef- to drop drastically from above 850 °C to below 400 °C when supported
3
J. Chen, Y. Xu, P. Liao et al.
Table 1
Summary of the ICCC-Met reaction systems using Ni-based DFMs.
DFMs Operation conditions
Sorbent Catalyst Promoter Support CO2 capture CO2 conv. CO2 uptake capacity (mol/kg) CO2 conv. (%) CH4 yield (mol/kg) Sel. (%) Ref.
MgO Ni Al2 O3 300°C, 50%CO2 , 30min, 350°C, H2 , 2.27 90 2.85 89 (Liu et al., 2022)
1bar, 50ml/min 1bar, 600ml/min
/ Ni (15%) 85%ZrO2 350°C, 350°C, 20 - 89 (Hu and
K (5%) 80%ZrO2 4.7% CO2 /He 100% H2 51 - 98 Urakawa, 2018)
La (5%) 80%ZrO2 32 - 99
CaO Ni (1%) CeO2 550°C, 15% CO2 , 60min, 550°C,100%H2 , 60min, 15.3 62 8 84 (Sun, H. et al.,
1bar, 50ml/min 1bar, 50ml/min 2021)
Na2 O (6.1%) Ni (10%) 𝛾-Al2 O3 320°C, 320°C, 0.11 0 0 (Arellano-Treviño
1%Pt 7.5%CO2 / 15% H2 /N2 0.35 87 0.25 et al., 2019b)
0.1%Pd 4.5%O2 /15%H2 O/N2 0.47 57 0.18
1%Ru 0.53 (20th cycle) 95 (20th cycle) 0.37 (20th cycle)
MgO Ni (Ni/Al=2) Al2 O3 200°C, 200°C, 1.42 wt% up to 100 (Zhou et al., 2020)
15% CO2 /N2 100% H2
CaO (15%) Ni (15%) Al2 O3 520°C, 520°C, 0.17 0.142 (Bermejo-López
10% CO2 /Ar 10% H2 /Ar et al., 2019b)
Na2 CO3 (10%) 400°C, 400°C, 0.21 0.19
10% CO2 /Ar 10% H2 /Ar
CaO (10%) Ni (10%) 𝛾-Al2 O3 320°C, 320°C, 0.31 46 0.14 (Chai et al., 2020)
Na2 CO3 (10%) 9.5% CO2 /N2 10% H2 /N2
CaO Ni (10%) 400°C, 400°C, 7.4 0 0 (Jo et al., 2020)
4
10%CO2 / 10%H2 O/N2 90% H2 /N2

500°C 500°C 8.96 8.34 93
600°C 600°C 15.49 14.94 96
700°C 700°C 16.22 4.7 29
MgO Ni Li-Na-K CeO2 300°C, 300°C, 2.74 40 1.1 89 (Huang et al.,
65% CO2 /N2 5% H2 /N2 2021)
Ni (15%) 𝛾-Al2 O3 450°C, 450°C, 0.01 0.01 (Kosaka et al.,
Na (15%) Ni (15%) 5% CO2 /N2 100% H2 0.21 96 0.19 93 2021)
K (15%) Ni (15%) 0.23 96 0.13 61
Ca (15%) Ni (15%) 0.07 82 0.06 97
CaO Ni (10%) 600°C, 600°C, 5.8 20th cycle 93 (20th cycle) 4.1 70 (Ma et al., 2021)
CaO Ni (10%) M (M=Mg, Al, Mn, 15% CO2 /N2 66.7% H2 /N2 9 for Ni-CaZr in 20 cycles 94 for Ni-CaZr 6.7 for Ni-CaZr 74
Y, Zr, La, or Ce)

Ca/M=9:1
CaO Ce 550°C, 550°C, 14.9 39 0 (Sun, S. et al.,
CaO Ni (1%) 15% CO2 /N2 100% H2 9.2 38 2.0 58 2021a)
CaO Ni (10%) 8.1 45 2.0 69
CaO Ni (1%) Ce 10.6 42 3.3 74
CaO Ni (1%) CeO2 nanorod 15.3 62 8 84
CaO CeO2 550°C, 550°C, 14.9 mmol/g-CaO 40 0
CaO Ni (0.5% to CeO2 ) CeO2 5%CO2 /N2 100% H2 17.7 mmol/g-CaO 50 1540 mmol/g-Ni; 86 (Sun, H. et al.,
CaO Ni (1% to CeO2 ) CeO2 15.2 mmol/g-CaO 62 800 mmol/g-Ni; 84 2022)
CaO Ni (5% to CeO2 ) CeO2 14.3 mmol/g-CaO 68 168 mmol/g-Ni; 86
Li4 SiO4 Ni (10 %) 550°C, 550°C, 4.49 (5th cycle) 100 4.56 mmol/g-Ni; (5th 100 (Jo et al., 2022a)
10% CO2 /10%H2 O/N2 90 % H2 /N2 cycle)
Table 2
Summary of the ICCC-Met reaction systems using Ru- and Rh-based DFMs.
DFMs Operation conditions CO2 uptake capacity CH4 yield

(mol/kg) CO2 conv. (%) (mol/kg) Sel. (%) Ref.
Sorbent Catalyst Support CO2 capture CO2 conv.
CaO (10%) Ru (5%) 𝛾-Al2 O3 320°C, 320°C, 5%H2 /N2 0.41 76 0.31 100 (Duyar et al., 2015)
10%CO2 /Air
320°C, 10%CO2 /21%H2 O/Air 320°C, 5%H2 /N2 – – 0.27 100
CaO (10%) Ru (5%) SBA-150 320°C, 10%CO2 /N2 320°C, 4%H2 /N2 – – 0.4 – (Duyar et al., 2016)
CaO (10%) Rh (0.1%) – – 0.5 –
CaO (10%) Rh (1%) – – 0.7 –
CaO (10%) Rh (5%) – – 0.7 –
CaO (10%) Rh (10%) – – 0.9 –
K2 CO3 (10%) Ru (5%) – – 0.91 –
Na2 CO3 (10%) Ru (5%) – – 1.05 –
CaO (10%) Ru (5%) Al2 O3 powder 320°C, 320°C, 5%H2 /N2 0.28 48 0.13 – (Zheng et al., 2016)
Al2 O3 TH200 7.5%CO2 /15%H2 O/4.5%O2 /N2 0.14 91 0.14 –
5
Al2 O3 TH100 0.17 87 0.2 –

Al2 O3 beads 0.18 58 0.12 –
Na2 CO3 (10%) Ru (5%) SBA-150 320°C, 7.5%CO2 /N2 320°C, 5%H2 /N2 – 61 – – (Wang et al., 2017)
320°C, 320°C, 5%H2 /N2 – 90 – –
7.5%CO2 /15%H2 O/4.5%O2 /N2
22%K2 CO3 /Al2 O3 4%Ru/Al2 O3 20-25°C, Air 300°C, 100% H2 19.7ml CO2 /g-sorbent 94 – – (Veselovskaya et al.,
2018b)
14%K2 CO3 /Al2 O3 25°C, Air 300°C, 100% H2 – – 98% – (Veselovskaya et al., 2020)
Na2 O (6.1%) Ru (5%) 𝛾-Al2 O3 300°C, 300°C, 15%H2 /N2 98.66 ml 79 – – (Wang et al., 2018)
7.5%CO2 /15%H2 O/4.5%O2 /N2
CaO (5%) Ru (4%) Al2 O3 400°C, 400°C, 10%H2 /N2 0.46 – 0.41 98 (Bermejo-López et al.,
CaO (10%) 1.4% CO2 /Ar 0.29 – 0.26 98 2019a)
CaO (15%) 0.10 – 0.10 88

Na2 CO3 (5%) 310°C, 310°C, 10%H2 /N2 0.15 – 0.13 98
Na2 CO3 (10%) 1.4% CO2 /Ar 0.41 – 0.38 94
Na2 CO3 (15%) 0.41 – 0.38 92
(continued on next page)
Table 2 (continued)
DFMs Operation conditions CO2 uptake capacity CO2 conv. (%) CH4 yield Sel. (%) Ref.
(mol/kg) (mol/kg)
Sorbent Catalyst Support CO2 capture CO2 conv.
6.1%Na2 O Ru(5%) 320°C, 320°C, 15%H2 /N2 0.39 75 0.29 – (Arellano-Treviño et al.,
7.5%CO2 /15%H2 O/4.5%O2 /N2 2019a)
6.1%Na2 O Ru(5%) 320°C, 10%CO2 /N2 320°C, 10%H2 /N2 0.65 96 0.61 –
6.1%Na2 O Rh(0.5%) 0.63 69 0.42 –
7.1%K2 O Ru(5%) 0.50 96 0.47 –
10%CaO Ru(5%) 0.68 96 0.61 –
10%MgO Ru(5%) 0.23 91 0.21 –
MgO Ru (2.5%) CeO2 300°C, 300°C, 5%H2 /N2 2.9 (10th cycle) 39 (10th cycle) 1.13 (10th cycle) – (Sun et al., 2020)
MgO Ru (5%) CeO2 65% CO2 /N2 4.2 (10th cycle) 79 (10th cycle) 3.36 (10th cycle) –
MgO Ru (10%) CeO2 3.3 (10th cycle) 69 (10th cycle) 2.31 (10th cycle) –
6.1%Na2O Ru (0.5%) 𝛾-Al2 O3 320°C, 400ppmCO2 /21%O2 /N2 320°C, 15%H2 /N2 0.21 (4th cycle) 82 0.17 (4th cycle) 100 (Jeong-Potter and
320°C, 7.5CO2 /N2 , 320°C, 15%H2 /N2 0.34 – 0.27 90 Farrauto, 2021)
320°C, 7.5%CO2 /15%H2 O/N2 320°C, 15%H2 /N2 0.26 – 0.22 100
Li (1%) Ru (1%) 𝛾-Al2 O3 350°C, 1%CO2 /He 350°C, 4%H2 /He 0.002 – 0.002 – (Porta et al., 2021a)
Na (3%) 0.05 100 0.05 100
6
K (5%) 0.19 100 0.18 94

Mg (3.2%) 0.004 100 0.004 100
Ca (5.1%) 0.14 78 0.11 99
Ba (16%) 0.23 69 0.15 99
NaNO3 (17%)/MgO Ru (1%) 𝛾-Al2 O3 300°C, 10%CO2 /N2 , 11% 300°C, 10%H2 /N2 2.62 62 1.51 – (Park et al., 2021)
absolute humidity 0.4 119 0.38 –
BaO(16%)/𝛾-Al2 O3 Ru(1%)/𝛾-Al2 O3 350°C, 1%CO2 /He 350°C, – – 0.10 (3rd cycle) 100 (Porta et al., 2021b)
BaO (16%) Ru(0.84%) 𝛾-Al2 O3 4% H2 /He – – 0.15 (3rd cycle) >98
Na2 O (10%) Ru (1%) 𝛾-Al2 O3 25°C, 300°C, 15%H2 /N2 0.52 (10th cycle) – 0.28 (10th cycle) 100 (Jeong-Potter et al., 2022)
CaO (10%) 400ppm CO2 , air 0.46 (3rd cycle) – 0.35 (3rd cycle)
Na2 O (10%) 25°C, 400ppm CO2 /air, 2%H2 O 1.25 (5th cycle) – 1.07 (5th cycle)
CaO (10%) 0.25 (3rd cycle) – 0.18 (3rd cycle)
LiNaK-MgO Ru (2%) CeO2 -rod 300°C, 35%CO2 /N2 300°C, – 56 0.33 100 (Sun, S. et al., 2022)

LiNaK-MgO Ru (2%) CeO2 -particle 5% H2 /N2 – 60 0.29
LiNaK-MgO Ru (2%) CeO2 -cube – 3 0.03
8%Na2 CO3 -8%CaO Ru (4%) 𝛾-Al2 O3 400°C, 10%CO2 /Ar 400°C, 10%H2 /Ar 0.35 – 0.36 98 (Bermejo-López et al.,
16%Na2 CO3 – – 0.28 92 2022)
16%CaO – – 0.34 97
Li (5%) Ru (0.89%) 𝛾-Al2 O3 280°C, 10%CO2 /N2 280°C, 10%H2 /N2 – – 0.5 100 (Cimino et al., 2022)
Li (5%) 318°C, 10%CO2 /N2 318°C, 10%H2 /N2 – 95 0.29 100
on Al2 O3 . Wang et al. (Wang et al., 2018) investigated the system pa-
rameters such as temperature on the ICCC-Met performance using Ru-
Na2 O/Al2 O3 DFMs. They observed that the CO2 carbonation rate and
conversion rate decreased slightly as the temperature increased with
thermodynamics because the exothermic reactions are more favorable
at a lower temperature, as shown in Fig. 3a. For the MgO-based DFMs,
the ICCC-Met process always operates at 250−350 °C, when the MgO
is the major contributor to CO2 carbonation (Sun et al., 2020; Sun, S.
et al., 2022; Zhou et al., 2020). For the CaO-based DFMs, Bermejo-López
et al. (Bermejo-López et al., 2019a) studied the effect of temperature on
the ICCC-Met performance using Ru15%CaO/Al2 O3 isothermally from
280 to 400 °C, and observed that the maximum CH4 yield of 414 𝜇mol/g
was obtained at 400 °C. Jo et al. (Jo et al., 2020) further investigated the
effect of temperature on the ICCC-Met performance using 15%Ni/CaO
isothermally from 400 to 700 °C. They stated that no CH4 was formed
at the operation temperature of 400°C. A maximum CH4 yield of 14.94
mmol/g was achieved at 600°C. With the increase of the temperature
to 700°C, the CO2 uptake capacity was increased due to the enhanced
kinetics, and both the CH4 selectivity and yield were decreased signif-
icantly due to the formation of CO via RWGS reaction, as shown in
Fig. 4. Although CO2 uptake capacity and CH4 yield at 500°C were lower
than those at 600°C, 500°C was recommended as the optimal operating
temperature since the Tammann temperature of CaCO3 was 533°C. Re-
cently, Jo et al. (Jo et al., 2022a) proposed and investigated a kind of
Li4 SiO4 -based DFM at 550 °C for the ICCC-Met process. They reported
that the carbonated DFMs were entirely regenerated at a lower temper-
ature than the conventional decarbonation (∼ 750 °C). Thermodynamic
equilibrium analysis showed that the CH4 composition was decreased
drastically when the reaction temperature was increased to 350 °C due
to the undesirable RWGS and DRM side reactions. As the same time, low-
ering the reaction temperature improved the CH4 selectivity but spoiled
the CO2 conversion. The formation rate of CH4 was higher when a lower
temperature like 400 °C was used as the reaction temperature. Hence,
to achieve a high reaction rate and high CH4 selectivity, the reaction
temperature should be comprehensively considered from a trade-off be-
tween thermodynamics and kinetics.
In addition to the reaction temperature, the reaction gases also play
a pivotal role in the ICCC-Met process, and the contaminants in the re-
action gas, such as NOx , SOx , H2 O, and O2 , may alter the CO2 capture
and conversion performance. Arellano-Treviño et al. (Arellano-Treviño
et al., 2019a) observed that the methanation failed to proceed at 320
°C after O2 poisoning, making the DFMs unsuitable for application in
the ICCC-Met process. This was because the Ni was partially oxidized to
NiO after the exposure to O2 , which was not able to be reduced com-
pletely even after 6 h of 15%H2 /N2 exposure at 320°C. Besides, Zheng
et al. (Zheng et al., 2016) demonstrated that the presence of H2 O (with-
out O2 ) decreased the CO2 sorption, and the presence of O2 and H2 O
drastically decayed both the CO2 sorption and subsequently CH4 gen-
eration. The presence of H2 O slightly suppressed the CO2 sorption by
the competitive sorption and subsequently affected the spillover of CO2
from the sorption sites to the catalytic sites (Zheng et al., 2016). When
exposed to the O2 , the catalytic sites were oxidized and deactivated.
Moreover, it has been observed that H2 O promoted CO2 decarbonation
for the reason that H2 O had the ability of regenerating the sorption sites
that contain irreversibly sorbed CO2 , which accordingly resulted in bet-
ter CH4 formation performance (Miguel et al., 2017).
The sorption time is another factor that affects the ICCC-Met pro-
cess. Wang et al. (Wang et al., 2018) investigated the effect of sorption
time on the CO2 capture and methanation performance using 5%Ru-
6.1%Na2 O/Al2 O3 (Fig. 3b), and demonstrated that the CO2 uptake ca-
pacity was initially enhanced with the increase of sorption duration, but
it reached a plateau after 20 min. CH4 generation also increased slightly Fig. 3. Effect of (a) various reaction temperatures (1042 h−1 ), (b) reaction du-
ration (320 °C, 868 h−1 ) and (c) various feed GHSV (320 °C) on the ICCC-Met
when more CO2 was sorbed and available for conversion; however, the
performance of Ru-Na2 O/Al2 O3 DFMs. Nomenclature: Desorbed 3 = CO2 des-
desorbed CO2 was also increased, indicating that more Ru/Al2 O3 should
orbed during 3-min N2 purge; Desorbed M = CO2 desorbed during methanation.
be used to achieve higher methanation rate. Similar results were ob- Methanation was performed under 15%H2 /N2 (Wang et al., 2018).
served by Zheng et al. (Zheng et al., 2016), who studied the effect of
7
shown in Fig. 6, Bobadilla et al. (Bobadilla et al., 2016) investigated

the effect of CO2 concentration, reaction temperatures, and H2 O and/or
O2 contaminants on the CO2 uptake capacity, CO2 conversion rate, and
CO selectivity using K2 CO3 -FeCrCu hydrotalcite DFMs. They found that
higher temperatures improve both CO2 conversion and CO yield due to
the endothermic properties of RWSG and CO2 decarbonation, which was
also reported by other studies (Sun et al., 2019; Sun, S. et al., 2021a).
However, the CaO-based DFMs always run isothermally at 600−700 °C
in the ICCC-RWGS (Sun et al., 2019; Sun, S. et al., 2021a). Sun et al.
(Sun, S. et al., 2021a) studied the effect of reaction temperature from
600 to 700 °C on the CO production performance using CaO alone, which
yielded 0.34, 1.53, and 4.15 mmol/g at 600, 650, and 700 °C after 28
min of CO2 hydrogenation, as shown in Fig. 7. However, the CO2 con-
version rate was slightly dropped when increasing the RWGS reaction
temperature, which was 88.1% at 600 °C and 75.5% at 700 °C because
of the enhanced CO2 decarbonation kinetics. Shao et al. (Shao et al.,
2021a) also explored the effect of reaction temperature from 600 to
700 °C on the ICCC-RWGS performance using Fex Coy Mg10 CaO DFM and
Fig. 4. Effect of temperature on the CO2 capture and methanation over the
10wt%Ni/CaO (Jo et al., 2020). found that the DFMs achieved an excellent and stable high-temperature
CO2 uptake capacity of 9.0-9.2 mmol/g-DFMs , CO2 conversion efficiency
of 90%, and CO selectivity of 100% at 650 °C in the ICCC-RWGS process.
sorption time on the CO2 capture and methanation performance using Generally, the contaminants in the flue gas, such as O2 and H2 O,
5%Ru-10%CaO/Al2 O3 , as shown in Fig. 5a and b. The CH4 yield in- have negative effects on both CO2 capture and the RWGS process
creased with an increase in the sorption time from 10 to 20 min. How- (Bobadilla et al., 2016). It was reported that the presence of H2 O and O2
ever, it decreased with further increasing the sorption time, which was on the surface of DFMs hindered their RWGS activity due to the oxida-
due to the deactivation of the DFMs caused by the sintering and oxidation or poisoning of the DFMs, as shown in Fig. 6. Besides, lowering the
tion over the longer sorption time. CO2 concentration in the CO2 capture stage from 8% to 4% resulted in
Besides, the effect of flow rate or GHSV on the ICCC-Met perfor- lower CO2 capture efficiency due to the quicker saturation of the DFMs
mance was investigated by Zheng et al. (Zheng et al., 2016) and Wang with CO2 .
et al. (Wang et al., 2018). When increasing the GHSV from 694 to 868
h−1 , the CO2 sorption amount increased, while further increase of the
GHSV to 1215 h−1 led to a decrease of the CO2 sorption amount (Fig. 3c) ICCC-DR process
(Wang et al., 2018). The feed flow rate of methanation influences the
reaction due to the following reasons: i) a higher methanation flow rate, Note that CH4 is also a greenhouse gas and has a much higher po-
viz., higher space velocity, resulted in shorter residential time and lower tential for the greenhouse effect (∼ 22 times) than CO2 . Hence, the dry
conversion rate; and ii) H2 flow not only reduced the CO2 but also re- reforming of methane (DRM), which converts these two major green-
generated the Ru-species. Hence, the reactors should be designed and house gases (CO2 and CH4 ) into syngas, has received wide attention.
operated at moderate flow rates to provide a high H2 linear velocity Considering the fact that the DRM process occurs spontaneously
and sufficient residence time to make sure complete CO2 conversion (Δ𝑟 𝐺 < 0) when the reaction temperature is above 630 °C, Tian et al.
to CH4 . For example, Zheng et al. (Zheng et al., 2016) observed that (Tian et al., 2019) put forward and demonstrated the integrated CO2
the 5%Ru/CaO-Al2 O3 DFMs presented the best ICCC-Met performance capture and conversion using Ni-CaO bifunctional catalyst, i.e., ICCC-
when carbonated at a GHSV of 11236 h−1 and methanated at a GHSV DRM process, and reported that the energy consumption of the ICCC-
of 2611 h−1 . DRM process was 22% lower than that of conventional CH4 dry reform-
The ICCC-Met process is initially proposed to capture and convert ing for CO2 utilization (calculated by Gibbs free energy, enthalpy, and
the CO2 from flue gas into CH4 . However, recently, Veselovskaya et al. thermodynamic equilibrium), which means that the ICCC-DRM concept
(Veselovskaya et al., 2018a) reported that the ICCC-Met could also be for CO2 utilization was a promising option to recycle CO2 from flue
applied to capture the CO2 from ambient air. The CO2 from the ambient gases into high-valuable hydrocarbons.
air could be converted into CH4 with a high conversion (> 98%) at The ICCC-DRM process always starts from a CO2 capture stage by
325−400 °C using the activated K-promoted Ru/Al2 O3 catalyst. This the CO2 sorption sites, which is followed by an isothermal conversion
study was inspiring since it provided new insights into ICCC combined stage by the catalytic sites, when the absorbed CO2 spillovers to the cat-
with direct air capture (DAC). alytic sites and reacts with the CH4 . The ICCC-DRM process has been
proved to be much more cost-effective than the separated CO2 capture
ICCC-RWGS process and DRM process due to the avoided CO2 capture, compress, and trans-
portation processes. However, the effect of process parameters such as
The ICCC-RWGS process consists of a CO2 capture stage and an temperature, contaminant gases, and CO2 concentration on the ICCC-
RWGS stage, which generates the basic chemical product (i.e., CO) for DRM performance should be well investigated before industrial applica-
valuable hydrocarbons via Fischer-Tropsch reactions. The RWGS is a tion. Table 4 lists some of the typical ICCC-DR systems and summarizes
typical endothermic process, as illustrated in Eq. 2. The process param- the effects of the reaction parameters on the CO2 capture and in-situ DR
eters such as reaction temperature, CO2 sources, and contaminants play reaction performance.
pivotal roles in the ICCC-RWGS. Table 3 lists some typical ICCC-RWGS It has been observed that the CH4 conversion increased with the
systems and summarizes the effects of reaction system parameters on the increase of reaction temperature, while the selectivity of CO showed an
CO2 capture and in-situ RWGS reaction performance. For the BaO- and opposite trend due to the side reactions like CH4 decomposition (coking)
K2 O-based DFMs, the ICCC-RWGS process is always operated at around (Molina-Ramírez et al., 2020). A higher temperature in the system is a
350 °C because the decomposition temperature of BaCO3 and K2 CO3 benefit for the ICCC-DRM reaction in kinetics; however, it results in the
dropped drastically from 1350 and 890 °C to about 300 °C due to the reduction of the CO2 uptake capacity at equilibrium, and promotion of
enhanced surface carbonates composition (Bobadilla et al., 2016). As side reactions such as RWGS and CH4 cracking, which affects the ratio
8
Table 3
Summary of the ICCC-RWGS reaction systems.
DFMs Operation conditions CO2 uptake capacity CO yield

(mol/kg) CO2 conv. (%) (mol/kg) CO sel. (%) Ref.
Sorbent Catalyst Promoter Support CO2 capture CO2 conv.
CaO Ni Ce 650°C, 650°C, 14.1 52 7.3 100 (Sun et al.,

15% CO2 / N2 5% H2 /N2 2019)
Carbide slag Ni (10%) 650°C, 650°C, 13.28 39 5.12 100 (Wang, G. et al.,
10% CO2 /N2 5% H2 /N2 2022)
CaO (81%) Ni (10%) CeO2 (9%) 600°C, 15%CO2 , 25min, 600°C, 66.7%H2 , 60min, 9 (20th cycle) 20 (Ma et al., 2021)
100ml/min 30ml/min
K (10%) FeCrCu hydrotalcite 450°C, 450°C, ∼100% captured 80 91 (Bobadilla et al.,
(Mg/Al=0.29) 5.8%CO2 /N2 100%H2 2016)
450°C, 450°C, 100%H2 ∼100% captured 45 92
5.8%CO2 /5%O2 /4%H2 O/N2
550°C, 550°C, 100%H2 ∼100% captured 55−60 >95
9
5.8%CO2 /5%O2 /4%H2 O/N2

K Cu Al2 O3 350°C, 4.4%CO2 , 5min, 350°C, H2 , 5min, Capture efficiency 93 (Hyakutake
50ml/min, 50ml/min =48.4% et al., 2016)
Fe5 Co5 Mg10 CaO 650°C, 650°C, 9.2 90 8.28 100 (Shao et al.,
Fe10 Mg10 CaO 10%CO2 /N2 100% H2 9.09 80 7.2 99 2021a)
Co10 Mg10 CaO 8.9 75 6.54 98
Na2 O (3%) Pt (1%) Al2 O3 350°C, 1%CO2 /10%O2 /N2 350°C, 5%H2 /N2 0.19 89 0.16 93 (Li et al., 2022)
MgO (3%) Pt (1%) Al2 O3 0.12 22 0.01 51
K2 O (6%) Pt (1%) Al2 O3 0.12 19 0.007 31
CaO (6%) Pt (1%) Al2 O3 1.07 5 0.04 84
Na2 O (3%) Ru (1%) Al2 O3 0.61 6 0.006 17
Na2 O (3%) Cu(1%) Al2 O3 0.13 8 0.003 50

Na2 O (3%) Pt (1%) MgO 0.13 57 0.06 82
Na2 O (3%) Pt (1%) SiO2 0.32 4 0.006 48
Na2 O (3%) Pt (1%) TiO2 0.39 12 0.03 61
Fig. 5. Effect of sorption time-on-stream (TOS, 60, 20, or 10 min) on CO2 capture and methanation performance: (a) CO2 uptake capacity and (b) CH4 generation
during the methanation step (Zheng et al., 2016).
Fig. 6. CO2 capture efficiency, conversion, and

CO selectivity as a function of (a) CO2 concen-
tration (5.8 – 9.5%) and (b) reaction tempera-
ture (Bobadilla et al., 2016).
of H2 /CO in the outlet syngas and even destroy the catalytic sites in the Ramírez et al. (Molina-Ramírez et al., 2020) investigated the effect of
DFMs. reaction temperature from 600 to 700 °C on the ICCC-DRM performance
Thus far, almost all the sorbents used in the ICCC-DRM process are using BaO-based DFMs. They observed that 600 °C was the best reaction
high-temperature CO2 sorbents, like CaO, SrO, BaO, and Li4 SiO4 . How- temperature for the BaO-based DFMs in the ICCC-DRM system when it
ever, the optimum reaction temperature for the different ICCC-DRM achieved a net CO2 capture capacity of 0.232 mmol/g, a CO2 conversion
systems may be different. SrO-based sorbents are always operated at rate of 14%, and a CH4 conversion rate of 11%. The CaO-based DFMs
super high temperature windows (1100−1400 °C); however, Gu et al. have been explored for the ICCC-DRM process at various temperatures,
(Gu et al., 2022) reported that the SrO-based DFMs could be operated like 600 °C (Cruz-Hernández et al., 2017), 650 °C (Jo et al., 2022b),
at 875 °C for the reason that the double replacement of Ni and Ce al- and 720 °C (Hu et al., 2021b; Kim et al., 2018). After comparison, Jo
tered the phase structure of SrO, which not only adjusted the carbona- et al. (Jo et al., 2022b) reported that the Ni/CaO DFMs presented a rel-
tion/decarbonation thermodynamics to facilitate SrCO3 decomposition atively stable CH4 conversion rate for the reason that the Boudouard
at relatively low temperatures but also inhibited sintering of the DFMs; reaction is unfavorable when the temperature is above 700 °C. How-
finally, excellent activity and stability were presented in the ICCC-DRM ever, the amount of CO generated from DFM at 700 °C was relatively
process (>91% CH4 conversion, >72% CO2 capture efficiency). Molina- low due to the low CO2 capture capacity of the DFMs. Recently, Lv et al.
10
Table 4
Summary of the ICCC-DR reaction systems.
DFMs Operation condition CO2 uptake capacity CO2 conv. Yield

(mol/kg) (%) (mol/kg) Ref.
Sorbent Catalyst Promoter Support CO2 capture CO2 conv.
MgO Ni (10%) K Al2 O3 650°C, 650°C, 0.2 14 (Al-

MgO Ni (10%) Na 10% CO2 / N2 5% C2 H6 / N2 0.16 60 Mamoori
CaO Ni (20%) K 0.99 65 25%CH4 ; 40%H2 ; et al., 2018)
44% CO
CaO Ni (20%) Na 0.63 75
CaO Ni (8 mol%) MgO-Al2 O3 720°C, 720°C, 9 mol/kg-CaO 95 92% (H2 ); 87% (CO) (Kim et al.,
20% CO2 / N2 2.4%CH4 / N2 2018)
CaO Ni (10 mol%) 600°C, 800°C, 60 10.4 (Tian et al.,
100% CO2 100% CH4 2019)
CaO Ni (5%) 650°C, 650°C, 5.85 mol/kg-CaO 0.05mol /s/kg-Ni; (Hu et al.,
10 % CO2 /Ar 6 % CH4 /Ar 0.1mol-CO/s/kg-Ni 2021a)
CaO Ni (5%) CeO2 (molarCa: 14.2 mol/kg-CaO 0.24mol-H2 /s/kg-Ni
Ce=85:15) 0.32mol-CO/s/kg-Ni
Ca@Zr Ni (5%) 720°C, 720°C, 3.4 mol/kg-CaO (25th cycle) 31 (Hu et al.,
Ca@Zr NiCe (5%) Ce 5 % CO2 /Ar 8l% CH4 /Ar 5 mol/kg-CaO (25th cycle) 45 2021b)
Sr (50mol%) Ni (50mol%) 875°C, 875°C, (Gu et al.,
Sr (50mol%) Ni (25mol%) Ce (25mol%) 25% CO2 /Ar 10% CH4 / Ar > 63% for 30 cycles 100% 2022)
posed an ICCC process that couples the CO2 capture and in-situ dry
reforming of ethane, i.e., ICCC-DRE, at 650 °C using Ni20 @(K-Ca)50 /(𝛾-
Al2 O3 )50 , and observed that it illustrated a relatively stable performance
during 600 min of reaction, with only a 5% drop in activity. This study
provided insights to the dry reforming of hydrocarbons other than CH4
in the ICCC-DR process.
Development of DFMs
The development of DFMs is the cornerstone of the ICCC. DFMs are

generally composed of sorbent materials and catalytic components for
the purpose of CO2 capture and in-situ conversion, respectively. Alkali
and alkaline earth metals in their oxide or carbonate forms are usually
used in DFMs for CO2 capture from a CO2 diluted flue gas (e.g., a CO2
concentration of 12% from coal-fired power plants) or even air directly
(Buckingham et al., 2022; Wang, Y. et al., 2022). At the same time, metal
species such as 3-d transition metals and noble metals serve as the ac-
tive sites for the catalytic conversion of captured CO2 . Even though the
two major components in DFMs play different roles in ICCC, synergistic
effects between sorbent and active metals are widely observed, which
Fig. 7. Effect of the reaction temperature on the ICCC-RWGS performance can positively affect the ICCC process. In this section, we critically re-
using CaO alone (carbonation: 15%CO2 /N2, 500ml/min, 30 min; RWGS: H2, view and discuss the development of DFMs categorized by the active
500ml/min, 28 min) (Sun, S. et al., 2021a). metals used for catalytic conversion, i.e., Ni-based, Ru-based, and other
metal-based materials.
(Lv et al., 2021) explored the effect of reaction temperature from 600 Ni-based DFMs
to 650 °C on the ICCC-DRM performance using Li4 SiO4 -based DFMs,
and reported that 625 °C was the optimum reaction temperature for the Ni-based DFMs have been widely investigated in catalytic conversion
Li4 SiO4 -based DFMs in the ICCC-DRM system, as shown in Fig. 8. of CO2, including methanation, reverse water gas shift (RWGS), and dry
The reaction duration also plays an important role in the ICCC-DRM reforming of alkanes such as methane and ethane. In comparison to the
performance. Kim et al. (Kim et al., 2018) have investigated the effect of Ru-based and other metal-based DFMs, Ni-based DFMs have the advan-
sorption time and the subsequent dry reforming time on the ICCC-DRM tages of relatively low cost, high abundance, and acceptable activity.
performance using Ni/MgO-Al2 O3 -limestone in a fluidized bed reactor, Tables 1, 3, and 4 summarize the performance of Ni-based DFMs in re-
and found that the CO2 uptake of the material was initially increased lation to their compositions and reaction conditions.
rapidly with the increase of the sorption duration, while it reached a
plateau after about 12 min when the reaction turned from the fast reac- Use of Ni-based DFMs for the ICCC-Met process
tion stage controlled kinetically to the slow reaction stage controlled by Methanation reaction was also frequently reported to be coupled
product layer diffusion. Besides, the ratio of H2 to CO is approximately with the CO2 capture over the Ni-based DFMs, but usually at much
1.1 during the initial 15 min of the DRM process, while it increased lower operation temperatures than the DRM due to the different ther-
rapidly afterwards due to significant coking. modynamic limitations for these two reactions, as discussed in Section
DRM is highly endothermic process and high temperatures 2. Ma et al. investigated the performance of the ICCC-Met process using
(800−900°C) are needed to achieve equilibrium conversion. In contrast, 10%Ni/CaO modified with different metals (M=Mg, Al, Mn, Y, Zr, La,
dry reforming of ethane (DRE, as shown in Eq. 4), which is operated at or Ce, at a Ca:M molar ratio of 9:1) (Ma et al., 2021). Ni promoted the
slightly lower temperatures, i.e., 100 °C below that of DRM, has been decarbonation of CaCO3 at lower temperatures in the case of H2 avail-
investigated recently. Al-Mamoori et al. (Al-Mamoori et al., 2018) pro- ability. But on the pristine Ni/CaO, particle coalescence and sintering
11
Fig. 8. Effect of reaction temperatures on the ICCC-DRM performance using Li4 SiO4 -based DFMs: (a) 625°C; (b) 600°C; (c) 650°C (Lv et al., 2021).
occurred in the cyclic operation. The yield of CH4 decreased from 8.5 capacity of 2.74 and 3.17 mmol/g at 300 and 350°C, respectively. The
to 4.1 mmol/g over 20 cycles. Zr modification showed the best promot- doped alkali metal nitrates were thought to be in the molten state to
ing effect, which was likely related to its good thermal stability. The promote the dissolution of CO2 and enhance the carbonation activity of
CO2 uptake capacity decreased from 9.9 to 9 mol/kg after 20 cycles, MgO at 300–350°C. In the subsequent methanation stage, 1.1 mmol/g
and CH4 yield stabilized at ∼ 6.7 mol/kg on average over 20 cycles for CH4 was generated at 300°C with the generation of a small amount of
10%Ni/CaZr. On the other hand, Mn modified samples showed the worst CO (selectivity of ∼11%). 2D-layered Ni-MgO-Al2 O3 was prepared by
performance and the highest degree of sintering mainly due to the low co-precipitation method and was used for the ICCC-Met process isother-
Tammann temperature of MnO2 (287°C). The promotional effects of the mally at 200−300°C (Zhou et al., 2020). It was reported that the car-
metals were in the order of Ni/CaO ≈ Ni/CaMg ≈ Ni/CaMn ≈ Ni/CaY bonated samples could be fully regenerated in the H2 stream without
≈ Ni/CaCe < Ni/CaLa < Ni/CaAl < Ni/CaZr based on the CH4 yield at a significant loss of capacity, but only three cycles were conducted. By
the 20th cycle. tuning the carbonation and methanation time, the complete capture and
The synergistic effect between Ni and Ce on the performance of the conversion of CO2 can be achieved at temperatures as low as 200°C.
ICCC-Met process was studied by Sun et al. (Sun, H. et al., 2022). The About 60% of the input H2 was consumed in the methanation stage of
Ni-based DFM was synthesized by a physical mixture of porous CaO as the adsorbed CO2 .
the CO2 sorbent and Ni-doped CeO2 nanorods as the catalyst. On CaO- Na2 CO3 and CaO coupled with Ni/Al2 O3 were compared for their
CeO2 , the reduction product was solely CO, which assumed that the CO2 capture and methanation performances (Bermejo-López et al.,
oxygen vacancies in CeO2 enhanced the CO2 cleavage. However, with 2019b; Chai et al., 2020; Kosaka et al., 2021). Even though the CO2
the addition of Ni, the dominance product was shifted from CO to CH4 uptake capacity on Ni-Na2 CO3 /Al2 O3 was lower than that on Ni-
due to the strong interaction between metallic Ni and CO. With increas- CaO/Al2 O3 , the CH4 yield was higher, causing the higher CO2 con-
ing the Ni loading from 0.5 to 5 wt%, the CH4 yield increased slightly, version efficiency (71% vs. 46%) (Chai et al., 2020). The stability of
but the atomic utilization rate of Ni significantly decreased, because the formed carbonate on Ni-Na2 CO3 was lower comparing to Ni-CaO due
unit CH4 yield decreased from 1540 mmol/g-Ni for 0.5%Ni/CeO2 -CaO to its higher total basicity. Thus, CH4 formed with a larger amount in
to only 168 mmol/g-Ni. For the cyclic stability, the CO2 uptake capacity the temperature range of 200–600°C on Ni-CaO, while a lower range
and CH4 yield were decreased from 18 and 7.9 to 12.4 and 5.2 mmol/g. of 200−400°C on Ni-Na2 CO3 as observed in temperature-programmed
No carbon deposition was found on the DFM surface, thus the deactiva- surface reaction (TPSR) tests (Bermejo-López et al., 2019b). In perfor-
tion was proposed to be caused mainly by the sintering of the sorbents. mance tests, the CH4 yield of Ni-CaO increased monotonously with in-
Apart from the widely applied CaO, other alkali and alkaline earth creasing temperature from 280 to 520°C with the maximum amount of
metals were also reported as the CO2 sorbent in DFMs. With MgO as 142 mmol/kg, while the highest yield reached 186 mmol/kg at 400°C
the sorbent, the Ni-based DFMs are effective at lower operation tem- for Ni-Na2 CO3 . On the Na-containing samples, the production of CO
peratures than that with CaO as the sorbent. Alkali metal nitrates (Li- was higher, causing a relatively low CH4 selectivity comparing to Ca, as
K-Na altogether) promoted MgO as the sorbent was physically mixed shown in Fig. 9 (Bermejo-López et al., 2019b) and other studies (Kosaka
with Ni-CeO2 at a mass ratio of 2:1 for the capture and methanation et al., 2021). Stable performance was observed over 20 consecutive cy-
isothermally (Huang et al., 2021). The DFMs exhibited high CO2 uptake cles for Ni-Na2 CO3 at 400°C, indicating the good stability of the catalyst.
12
tivity of 89% at the operation temperature of 350°C (the rest being CO).
The addition of K and La significantly improved the CO2 uptake capac-
ity and the CH4 selectivity increased to 98% and 99%, respectively. Due
to the strong affinity of K to CO2 compared to La, much less CO2 was
released, causing a higher CO2 conversion efficiency (51% vs. 32% at
350°C). Nonetheless, at the low temperature of 250°C, the capacity and
subsequent reduction performance deteriorated and became even worse
than that of Ni/ZrO2 .
The synthesis methods of Ni-based DFMs play an essential role in the
performance of the ICCC-Met process. Sun et al. (Sun, S. et al., 2021a)
prepared the CeCaO support using the citric acid sol-gel method and
subsequently impregnated it with Ni to form Ni/CeCaO. For compari-
son, Ni was impregnated on CeO2 nanorods and then physically mixed
with CaO to form Ni/CeO2 -CaO-phy. It was found that the physically
mixed sample, i.e., Ni/CeO2 -CaO-phy, showed better performance than
the Ni/CeCaO. The CH4 yield increased from 3.3 to 8 mmol/g and CO2
conversion increased from 42% to 62% at 550°C. The better perfor-
mance of the physical mixing was attributed to the well-dispersed Ni
active sites on the surface of CeO2 , which avoided being covered by the
newly formed CaCO3 during the carbonation-decarbonation cycles.
Use of Ni-based DFMs for the ICCC-RWGS process

With a RWGS catalyst at a relatively higher temperature, H2 re-
duction of the carbonated DFMs can also produce CO rather than CH4
(Sun et al., 2019; Wang, G. et al., 2022). For example, a sol-gel com-
bustion method was used to synthesize CaNi0.1 with the modification
of Ce (Sun et al., 2019). The carbon capture and subsequent RWGS
were operated at 650−700°C isothermally. The CaNi0.1 Ce0.033 showed
optimum performance at 650°C with the CO2 conversion of 51.8% and
CO yield of 7.3 mmol/g-DFM (∼100% selectivity). Cyclic performance
tests showed an obvious decay of carbonation-conversion over 20 cy-
Fig. 9. Gas concentration profiles during the CO2 sorption and hydrogenation cles for CaNi0.1 , mainly attributed to the agglomeration and sintering
process at 400°C with (a) Ni-CaO and (b) Ni-Na2 CO3 (Bermejo-López et al., of CaO. For CaNi0.1 Ce0.033 , the performance kept unchanged after 20
2019b). cycles, demonstrating much better stability due to CeO2 modification.
Two benefits were proposed for CeO2 modification: one was that the
oxygen vacancies in CeO2 could reduce the dissociated CO2 released
The promotion effects of Na, K, and Ca (15 wt% against Al2 O3 ) were in- from the DFMs, facilitating the CO yield; the other was that the well-
vestigated on Ni/𝛾-Al2 O3 by Kosaka et al. (Kosaka et al., 2021). It was dispersed CeO2 could act as a physical barrier to prevent the growth and
found that Ni/𝛾-Al2 O3 had negligible CO2 capture ability and thus low agglomeration of CaO and Ni particles. Compared to the conventional
methanation yield. The CH4 yield increased to 188 and 134 mmol/kg- RWGS reaction (CO2 and H2 co-feeding), the performance of the ICCC-
DFM after Na and K modification, respectively. The CO2 uptake capacity RWGS process exhibits a higher CO2 conversion, a more remarkable CO
of K modification was higher than Na, but the CH4 selectivity was much selectivity, and a better stability.
lower (93% vs. 61%) with a considerable production of CO. Ca modifi- Recently, the effects of preparation methods for using carbide slag
cation showed a much weaker promotion effect, with the CH4 yield of (CS) as the sorbent and support for 10 wt%Ni were reported (Wang, G.
58 mmol/kg-DFM, possibly because of the high stability of CaCO3 at the et al., 2022). The wet-mixing (Ni/CS), acidification with 30% propionic
operation temperature of 450°C, which was thought to be incompatible acid and impregnation (Ni/CS-P30), and acidification/impregnation
with the CaCO3 decarbonation temperature. combined with citric acid complexation (Ni/CS-P30-C) were prepared
Li4 SiO4 supported 10wt% Ni was prepared with Li2 CO3 , SiO2 , and and compared for their performance in RWGS reaction at 650°C. The
NiO as the precursors by Jo et al. (Jo et al., 2022a). Its capture and Ni/CS-P30-C with propionic acid pretreatment and citric aids complex
methanation performance was compared to 10 wt%Ni/CaO at 550°C. showed higher surface area and expanded pore structure, facilitating Ni
The reversible reaction between Li4 SiO4 and CO2 is shown in Eq. 6. With accommodation and uniform dispersion. Citric acid was also reported
the addition of Ni, the sorbent could be regenerated at a lower temper- to be able to prevent the Ni particle agglomeration and maintain the
ature compared with the traditional decarbonation, as also reported for particle size, thus providing considerable active sites for the hydrogena-
Ni/CaO DFMs. During the reduction of the carbonated Ni/Li4 SiO4 , the tion. The CO productivity was 5.12 mmol/g with a selectivity of 100%
desorbed CO2 was completely converted to CH4 with a selectivity of on Ni/CS-P30-C, comparing to the 2.86 and 0.78 mmol/g for Ni/CS-P30
100%. The activity remained stable (4.53 to 4.56 mmol/g CH4 ) and no and Ni/CS, respectively.
sign of sintering was observed after five cycles. For Ni/CaO, even though It is worth mentioning that multiple gas components in the flue gas
the uptake capacity and CH4 yield were much higher than Ni/Li4 SiO4 may have detrimental effects on the stable operation of the Ni-based
in the first cycle, they decreased significantly and became even worse DRM. The presence of O2 in the gas stream was found to be adverse
than Ni/Li4 SiO4 in the working capacity. when only Ni was supported on the sorbent. For example, 10% Ni sup-
ported on 6.2% Na2 O/Al2 O3 was applied for methanation after the DFM
Li4 SiO4 + CO2 ↔ Li2 SiO3 + Li2 CO3 (6) was used for CO2 capture in O2 containing flue gas (Arellano-Treviño
et al., 2019a; Arellano-Treviño et al., 2019b). No methane was detected
Hu et al. (Hu and Urakawa, 2018) impregnated 15 wt% Ni on ZrO2 during the conversion stage as Ni was in the form of oxides which can-
with K or La as a promoter for the isothermal ICCC-Met process. It was not be reduced at low temperatures (320°C in this study). The doping
found that 20% of the captured CO2 was converted to CH4 with a selec- with a small number of Pt-group metals (Ru and Pt) was found to en-
13
Fig. 10. (a) Schematic of the proposed ICCC-DRM directly convert CO2 into synthesis gas; (b) ICCC during the 1st cycle; (c) cyclic CO2 capture of CaO evaluated
using TGA and fluidized bed (Kim et al., 2018).
hance the reducibility and activity of Ni at low temperatures. Even in

the carbonation stage, both Ru and Pt could be oxidized in the presence
of O2 , but the formed PtOx and RuOx were reduced rapidly to their
metallic forms and aided the reduction of the NiOx by splitting hydro-
gen atoms. Pt-modified samples showed a lower CO2 uptake capacity
and slower methanation rate compared to the Ru counterpart. Due to
the highest exothermic heat rate of Ru, CO2 spillover was enhanced,
leading to more sites available for subsequent sorption. A CO2 conver-
sion of 90% on 1%Ru-modified DFM was achieved with the CH4 for-
mation rate of 0.39 mmol/g. The presence of a trace amount of sulfur
species, nitrogen oxide, dust, and H2 O in the CO2 -containing flue gas
may also affect the long-term performance of the DFMs, which needs
further in-depth investigations.
Use of Ni-based DFMs for the ICCC-DR process

The carbon capture and dry reforming of methane (DRM) coupled in
a single reactor is demonstrated to be feasible with Ni-CaO as the DFM
(Kim et al., 2018). In this study, Ni supported on MgO-Al2 O3 was pre-
pared via co-precipitation and then mixed with CaO as a DFM compos-
Fig. 11. Decabonation rate at 800° for Ni-CaO sorbent-catalyst after carbona-
ite. It was used for cyclic CO2 capture and DRM in a fluidized bed reactor
tion (Tian et al., 2019).
(Fig. 10a). The CO2 capture and conversion process occurred isother-
mally at the temperature of 720°C, to match the CO2 release rate with
the DRM activity of the Ni-based catalyst. They found negligible CO2 The CO2 capture and DRM were further investigated by Tian et al.
(less than 0.08%) was released in the off-gas during the conversion pro- (Tian et al., 2019), using Ni-CaO sorbent-catalyst synthesized by a sol-
cess, and almost all of the CH4 was converted in the pre-breakthrough gel method as the DFM. The process was operated in a temperature
stage (as shown in Fig. 10b). It should be noted that the ratio of H2 swing mode, in which the CO2 capture occurred at 600°C while the DRM
to CO was about 1.1, exceeding the theoretical value (∼ 0.94 at 720 occurred at 800°C. About 60% and > 80% conversion efficiency were
°C) and probably ascribed to the occurrence of methane decomposition achieved for CO2 capture and DRM over ten cycles, respectively, which
(Eq. 7). In addition, the cyclic stability of the DFM composite was tested, was competitive with other novel methane reforming. The cyclic CO2
in which the high conversion efficiency of CH4 (97.1% to 96.4%) and uptake capacity was also decreased due to the sintering of CaO, which
CO2 (96.3% to 95.3%) were maintained over ten cycles. However, due caused less CO2 available in the subsequent conversion stage for CO
to the low Tammann temperature of CaCO3 (533°C), serious sintering production. The H2 /CO ratio (∼ 1.1) was higher than the theoretical
and agglomeration of CaO were observed during cycling, causing the DRM (i.e., ∼ 1), indicating the concurrence of CH4 decomposition and
loss of CO2 uptake capacity (Fig. 10c). dry reforming in the conversion stage, as also reported by Kim et al.
(Kim et al., 2018). The presence of Ni accelerated the decomposition
CH4 → 2H2 + C (7) of CaCO3 due to the continuous consumption of CO2 by CH4 reform-
ing, providing an additional driving force for CaCO3 decarbonation (La
Ni was impregnated on the CaO surface for CO2 capture, followed Chatellier’s principle). Thus the decarbonation rates were significantly
by DRM to generate syngas dynamically (Cruz-Hernández et al., 2017). improved compared to the CaCO3 alone, as shown in Fig. 11. With in-
The CO2 capture was conducted by increasing the temperature from creasing the Ni content, both the CO2 and CH4 conversion increased.
30 to 600°C, then maintained at 600°C for one hour and cooled down to To improve the activity and stability of Ni/CaO DFM for ICCC-DRM,
200°C to complete the whole capture step. In the subsequent DRM stage, CeO2 was used to modify the CaO by a template hydrothermal method
2% CH4 was introduced while increasing the temperature from 200 to (Hu et al., 2021a). It was found that Ca: Ce at a molar ratio of 85:15 as
900°C. During the DRM process, syngas was produced at two different a support for Ni exhibited the best promoting effect. For the unmodified
temperature range: between 500 and 650°C, and at temperatures over Ni/CaO, the syngas space time yield (H2 +CO) decreased from 0.43 to
800°C, corresponding to the DRM and CH4 partial oxidation, respec- 0.15 mol/s/kg-Ni from the 1st to 10th cycle. For Ni/CaO-CeO2 by com-
tively. The Ni-impregnated CaO was compared with the CaO-NiO phys- parison, the value only decreased from 0.65 to 0.56 mol/s/kg-Ni. The
ical mixture, and it was found that Ni-impregnated CaO always showed addition of CeO2 with a much higher Tammann temperature enhanced
better performance than the latter. the sintering resistance of CaO during the carbonation/decarbonation
14
cycle, and therefore led to less agglomeration of the supported Ni parti- Reaction mechanisms for the ICCC process using Ni-based DFMs
cles. The Ni dispersion and the reducibility of NiO were also found to be Unraveling the reaction pathways and underlying mechanisms of the
improved after CeO2 modification, contributing to the low-temperature ICCC process is of vital importance for the design of suitable DFMs and
activity for DRM at as low as 650°C. The same group further reported the selection of operation conditions. Nonetheless, the reaction mecha-
that coating ZrO2 layer on CaO surface (Ca@Zr) could also effectively nism has not yet been fully understood (Hu and Urakawa, 2018). Since
suppress the severe sintering of CaO and Ni during the cycles (Hu et al., CH4 , CO, and CO2 coexisted in the methanation off-gas, the CO2 con-
2021b). For the ZrO2 coated material, the grain size of Ni was stable, version was proposed to be a two-step process, namely, the release of
and the decrease in the surface area of the ZrO2 coated Ni/CaO was CO2 from CaCO3 and the reaction with H2 to produce CH4 and CO (Ma
much slighter than the uncoated one. Interestingly, when preparing Zr- et al., 2021). By comparing the CaO, 1wt%Ni/CaO, and 10wt%Ni/CaO
Ca through precipitation, forming Cax Zry Oz (CaZr) as Ni support, the in TPSR tests, it was found that CO was generated on carbonated CaO
activity of Ni/CaZr also decreased significantly similar to that of the even though no Ni was added. With increasing the Ni from 1 to 10 wt%,
Ni/CaO, indicating the cyclic stability was sensitive to the structure of the CH4 yield significantly decreased while CO production was compa-
the sorbent composite. The modification of Ce was found to further im- rable. It was thus inferred that the methanation reaction happened on
prove the catalytic performance of Ni/Ca@Zr. The redox properties of the Ni site, while the RWGS mainly happened on CaO with the gener-
CeO2 were reported to facilitate the CH4 and CO2 activation during the ation of CO (Ma et al., 2021). The generation of CO rather than CH4
reforming step, thus promoting syngas production. In the in-situ diffused was also reported by Sun et al. when using Ce-CaO (without addition of
reflectance infrared Fourier transform spectroscopy (DRIFTS) study, the Ni) in the carbonation-methanation cycle (Sun, H. et al., 2022; Sun, S.
formate and CO species formed after introducing CH4 , while the car- et al., 2021a). On Ni/CeO2 -CaO surface, it was found formate, calcite
bonate peak intensity decreased. This suggests the H species from CH4 carbonate, bicarbonate species, and CO species presented after CO2 cap-
decomposition react with the carbonate species with the formation of ture with the in-situ DRIFTS study. After introducing H2 , the intensity
formate, which decompose to CO further (Hu et al., 2021b). of formate and calcite carbonate remained unchanged, while that of
Besides using CaO as the CO2 sorbent component in the Ni-based CO decreased. This indicates that the CO is possibly the main interme-
DFM, SrO can also be used as the CO2 sorbent component. SrO- diate being converted to CH4 (Sun, H. et al., 2022), as illustrated in
supported Ni was recently developed for the ICCC-DR process (Gu et al., Fig. 12. By contrast, the surface formate and carbonate species intensity
2022). Similar to the CaO-supported Ni, the CO2 uptake capacity of SrO- decreased upon H2 injection with the generation of gas-phase CH4 on
supported Ni decreased significantly due to the sorbent sintering. Larger Ni-MgO-Al2 O3 (Zhou et al., 2020). The authors found that CO is less
Ni clusters were found on the surface, causing relatively low CH4 conver- likely to be the intermediate for methanation as no signal of CO was
sion. However, after the introduction of Ce in the system (SrCe0.5 Ni0.5 ), detected during the FTIR test, indicating that methanation should pro-
uniform distribution of Ni was observed. Moreover, the CO2 capture sta- ceed with direct hydrogenation of formate. Additionally, the carbonate
bility improved significantly, and no decay was found in the CO2 cap- is more likely to bond with metal oxides, it was assumed that the hy-
ture performance over 35 carbonation/decarbonation cycles. This was drogenation was accompanied by the migration of CO2 to the metallic
because a new phase transition, i.e., SrCeO3 /Sr2 CeO4 , took place in the Ni surface (Zhou et al., 2020), namely the spillover of CO2 as reported
carbonation/decarbonation through Eqs. 8 and 9; thus, the phase change by Farrauto et al. (Arellano-Treviño et al., 2019b).
between SrCO3 and SrO (Eq. 10) in the conventional cycles causing sor- For the production of CO (RWGS), the carbonyl and formate species
bent sintering could be inhibited. Furthermore, the synergy between were detected on CaNi0.1 Ce0.033 with in-situ DRIFTS tests, indicating
Ce and Ni facilitated the CH4 activation because the syngas generation both the redox process and formate mechanism. Without Ce, CO2 would
shifted to a lower temperature range than the SrO-supported Ni as ob- spill over to Ni active sites with the formation of CO and NiO (NiO
served by the CH4 -TPR. A stable CH4 conversion rate of 98% over 30 was then reduced by H2 ); in the presence of Ce, CO2 interacted with
cycles was observed for SrCe0.5 Ni0.5 , compared to less than 85% for SrO- oxygen vacancy in CeO2 and was released as CO, and then H2 consumed
supported Ni at 850°C. For the whole capture and reforming process, the the lattice oxygen from ceria to restore the oxygen vacancy (Sun et al.,
H2 /CO ratio can be tuned by varying the CH4 injecting or carbonation 2019).
time, offering the flexibility of the ICCC process. Furthermore, the modification with promoters may alter the reac-
tion pathways. For example, On Ni/ZrO2 , formate species was observed
SrCeO3 /Sr2 CeO4 + CO2 → SrCO3 + CeO2 (8) as the main intermediate for CH4 production as suggested by the space
and time-resolved operando DRIFTS investigation. After K modification,
SrCO3 + CeO2 → SrCeO3 /Sr2 CeO4 + CO2 (9) the formyl species cooperated with bidentate carbonates were found
to be the active phase for methanation. While for La modification, the
SrCO3 ↔ SrO + CO2 (10) reaction pathway remained unchanged, as shown in Fig. 13 (Hu and
Urakawa, 2018). On Ni-“Na2 O”/Al2 O3 surface, CO2 was adsorbed as
During the DRM process, carbon deposition is widely reported on bicarbonate and bidentate carbonates regardless of the oxidizing atmo-
the Ni-based DFMs, especially in the later stage of the reforming reac- sphere. After loading with 1% Pt, CO-Pt species provided additional CO2
tion with the consumption of CO2 (Gu et al., 2022; Hu et al., 2021b; sorption site during carbonation. During hydrogenation, CO2 -related
Kim et al., 2018). Nonetheless, the deposited carbon can be removed in species (bicarbonate, bidentate carbonates, and CO-Pt) spill over to the
the subsequent CO2 capture process via the reverse Boudouard reaction Ni site for methanation since Pt was inactive for the methanation re-
(Eq. 11). For example, over the 10Ni-CaO DFM, carbon deposition due action. While for Ru modification, CO2 was proposed to spill over to
to CH4 decomposition (Eq. 7) caused a significant decrease in the sur- both Ni and Ru sites for methanation via formate intermediate, thus Ru
face exposure of Ni from 262 to 10 𝜇mol/g. However, after the capture demonstrated a greater promotional effect (Proaño et al., 2020).
stage, the deposited carbon was removed by the reverse Boudouard re-
action, and the exposure of Ni was restored to 255 𝜇mol/g (Kim et al., Ru-based DFMs
2018). Moreover, it was also reported that the modification of CeO2
was capable of suppressing the accumulation of inactive carbon on Ni Use of Ru-based DFMs for the ICCC-Met process
due to the high mobility of lattice oxygen in CeO2 (Hu et al., 2021b). To the best of our knowledge, Ru-based DFMs are mostly used for
Furthermore, other methods, such as manipulating the Ni particle sizes the ICCC-Met process, as shown in Table 2. The feasibility study of the
and using bimetallic Ni-based catalysts, were suggested to alleviate the Ru-based DFMs was first conducted and pioneered by Farrauto and co-
carbon deposition (Tian et al., 2019). workers (Duyar et al., 2015). Ru supported on 𝛾-Al2 O3 has been widely
CO2 + C ↔ 2CO (11) reported to be effective for CO2 methanation. After the addition of CaO,
15
Fig. 12. Reaction mechanism on (a) CeO2 -CaO (b) Ni/CeO2 -CaO for CO2 capture and methanation (Sun, H. et al., 2022).
Fig. 13. Space- and time-resolved operando DRIFT spectra of ZrO2 , Ni/ZrO2 , Ni-K/ZrO2 , Ni-La/ZrO2 under 350 °C for ICCC-Met (Hu and Urakawa, 2018).
the sorbent/catalyst composites produced much more CH4 than the spillover and methanation was observed. The optimum performance was
Ru/𝛾-Al2 O3 . A similar result was also reported by Bermejo-López et al. reached for 5%Ru-10%CaO/𝛾-Al2 O3 in terms of the CH4 yield per kg of
(Bermejo-López et al., 2019a), which showed the dual functionality of DFM. By changing the active metals as well as the sorbent materials,
the material. Yet CO2 methanation on CaO/𝛾-Al2 O3 was not observed, the performances of DFMs were further investigated by Farrauto et al.
indicating the synergistic effect of the sorbent and catalyst in DFMs. (Duyar et al., 2016). The CH4 capacity of the 0.1%Rh-10%CaO/𝛾-Al2 O3
With an increase in the CaO:Ru in the DFMs, a greater extent of CO2 was found to be similar to that of 5%Ru-10%CaO/𝛾-Al2 O3 (0.4 vs. 0.5 g-
16
Fig. 14. Evolution of CO2 storage and CH4 and CO production with temperature for Ru-CaO/Al2 O3 (a, b, and c, respectively) and Ru-Na2 CO3 /Al2 O3 (d, e, and f,
respectively) with different sorbent contents (Bermejo-López et al., 2019a).
mol/kg), possibly due to the higher methanation activity of Rh at lower By using the mixed NaCO3 and CaO as sorbents, the basicity of the Ru-
temperatures. Nonetheless, the Ru-based DFMs showed a faster reaction based DFMs could be modulated (Bermejo-López et al., 2022). It was
rate of methanation than Rh-based DFMs, as the methane generation found that Ru-8Na/8Ca DFM, the optimum selection, showed a higher
peak was sharp and completed within 25 min on 5%Ru-6.1%Na2 O/𝛾- CH4 yield in the whole temperature range tested (280 – 400°C) com-
Al2 O3 compared to ∼ 35 min for 0.5%Ru-6.1%Na2 O/𝛾-Al2 O3 (Arellano- pared to the DFMs with the single sorbent, which was suggested to be
Treviño et al., 2019a). Considering the lower price ($19.9 USD/g for Ru caused by the highly dispersed Ru and the promoted basic sites with
vs. $498.3 USD/g for Rh) (Daily Metal Prices, 2022) and higher stabil- medium strength on the Na-Ca combined sorbent surface.
ity of Ru, Ru-based DFMs are still promising compared to the Rh-based The effects of Li (1.73%), Na (4.34%), and K (5.66%) addition in
DFMs (Arellano-Treviño et al., 2019a; Duyar et al., 2016). the 1%Ru/Al2 O3 were investigated on its capture/methanation perfor-
Due to the greater CO2 uptake capacity of 10%K2 CO3 /𝛾-Al2 O3 and mance (Cimino et al., 2020). It appeared that the Li-modified sample
10%Na2 CO3 /𝛾-Al2 O3 than 10%CaO/𝛾-Al2 O3 at low temperatures (e.g., showed higher methanation activity (H2 and CO2 co-feeding test) com-
320 °C), the methanation capacity of Ru loading on K2 CO3 and Na2 CO3 pared to its Na and K doped counterparts. The CO2 uptake capacity was
were also found to be higher. The CH4 yield of 5%Ru-10%Na2 CO3 /𝛾- found to be increased in the order of Na ≤ K < Li. The integrated cap-
Al2 O3 (1.05 g-mol CH4 /kg) was about two times that of the 5%Ru- ture/methanation experiments showed a much higher CH4 generation
10%CaO/𝛾-Al2 O3 (0.50 g-mol CH4 /kg) at 320°C. This indicated that rate for Li-Ru/Al than that for Na-Ru/Al, indicating the effectiveness
Na2 CO3 could be an attractive sorbent component for DFMs develop- of the developed Li-Ru/Al in the ICCC-Met process. The stable cyclic
ment in the ICCC-Met process (Duyar et al., 2016). When using Na2 CO3 operation with the generation of pure CH4 could be achieved at the
as a CO2 sorbent in Ru-based DFMs, the carbonates decomposition and temperature as low as 230°C. With the addition of Li to the Ru/Al2 O3 ,
the subsequent hydrogenation happen at lower temperatures than us- mixed Li-Al phases (LiAl5 O8 , LiAlO2 , and Li2 Al4 (CO)3 (OH)12 -3H2 O)
ing CaO due to the stability of the formed carbonates on CaO (Bermejo- were formed. These phases have been reported to suppress the formation
López et al., 2019a). The maximum CH4 yield was 414 mmol/kg for of highly stable carbonate species that were difficult to hydrogenate,
the 4%Ru-15CaO/Al2 O3 DFM at 400°C. At a lower operation tempera- and the synergism was found between the Li-Al phases and the Ru size,
ture of 310°C, a comparable yield of 380 mmol/kg can be achieved for which enhanced the methanation activity of the DFM (Cimino et al.,
the 4%Ru-15Na2 CO3 /Al2 O3 , as shown in Fig. 14, due to the higher Ru 2022). In another study, different alkali (Li, Na, K) and alkaline earth
dispersion coupled with lower stability of the formed carbonates. With metals (Mg, Ca, Ba) were investigated for their effects on the capture
increasing the loading amount of CaO, the dispersion of Ru was found and methanation performance of 1%Ru/𝛾-Al2 O3 at the operation tem-
to decrease gradually, and the particle size of Ru increased. In contrast, perature of 350°C (Porta et al., 2021a). The molar ratio of different sor-
an opposite trend was observed for Na2 CO3 containing DFMs (Bermejo- bent metals was constant compared to Ru (∼ 14). However, different re-
López et al., 2019a). Furthermore, it was found that the time required sults were reported from the previous study (Cimino et al., 2020). It was
for completing the methanation of the adsorbed CO2 for CaO-DFM was found that the Li-modified DFM showed similar performance to Ru/𝛾-
much longer than Na2 O-DFM, due to the thermal stability of the formed Al2 O3 , being worse than other metals modification. The Ru and Ru-Li
carbonates on CaO (Arellano-Treviño et al., 2019a). In the same study, samples were reported to lack sorption sites for CO2 at 350°C based on
the effects of different sorbents, including Na2 O, K2 O, CaO, and MgO, CO2 -TPD and H2 -TPSR tests. In terms of the CH4 yield, the modifica-
were investigated on the methanation performance of 5%Ru-𝛾-Al2 O3 at tion promotion was in the order of Ru-K > Ru-Ba > Ru-Ca > Ru-Na >>
the operation temperature of 320°C. The CO2 uptake capacity followed Ru-Mg > Ru-Li ≈ Ru.
the order of CaO > Na2 O > K2 O > MgO, while the CH4 yield was in the In addition to the sorbent, support may also significantly affect the
order of Na2 O > CaO > K2 O > MgO (Arellano-Treviño et al., 2019a). capture/methanation performances of Ru-based DFMs. For the widely
17
used Al2 O3 support, the effect of different types of 𝛾-Al2 O3 in powder, to the oxidation of some Ru, causing the loss of active sites (Duyar et al.,
pellet, and sphere forms as the support for 5%Ru-10%CaO was investi- 2015; Zheng et al., 2016). Nonetheless, this deactivation can be restored
gated on their performance in the ICCC-Met process (Zheng et al., 2016). by extending the H2 exposure time or using a higher H2 concentration
The Al2 O3 carrier in pellets showed the best performance in methana- stream during the methanation stage (Wang et al., 2017). It was shown
tion, which may be ascribed to the large surface area and pore size of that a concentration of 15% H2 was sufficient for the oxidized Ru (5%
the alumina pellets. Moreover, CeO2 was also used as the support for the Ru-6.1Na2 O/𝛾-Al2 O3 ) to be reduced in the methanation stage (Wang
Ru-based DFMs. Ru/CeO2 was physically mixed with MgO for the CO2 et al., 2018). This property makes the Ru a more suitable DFMs candi-
capture and methanation at 300°C (Sun et al., 2020). An optimum load- date than Ni in the ICCC-Met of real industrial flue gas containing both
ing amount of Ru was found to be 5% on CeO2 due to its better stability oxygen and steam (Arellano-Treviño et al., 2019a).
over the ten cycles test. The CH4 yield and CO2 conversion reached 3.36 However, different observations for the effect of H2 O and O2 were
mol/kg and 79% for 5%Ru/CeO2 -MgO, respectively, which were much also reported. The storage capacity of 0.8%Ru-BaO/Al2 O3 was inhibited
higher than those on 2.5%Ru/CeO2 -MgO (1.13 mol/kg and 39%) and by H2 O and O2 , which could be ascribed to the competition of hydrates
10%Ru/CeO2 -MgO (2.31 mol/kg and 69%) after ten cycles operation. and carbonates for the same sorption sites (Porta et al., 2021b). CO2 TPD
This was attributed to more oxygen vacancies generated in 5%Ru/CeO2 - result indicated that the weaker CO2 ad-species reduced in the presence
MgO because of the suitable metal-support interaction. A similar result of H2 O and O2 . The detrimental effect was also found for CH4 yield
was reported by Duyar et al. on 10CaO/Al2 O3 (Duyar et al., 2015), in (0.153 vs. 0.08 mol/kg), which was possibly due to the sintering of Ru
which the optimum loading amount of Ru was also 5%. Because of the upon oxidation, as supported by the significant decrease of the metal-
large amount of sorbent used in the 10%Ru/CeO2 -MgO (10%Ru/CeO2 lic surface area (1/5 of the fresh sample) (Porta et al., 2021b). On the
to MgO mass ratio at 2:1), the CO2 uptake capacity and the CH4 yield alkali and alkaline earth metals (Li, Na, K, Mg, Ca, and Ba) modified
were much higher compared to previously reported values as listed in 1%Ru/𝛾-Al2 O3 , the addition of 2.5% H2 O and 3% O2 during the cap-
Table 2. Besides, the influence of CeO2 morphologies (i.e., rod, particle, ture stage (1%CO2 /He) caused the uptake capacity as well as the CH4
cube) on the CO2 capture and methanation performance was investi- yield to decrease significantly for all of the studies DFMs at 350°C (Porta
gated by the same group (Sun, S. et al., 2022). CeO2 with rod morphol- et al., 2021a). For Ru-Li, Ru-Na, Ru-Mg, almost no CH4 was generated
ogy demonstrated the best performance in terms of the CH4 yield (0.33 in the methanation stage due to the poor sorption of CO2 , and a reduc-
mol/kg) and cyclically catalytic stability, possibly due to the higher Ru tion in CH4 yield of 84%, 65%, and 47% for Ru−K, Ru−Ca, and Ru−Ba,
dispersion and support-metal interactions. respectively, were observed. This is quite different from other studies,
The synthesis approach and application method of the Ru-based however, where Na-Ru-Al DFMs (5%Ru-6.1%Na2 O/Al2 O3 (Arellano-
DFMs also play a critical role in their performance in the ICCC- Treviño et al., 2019a; Wang et al., 2018) and 0.5%Ru-6.1%Na2 O/Al2 O3
Met process. For example, when impregnating the 10.6%Ru over the (Jeong-Potter and Farrauto, 2021)) were reported to still have consider-
10%CaO/𝛾-Al2 O3 , it showed a higher CH4 yield than the DFM impreg- able CO2 uptake and methanation capacity with the co-presence of H2 O
nating 10%CaO over 10%Ru/𝛾-Al2 O3 . This was caused by the loss of Ru and O2 . This contradiction could possibly stem from the different Na
sites after doping with CaO, and/or the increased dispersion of Ru on the precursors used (carbonates vs. acetates), CO2 concentrations (7.5% vs.
CaO/𝛾-Al2 O3 surface (Duyar et al., 2015). When physically mixing the 1%), or impregnation sequence of sorbents and Ru on Al2 O3 etc. used
10%CaO/𝛾-Al2 O3 and 10%Ru/𝛾-Al2 O3 on the other hand, the materials in these studies.
showed inferior performance to the sample prepared with the impreg-
nation method, indicating the proximity of CaO and Ru should benefit Reaction mechanisms for the ICCC process using Ru-based DFMs
the methanation process (Duyar et al., 2015). In another study, physi- For the mechanism of the CO2 capture and methanation on Ru-based
cally mixed DFM of 17%NaNO3 /MgO and Ru/Al2 O3 at a mass ratio of 2 DFMs, Farrauto et al. (Duyar et al., 2015; Zheng et al., 2016) proposed
(sample labeled as MP) was compared with the configuration of putting that CO2 is mainly chemisorbed on CaO sites and spillover to the Ru
them in two separate beds (sample labeled as 2B) at the same mass ratio sites upon H2 introduction. Due to the methanation activity of Ru, CO2
by Park et al. (Park et al., 2021). The MP configuration showed much can then be reduced by H2 for the generation of CH4 on the Ru surface
lower CO2 uptake capacity (0.4 vs. 2.62 mol/kg), as well as methana- as shown in Fig. 15. An in-situ DRIFTS study was conducted to elucidate
tion capacity (0.38 vs. 1.51 mol/kg) than 2B regardless of Ru loading at the possible mechanism of 5%Ru-6.1%Na2 O/Al2 O3 DFM (Proaño et al.,
300°C. It was hypothesized that in the tightly bound MP sample, molten 2019). During the capture stage on the 5%Ru/Al2 O3 surface, CO2 was
NaNO3 may transfer to the Al2 O3 support causing the loss of promotion absorbed on the Al2 O3 OH groups and the Ru sites. After the addition of
functionality of the NaNO3 in CO2 sorbent (Park et al., 2021). The cat- Na2 O, the CO2 was mainly absorbed on Al-O− -Na+ sites with the forma-
alytic performance of an intimate mixture of Ru-BaO/Al2 O3 with that of tion of bidentate carbonates. The adsorbed bicarbonates and bidentate
the mechanical mixed BaO/Al2 O3 +Ru/Al2 O3 was compared by Porta et carbonates spillover to the Ru-support interface for methanation with
al. (Porta et al., 2021b). The mechanical mixture showed a much lower the formate species as intermediates, as shown in Fig. 16. Nonetheless,
CH4 yield (0.097 mol/kg) than the intimate mixture (153 mol/kg) at a it was assumed that the carbonyl was the intermediate on 1%Ru/Al2 O3 ,
similar Ru and Ba loading amount, even though the CO2 sorption ca- while on the 5%NaNO3 /1%Ru/Al2 O3 , both carbonyl, formate, carbon-
pacities were comparable. This indicated that the synergistic effect of ate, and biocarbonate species were likely to be the reaction intermedi-
Ru and Ba likely facilitated the fast spillover of CO2 to the Ru sites for ates for methanation (Park et al., 2021). On Li-Ru/Al2 O3 DFM, in-situ
methanation. For the intimate mixture, a small amount of CO was de- DRIFTS and TG-MS indicated that the formed Li-Al phases could facil-
tected with CH4 selectivity higher than 98%, while the CH4 selectivity itate the prompt sorption of CO2 in the form of bidentate carbonates,
was 100% for the mechanical mixture. with further adsorbed CO2 being absorbed as weakly bonded bicarbon-
Compared to the Ni-based DFMs, it appears that Ru-based DFMs are ates at a slower rate (Cimino et al., 2022). The spillover mechanism of
much less susceptible to the presence of oxygen and steam. It was found CO2 from Li-Al oxide to Ru sites for methanation was also confirmed by
that, even with the presence of high concentration of O2 (∼18%), the Ru- in-situ DRIFTS in this study.
CaO/𝛾-Al2 O3 showed relatively stable CO2 uptake capacity and metha- On Ru/CeO2 -MgO DFM, the formed formate species during the cap-
nation capacity, and the average CO2 conversion was 76% (Duyar et al., ture stage disappeared after injecting H2 , indicating that the formate
2015). With the presence of 20% steam, the CH4 yield decreased by 10% species were the main reaction intermediate for integrated methanation
to 0.27 g-mol/kg over 19 cycles of operation. The CaO dispersion was (Sun et al., 2020). In the following studies (Sun, S. et al., 2022), they
found to be greatly reduced by 87% after the cyclic test in the presence found that the formates and CO2 dissociation (Ru-CO) pathways were
of steam, yet the methanation capacity did not decrease significantly identified as the two possible pathways for CO2 capture and metha-
(Duyar et al., 2015). The decrease in the capacity was mainly attributed nation by in-situ DRIFTS on the 2%Ru/rod-CeO2 -Al2 O3 , as shown in
18
Fig. 15. Schematic mechanism of the CO2 capture and methanation on Ru-CaO/Al2 O3 DFM (Zheng et al., 2016).
Fig. 16. The proposed CO2 methanation mechanism on 5%Ru/Al2 O3 (right side) and 5%Ru-6.1%Na2 O/Al2 O3 (left and right side) (Proaño et al., 2019).
Fig. 17. With formates as the intermediate, the decarbonation of CO2 listed in Table 3. To the best of our knowledge, these DFMs have been
as the gas phase from carbonates was not required, leading to the com- mainly used for the ICCC-RWGS process thus far.
plete CO2 conversion and methanation. It is thus suggested to improve Cu as the active metal with and without the promotion of 10% K
the formates pathway to inhibit the CO2 release during the methanation or Ba was investigated for the ICCC-RWGS process (Hyakutake et al.,
step (Sun, S. et al., 2022). 2016). Cu/Al2 O3 and Cu-Ba/Al2 O3 were ruled out as suitable DFMs for
the ICCC process, due to their low CO2 uptake capacities, as well as the
conversion efficiencies. The modification of K significantly promoted
Other metal-based DFMs the CO2 uptake capacity and its conversion to CO on Cu (93.4% selec-
tivity) comparing to the unpromoted Cu/Al2 O3 . The amorphous nature
In addition to the widely investigated Ni and Ru, other catalysts, of K under the reaction condition was reported to facilitate the higher
including Cu, Fe, Co, etc., were also developed for the ICCC process, as dispersion of Cu with a smaller crystallite size. The coverage of Cu by
19
Fig. 17. Formation pathways for CO2 capture and methanation over Ru/rod-CeO2 -Al2 O3 (Sun, S. et al., 2022).
K species was supposed to be crucial to suppress the oxidation of Cu,

which was observed on Cu/Al2 O3 and Cu-Ba/Al2 O3 during the reaction.
The captured CO2 in the form of formate was reduced easier to CO on
the dispersed metallic Cu in Cu-K/Al2 O3 . Yet during the capture stage,
with the consumption of reactive surface species by CO2 , the oxidation
of metallic Cu seemed to happen with the release of CO. The switching
from capture to conversion stage before the CO2 front reached the end
of the catalyst bed was thus suggested to avoid not only CO2 release but
also CO formation during the capture stage (Hyakutake et al., 2016).
FeCrCu supported on hydrotalcite (PMG-20) with the modification of
10% K was further developed for the CO2 capture and conversion to
CO from diluted CO2 stream (5.8%) containing both O2 (5%) and H2 O
(4%) (Bobadilla et al., 2016). Complete capture of CO2 was reached,
with 45% being converted to CO (92% selectivity) and CH4 at 450°C. In
the absence of H2 O and O2 , CO2 conversion efficiency could reach as
high as 80%. With increasing the operation temperature, both the con-
version efficiency and CO selectivity increased in the range of 450 to
550°C. Further, 750 cycles operation (45 h) was conducted to evaluate
the stability of FeCrCu/K/PMG-20 at 550°C. The DFM activity was gen-
erally stable during the testing period under both model (CO2 in N2 ) or
realistic (H2 O and O2 contained) conditions, as shown in Fig. 18. The Fig. 18. Cyclic ICCC performance of the FeCrCu/K/PMG-20 under ideal
species that may cause the deactivation of DFM, such as coke, formate, (5.8%CO2 /N2 ) and realistic conditions (5.8%CO2 /5%O2 /4%H2 O/N2 ) over 750
and carbonates, were not observed, indicating the suitability of the de- cycles (Bobadilla et al., 2016).
veloped DFMs for ICCC of CO production (Bobadilla et al., 2016).
Fex Coy Mg10 CaO was developed with a one-pot sol-gel method and
evaluated for its performance in CO2 capture and in-situ RWGS isother- of Fe/Co, the newly formed Fermi level (0.74 V) in Fe5 Co5 Mg10 CaO
mally at 650°C (Shao et al., 2021a). The CO2 carbonation-decarbonation heterojunctions was much higher than the electric potential of CO2 /CO
cyclic stability of CaO was significantly improved due to the preven- (−0.52 V), and thus the absorbed CO2 around the bimetal catalytic sites
tion of CaO sintering by the melt-intercalation of Fe2 O3 into CaO could be easily reduced to CO (Shao et al., 2021a).
and the high-temperature refractory MgO. Fe5 Co5 Mg10 CaO showed the At a milder temperature of 350°C, the continuous CO2 capture and
best stability with a slight uptake capacity decrease from 9.58 to 9.20 reduction to CO from 1%CO2 /10%O2 /N2 were reported on Pt-Na/Al2 O3
mol/kg over ten cycles, much smaller than CaO (9.14 to 4.45 mol/kg), DFMs (Li et al., 2022). In this study, different basic metals (K, Na, Mg,
Fe10 Mg10 CaO (9.09 to 7.41 mol/kg), and Co10 Mg10 CaO (8.90 to 6.68 and Ca) were investigated for the modification of Pt/Al2 O3 in ICCC,
mol/kg). In the subsequent RWGS conversion stage, CO2 conversion among which, Pt-Na/Al2 O3 showed superior performance with much
efficiency of 90% was reached with a CO yield of 8.28 mol/kg for higher CO yield (0.158 mol/kg) and selectivity (89%). Na-modified Pt
Fe5 Co5 Mg10 CaO and remained stable for ten cycles. The varied valence nanoparticles (NPs) were formed on Al2 O3 , in which Na served as the
states of Fe2+ /Fe3+ and Co2+ /Co3+ provided additional oxygen vacan- CO2 capture sites adjacent to Pt NPs and suppressed the sorption of
cies for CO2 carbonation enhancement. It was found that Fe2+ /Fe3+ was formed CO, thus hindering the further hydrogenation of CO to CH4 and
the active catalytic site while Co acted as a promoter in the DFM. CO2 leading to higher CO selectivity. A 100 h (6000 cycles) continuous op-
was first reduced to CO by Fe3 O4 , and then the formed Fe2 O3 was fur- eration of the Pt-Na/Al2 O3 was conducted in dual fixed bed reactors by
ther regenerated by H2 through the promoter of Co. The heterojunction- switching the CO2 and H2 gas streams in between every 30 s, as shown
redox mechanism was proposed to understand the Fe-Co bimetallic cat- in Fig. 20. The uncaptured CO2 was about 540 ppm, corresponding to a
alytic RWGS reaction, as shown in Fig. 19. Due to the synergistic effect capture efficiency of ∼90% (inlet CO2 : 5000 ppm). The CO concentra-
20
Fig. 19. Heterojunction redox mechanism of

the Fe5 Co5 Mg10 CaO for the ICCC (Shao et al.,
2021a).
Fig. 20. (a) Reactor system of continuous ICCC operation, (b) 100 h (6000 cycles) long-term operation using the continuous reactor system with Pt-Na/Al2 O3 at
350°C (Li et al., 2022).
tion ranged from 2500 to 4200 ppm, while that of CH4 maintained below (1) Match of CO2 capture and conversion reactions. The ICCC
200 ppm. No significant decrease in the CO2 uptake and CO productiv- process integrates the CO2 decarbonation reaction and CO2 conversion
ity were observed. The continuous operation demonstrates the promise reaction in the same stage. So it is vital to match the operation condi-
of the ICCC for both CO2 reduction and utilization in one process under tions (reaction rates, temperatures, duration, etc.) of CO2 decarbonation
mild conditions (Li et al., 2022). Similar to previously reported studies, and conversion. Ideally, the captured CO2 is converted into the products
the addition of steam caused a decrease in CO2 conversion efficiency immediately once it is released from the sorbent components at the same
and CO yield in the continuous operation, indicating the necessity of temperatures. From a thermodynamic point of view, only the ICCC-Met
water removal before ICCC or developing water-resistant DFMs for the process is exothermic, which means no additional thermal input is re-
industrial flue gas applications. quired. While for the ICCC-RWGS and ICCC-DR processes, a significant
amount of heat is needed due to their endothermic nature. As a result,
Challenges and opportunities research should be carried out on not only the adjustment of operation
conditions of CO2 decarbonation and conversion but also the heat man-
The ICCC process using DFMs is an emerging and promising pro- agement in the endothermic ICCC-RWGS and ICCC-DR processes.
cess for simultaneous CO2 capture and conversion, which eliminates (2) Development of DFMs. DFMs play a critical role in the ICCC
CO2 compression and transportation, decreases the high temperature process, which combines the CO2 decarbonation reaction and CO2 con-
required for the sorbent regeneration, and reduces the number of re- version reaction and thus determines the performance and efficiency of
actors in the conventional separated processes. Consequently, plenty of the process. Therefore, great efforts have been paid to the development
research has been conducted on the development of the ICCC process, of DFMs. Different CO2 sorbents and catalysts have been coupled to-
i.e., ICCC-Met, ICCC-RWGS, and ICCC-DR. Nonetheless, the ICCC pro- gether to prepare DFMs. Alkali metal oxides or carbonates such as CaO,
cess is a brand new technology; thus, there are many considerable gaps MgO, SrO, Na2 O, Na2 CO3 , and K2 CO3 serve as the CO2 sorbent in the
required to be solved for its industrial applications. DFMs. Transition metals such as Ru, Rh, and Ni are used as the cata-
21
lyst in the DFMs. However, a noticeable decline has been observed in Table 5
CO2 capture and conversion performance of the DFMs due to sinter- Summary of CO2 concentrations and compositions of flue gases from different
ing and/or coking, as discussed in Section 3. Metal oxides with high sources (Bains et al., 2017).
Tammann temperatures (e.g., Al2 O3 , ZrO2, and CeO2 (Arellano-Treviño CO2 source CO2 concentration (%) Flue gas component
et al., 2019b; Bermejo-López et al., 2019b; Hu and Urakawa, 2018; Zhou
Petroleum power plant 3–8 CO2 , NOx , SOx , O2 , N2
et al., 2020)), as well as promoters (e.g., K and Na (Al-Mamoori et al., Natural gas power plant 3–5 CO2 , NOx , SOx , CO, O2 ,
2018; Xu et al., 2021)), have been used to modify the DFMs to improve N2
the performance of DFMs. However, to the best of our knowledge, such Coal-fired power plant 10–15 CO2 , NOx , SOx , CO, O2 ,
a deactivation still occurs during cyclic operations. Therefore, to obtain N2
Cement production 14–33 CO2 , H2 O, N2 ,
DFMs with remarkable CO2 uptake capacity, excellent catalytic activity,
hydrocarbons
high product selectivity, and good cyclic stability, more work should be Iron and steel 20–27 (for blast furnace) H2 , N2 , CO, CO2 , H2 S
conducted on the rational design of DFMs, such as the utilization of manufacturing 16–42 (for basic oxygen H2 , N2 , CO, CO2 , H2 S
strong metal-support interaction and the formation of bimetallic cat- furnace)
Air 0.03–0.04 N2 , O2
alyst. Except for the sorbents using alkali metal oxides or carbonates
and catalysts using metallic metals, a data-driven method by combining
computational chemistry and machine learning is highly recommended
to identify other desired sorbents and catalysts from tens of thousands convert CO2 to value-added products. However, note that N2 -diluted H2 ,
of candidates. Moreover, the performance of the ICCC process was pri- instead of pure H2 , was used in this stage in some work, which is not the
marily assessed using powdery DFMs in the TGA or fixed bed reactors. case in industrial situations. Therefore, when assessing the CO2 capture
But for the industrial applications of the ICCC process in the future, the and conversion performance of the DFMs, it is of practical significance
fluidized bed reactor is a better choice. In this case, powdery materials to use industrial relevant reaction conditions. Additionally, more work
are no longer suitable for fluidized bed reactors. So it is essential to ex- should be performed to explore the reaction mechanisms of the ICCC
plore pelletization approaches to synthesize DFMs particles with strong processes under industrial relevant reaction conditions, which provides
mechanical strength. At the same time, the cost of the pelletization ap- theoretical guidance for the design of the DFMs.
proaches should be taken into account as well as their potential to scale (5) Potential application for direct air capture and conversion.
up. Apart from the widely investigated ICCC for CO2 at high concentration
(3) Hydrogen source. H2 is inevitably used in the ICCC-Met and levels in industrially relevant processes as listed in Table 5, DMFs were
ICCC-RWGS processes. To avoid additional CO2 emissions, green H2 , also reported to be promising for direct air capture (CO2 at ppm levels)
produced via water electrolysis using renewable energy electricity and conversion by a few studies. It was demonstrated that the Ni/Na-
(Kondratenko et al., 2013), is recommended as the H2 source for these 𝛾-Al2 O3 could convert >90% of the captured CO2 from a gas stream
processes. However, currently, the production of green H2 is not ma- containing 100–400 ppm CO2 to more concentrated CH4 even in the
ture (Masoudi Soltani et al., 2021; Nnabuife et al., 2022). For in- presence of 20% O2 as shown in Fig. 21a (Kosaka et al., 2021). Ru-
stance, González-Garay et al. conducted a process simulation and life based DFMs were also investigated for the CO2 direct air capture and
cycle assessment of methanol production from CO2 and renewable H2 methanation. Jeong-Potter et al. used 0.5%Ru-6.1%Na2 O/𝛾-Al2 O3 for
(González-Garay et al., 2019). They found that the cost of producing the integrated capture of diluted CO2 in a simulated air stream (400
green H2 accounted for 27% to 79% of the total cost of methanol pro- ppm) and methanation at 320°C (Jeong-Potter and Farrauto, 2021).
duction, relying on the source of electricity (solar, nuclear, wind, or More than 82% of the absorbed CO2 can be effectively converted to
biomass). Similarly, alkanes such as methane and ethane are used in CH4 with a yield of 0.172 mol/kg and selectivity of 100% under dry
the ICCC-DR process, and the cost of alkanes should also be taken into conditions. The developed DFMs show great potential for combining di-
account. Therefore, research should also be conducted to lower the pro- rect air capture and methanation in one process. Nonetheless, the sorp-
duction cost of H2 and alkanes. tion of CO2 was conducted at 320°C meaning the energy consumption
(4) Performance tests under industrially relevant conditions. for heating up the air stream. The energy required for the temperature
Dynamic operations are necessary for the ICCC process to realize the swing mode of the direct air capture and methanation was estimated
continuous CO2 capture and conversion, either switching different gas to be 9 MJ/m3 -CH4 in another study, although with the CO2 sorbent
streams or transporting the DFMs between two (or even more) reactors and catalyst deployed in two separate reactors (Veselovskaya et al.,
(Bobadilla et al., 2016; Li et al., 2022; Wang, G. et al., 2022). There- 2020). Lower operation temperatures need to be conducted to reduce
fore, the continuous operation close to practical conditions should also the energy requirement (Jeong-Potter and Farrauto, 2021). In a further
be considered in further studies. Besides, reaction conditions used in the study, the 1%Ru-10%Na2 O/𝛾-Al2 O3 was used for the direct air capture
capture and conversion stages significantly affect the ICCC performance. of CO2 at ambient temperature and methanation at 300°C as shown in
For the CO2 capture stage, the compositions of the CO2 -contained flue Fig. 21b (Jeong-Potter et al., 2022). The CH4 yield of 1.067 mol/kg
gases are highly dependent on the flue gas sources (He et al., 2022). As with 100% selectivity was achieved. It was found that with the expo-
shown in Table 5, the CO2 concentration differs a lot from the variation sure of 0.5%Ru-6.1%Na2 O/𝛾-Al2 O3 to a high content of O2 (∼21%) for
of the CO2 source. The wide range of CO2 concentrations in the CO2 a long time, the Ru in DFM can be completely reactivated in the metha-
capture stage poses a big challenge for the DFMs. At the same time, the nation step (Jeong-Potter and Farrauto, 2021). In the presence of 2.0%
contaminants in the flue gas also have an influence on the DFMs. For in- H2 O in air, it can significantly improve both the sorption and metha-
stance, when the CO2 capture stage was conducted under an atmosphere nation performances of 1%Ru-10%Na2 O/𝛾-Al2 O3 , which were 2.4 and
of 7.5% CO2 /4.5%O2 /15%H2 O/N2 balance, the subsequent methana- 3.5 times greater respectively than that under dry condition. This was
tion reaction did not take place over the 10% Ni supported on 6.2% supposed to be caused by the formation of amorphous NaHCO3 in the
Na2 O/Al2 O3 (Arellano-Treviño et al., 2019a). This was because metal- presence of H2 O. On Ru-CaO/𝛾-Al2 O3 DFM, on the contrary, humid air
lic Ni was oxidized in the capture stage, which could not be reduced was found to adversely affect the sorption of CO2 (Jeong-Potter et al.,
back under a reducing atmosphere at a temperature of 320 °C. Besides, 2022). Considering the lower operation temperature of Na2 O-DFM com-
contaminants such as O2 , SOx , and NOx are present in the flue gas, as pared to CaO-DFM due to the higher stability of formed carbonates on
shown in Table 5. They are very likely to affect the sorbent and/or cat- CaO (Arellano-Treviño et al., 2019a; Bermejo-López et al., 2019a), it ap-
alytic components in the DFMs (e.g., formation of CaSO4 by the reaction pears that Na2 O containing Ru-based DFMs is more promising for direct
between CaO and SOx ), which should also be considered for the ICCC air capture/methanation under realistic conditions (Jeong-Potter et al.,
process. Turning to the CO2 conversion stage, H2 is commonly used to 2022).
22
Fig. 21. Schematic of diluted CO2 (atmospheric level) capture and conversion using DFMs in (a) isothermal and (b) temperature swing operation mode (Jeong-
Potter et al., 2022; Kosaka et al., 2021).
Nonetheless, intensive investigations are needed for integrated di- focused on the development of DFMs. Only a few works included pro-
rect air capture and conversion. For example, more DFMs need to be cess simulation, life cycle assessment, and techno-economic analysis. For
developed and tested for DAC applicability, thus guiding the frame of example, Shao et al. (Shao et al., 2021a) conducted an economic eval-
promising materials combination. Detailed and extended effects of O2 , uation and demonstrated that the ICCC-RWGS strategy would generate
H2 O, and other prevalent components on the sorption and catalytic ac- an additional profit of $9.38 million per year compared to the combina-
tivity of DFMs remain to be tested. Prolonged experimental tests should tion of individual CaL and RWGS processes to address around 100,000
be conducted in ambient air conditions to evaluate the robustness of the t/year of CO2 emission in an ethylene plant with a yearly operating time
developed DFMs. Methane is currently the only conversion product for of 8,000 h/year. Sun et al. (Sun, S. et al., 2021a) performed the techno-
the integrated DAC process. Other possible products can be investigated economic analysis of the ICCC-RWGS process. They reported that the
to achieve the diversity of the process. Appropriate operation tempera- cost of CO generating is $292/ton for the ICCC-RWGS using CaO alone,
tures for the sorption and subsequent conversion should be studied for which is much lower than that of a single RWGS process ($447/ton),
process optimization. Since the CO2 concentration is much lower, thus including conventional CaL process for CO2 capture, CO2 compression
the sorption duration of CO2 capture was much longer than that for the and transportation, RWGS, and the standard syngas purification process.
industrial flue gases to reach reasonable CO2 uptake. However, the time The costs of DFMs used for the ICCC process may also significantly affect
needed for the conversion was usually much lower than the sorption the practical applications. Yet the costs for the large-scale preparation
process (Kosaka et al., 2021). Therefore, the matching between these of DFMs are seldom discussed in open literature. The used active metals,
two consecutive processes should be properly designed and optimized sorbent materials, and preparation methods etc. need to be considered
for practical application. economically for DFMs development. Among the widely investigated
(6) Process simulation, life cycle assessment, and techno- metals, Ni being the cheapest one ($0.028 USD/g) with reasonable ac-
economic analysis. The majority of work concerning the ICCC process tivity comparing to the noble metals, i.e., Ru ($19.9 USD/g) and Rh
23
($498.3 USD/g) (Daily Metal Prices, 2022). However, it is more sensi- Bermejo-López, A., Pereda-Ayo, B., González-Marcos, J.A., González-Velasco, J.R., 2019a.
tive to O2 , which is widely presented in CO2 containing streams, and Mechanism of the CO2 storage and in situ hydrogenation to CH4 . Temperature and ad-
sorbent loading effects over Ru-CaO/Al2 O3 and Ru-Na2 CO3 /Al2 O3 catalysts. Applied
may loss the conversion activity especially at low operation tempera- Catalysis B: Environmental 256, 117845. doi:10.1016/j.apcatb.2019.117845.
tures (Arellano-Treviño et al., 2019a; Arellano-Treviño et al., 2019b) Bermejo-López, A., Pereda-Ayo, B., González-Marcos, J.A., González-Velasco, J.R., 2019b.
as discussed earlier. Thus it remains a big challenge for the developing Ni loading effects on dual function materials for capture and in-situ conversion
of CO2 to CH4 using CaO or Na2 CO3 . Journal of CO2 Utilization 34, 576–587.
of cost-effective DFMs. Currently, process simulation, life cycle assess- doi:10.1016/j.jcou.2019.08.011.
ment, and techno-economic analysis are limited for the ICCC, which are Bermejo-López, A., Pereda-Ayo, B., Onrubia-Calvo, J.A., González-Marcos, J.A., González-
important for the industrial applications of the ICCC process in the fu- Velasco, J.R., 2022. Tuning basicity of dual function materials widens operation tem-
perature window for efficient CO2 adsorption and hydrogenation to CH4 . Journal of
ture.
CO2 Utilization 58, 101922. doi:10.1016/j.jcou.2022.101922.
Bhattacharyya, S.S., Leite, F., Adeyemi, M.A., Sarker, A.J., Cambareri, G.S., Faverin, C.,
Tieri, M.P., Castillo-Zacarias, C., Melchor-Martinez, E.M., Iqbal, H.M.N., Parra-
Conclusions Saldivar, R., 2021. A paradigm shift to CO2 sequestration to manage global warming-
With the emphasis on developing countries. Science of the Total Environment 790,
ICCC is an emerging and promising process that can simultaneously 148169. doi:10.1016/j.scitotenv.2021.148169.
Bhown, A.S., Freeman, B.C., 2011. Analysis and status of post-combustion carbon diox-
reduce CO2 emissions and produce value-added products such as CH4 ide capture technologies. Environmental Science & Technology 45 (20), 8624–8632.
and syngas. Extensive studies have been performed on the ICCC pro- doi:10.1021/es104291d.
cess thus far. However, except for the ICCC-Met process, both the ICCC- Bobadilla, L.F., Riesco-García, J.M., Penelás-Pérez, G., Urakawa, A., 2016. Enabling con-
tinuous capture and catalytic conversion of flue gas CO2 to syngas in one process.
RWGS and ICCC-DR processes are endothermic from a thermodynamic Journal of CO2 Utilization 14, 106–111. doi:10.1016/j.jcou.2016.04.003.
perspective. Thus, heat management should be taken into account for Buckingham, J., Reina, T.R., Duyar, M.S., 2022. Recent advances in carbon diox-
these two processes. In addition, operation parameters, including re- ide capture for process intensification. Carbon Capture Science & Technology 2.
doi:10.1016/j.ccst.2022.100031.
action atmosphere, temperature, duration, and flow rate, play an im-
Bui, M., Adjiman, C.S., Bardow, A., Anthony, E.J., Boston, A., Brown, S., Fennell, P.S.,
portant role in the performance of the ICCC process. Among them, the Fuss, S., Galindo, A., Hackett, L.A., Hallett, J.P., Herzog, H.J., Jackson, G., Kem-
reaction temperature and reaction atmosphere show the greatest influ- per, J., Krevor, S., Maitland, G.C., Matuszewski, M., Metcalfe, I.S., Petit, C.,
ence on the CO2 capture and conversion in the ICCC system. In view of Puxty, G., Reimer, J., Reiner, D.M., Rubin, E.S., Scott, S.A., Shah, N., Smit, B.,
Trusler, J.P.M., Webley, P., Wilcox, J., Mac Dowell, N., 2018. Carbon capture and
the DFMs, Ni-based DFMs have been widely investigated for each ICCC storage (CCS): the way forward. Energy & Environmental Science 11 (5), 1062–1176.
process mentioned above, while Ru-based DFMs have been mostly in- doi:10.1039/c7ee02342a.
vestigated for the ICCC-Met process. Other metal-based DFMs, such as Chai, K.H., Leong, L.K., Wong, D.S.H., Tsai, D.H., Sethupathi, S., 2020. Effect of
CO2 adsorbents on the Ni-based dual-function materials for CO2 capturing and
Cu, Fe, Co, etc., have also been mainly developed for the ICCC-RWGS in situ methanation. Journal of the Chinese Chemical Society 67 (6), 998–1008.
process. The ICCC process is still in its infancy, and further studies such doi:10.1002/jccs.202000086.
as rational design and synthesis of the DFMs and conduction of process Chen, J., Donat, F., Duan, L., Kierzkowska, A.M., Kim, S.M., Xu, Y., Anthony, E.J.,
Müller, C.R., 2021. Metal-oxide stabilized CaO/CuO composites for the in-
simulation, life cycle assessment, and techno-economic analysis are es- tegrated Ca/Cu looping process. Chemical Engineering Journal 403, 126330.
sential for enhancing its performance and thus realizing its industrial doi:10.1016/j.cej.2020.126330.
applications. Chen, J., Duan, L., Sun, Z., 2019. Accurate Control of Cage-Like CaO Hollow Micro-
spheres for Enhanced CO2 Capture in Calcium Looping via a Template-Assisted
Synthesis Approach. Environmental Science & Technology 53 (4), 2249–2259.
Declaration of Competing Interest doi:10.1021/acs.est.8b06138.
Chen, J., Duan, L., Sun, Z., 2020. Review on the Development of Sorbents for Calcium
Looping. Energy & Fuels 34 (7), 7806–7836. doi:10.1021/acs.energyfuels.0c00682.
The authors declare that they have no known competing financial Cimino, S., Boccia, F., Lisi, L., 2020. Effect of alkali promoters (Li, Na, K) on the perfor-
interests or personal relationships that could have appeared to influence mance of Ru/Al2 O3 catalysts for CO2 capture and hydrogenation to methane. Journal
of CO2 Utilization 37, 195–203. doi:10.1016/j.jcou.2019.12.010.
the work reported in this paper. Cimino, S., Russo, R., Lisi, L., 2022. Insights into the cyclic CO2 capture and catalytic
methanation over highly performing Li-Ru/Al2 O3 dual function materials. Chemical
Engineering Journal 428, 131275. doi:10.1016/j.cej.2021.131275.
Acknowledgments Cruz-Hernández, A., Mendoza-Nieto, J.A., Pfeiffer, H., 2017. NiO-CaO materials as promis-
ing catalysts for hydrogen production through carbon dioxide capture and sub-
This work was supported by Natural Science Fund of Colleges sequent dry methane reforming. Journal of Energy Chemistry 26 (5), 942–947.
doi:10.1016/j.jechem.2017.07.002.
and Universities in Jiangsu Province, Young Scientific and techno- Cunningham, M.F., Jessop, P.G., 2019. Carbon Dioxide-Switchable Polymers:
logical Talents Project of Suzhou Association for Science and Tech- Where Are the Future Opportunities? Macromolecules 52 (18), 6801–6816.
nology, Tsinghua University Initiative Scientific Research Program doi:10.1021/acs.macromol.9b00914.
Daily Metal Prices. https://www.dailymetalprice.com/. (accessed on 2022 .05.20)
(20213080042), Huaneng Group Science and Technology Research Daniel, T., Masini, A., Milne, C., Nourshagh, N., Iranpour, C., Xuan, J., 2022. Techno-
Project (KTHT-U22YYJC12), and Tsinghua University-Shanxi Clean En- economic Analysis of Direct Air Carbon Capture with CO2 Utilisation. Carbon Capture
ergy Research Institute Innovation Project Seed Fund. Science & Technology 2, 100025. doi:10.1016/j.ccst.2021.100025.
Das, S., Perez-Ramirez, J., Gong, J., Dewangan, N., Hidajat, K., Gates, B.C., Kawi, S.,
2020. Core-shell structured catalysts for thermocatalytic, photocatalytic, and elec-
References trocatalytic conversion of CO2 . Chemical Society Reviews 49 (10), 2937–3004.
doi:10.1039/c9cs00713j.
Al-Mamoori, A., Rownaghi, A.A., Rezaei, F., 2018. Combined Capture and Utilization of De, S., Dokania, A., Ramirez, A., Gascon, J., 2020. Advances in the Design of Heteroge-
CO2 for Syngas Production over Dual-Function Materials. ACS Sustainable Chemistry neous Catalysts and Thermocatalytic Processes for CO2 Utilization. ACS Catalysis 10
& Engineering 6 (10), 13551–13561. doi:10.1021/acssuschemeng.8b03769. (23), 14147–14185. doi:10.1021/acscatal.0c04273.
Alper, E., Yuksel Orhan, O., 2017. CO2 utilization: Developments in conversion processes. Dunstan, M.T., Donat, F., Bork, A.H., Grey, C.P., Muller, C.R., 2021. CO2 Capture
Petroleum 3 (1), 109–126. doi:10.1016/j.petlm.2016.11.003. at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental
Anwar, M.N., Fayyaz, A., Sohail, N.F., Khokhar, M.F., Baqar, M., Yasar, A., Rasool, K., Aspects, Mechanistic Insights, and Recent Advances. Chemical Reviews 121 (20),
Nazir, A., Raja, M.U.F., Rehan, M., Aghbashlo, M., Tabatabaei, M., Nizami, A.S., 2020. 12681–12745. doi:10.1021/acs.chemrev.1c00100.
CO2 utilization: Turning greenhouse gas into fuels and valuable products. Journal of Duyar, M.S., Treviño, M.A.A., Farrauto, R.J., 2015. Dual function materials for CO2 cap-
Environmental Management 260, 110059. doi:10.1016/j.jenvman.2019.110059. ture and conversion using renewable H2 . Applied Catalysis B: Environmental 168-169,
Arellano-Treviño, M.A., He, Z., Libby, M.C., Farrauto, R.J., 2019a. Catalysts and adsor- 370–376. doi:10.1016/j.apcatb.2014.12.025.
bents for CO2 capture and conversion with dual function materials: Limitations of Ni- Duyar, M.S., Wang, S., Arellano-Treviño, M.A., Farrauto, R.J., 2016. CO2 utilization
containing DFMs for flue gas applications. Journal of CO2 Utilization 31, 143–151. with a novel dual function material (DFM) for capture and catalytic conver-
doi:10.1016/j.jcou.2019.03.009. sion to synthetic natural gas: An update. Journal of CO2 Utilization 15, 65–71.
Arellano-Treviño, M.A., Kanani, N., Jeong-Potter, C.W., Farrauto, R.J., 2019b. Bimetallic doi:10.1016/j.jcou.2016.05.003.
catalysts for CO2 capture and hydrogenation at simulated flue gas conditions. Chem- Gao, W., Liang, S., Wang, R., Jiang, Q., Zhang, Y., Zheng, Q., Xie, B., Toe, C.Y., Zhu, X.,
ical Engineering Journal 375, 121953. doi:10.1016/j.cej.2019.121953. Wang, J., Huang, L., Gao, Y., Wang, Z., Jo, C., Wang, Q., Wang, L., Liu, Y., Louis, B.,
Bains, P., Psarras, P., Wilcox, J., 2017. CO2 capture from the industry sector. Progress in Scott, J., Roger, A.C., Amal, R., He, H., Park, S.E., 2020. Industrial carbon dioxide cap-
Energy and Combustion Science 63, 146–172. doi:10.1016/j.pecs.2017.07.001. ture and utilization: state of the art and future challenges. Chemical Society Reviews
49 (23), 8584–8686. doi:10.1039/d0cs00025f.
24
Gao, X., Yang, S., Hu, L., Cai, S., Wu, L., Kawi, S., 2022. Carbonaceous materials as adsor- Kim, Y.-H., Kim, J.-J., Lee, C.-H., 2017. Adsorptive cyclic purification process for CO2
bents for CO2 capture: synthesis and modification. Carbon Capture Science & Tech- mixtures captured from coal power plants. AIChE Journal 63 (3), 1051–1063.
nology 3, 100039. doi:10.1016/j.ccst.2022.100039. doi:10.1002/aic.15440.
Gao, Y., Qian, K., Xu, B., Li, Z., Zheng, J., Zhao, S., Ding, F., Sun, Y., Xu, Z., Kondratenko, E.V., Mul, G., Baltrusaitis, J., Larrazábal, G.O., Pérez-Ramírez, J., 2013.
2020. Recent advances in visible-light-driven conversion of CO2 by photocata- Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, pho-
lysts into fuels or value-added chemicals. Carbon Resources Conversion 3, 46–59. tocatalytic and electrocatalytic processes. Energy & Environmental Science 6 (11),
doi:10.1016/j.crcon.2020.02.003. 3112. doi:10.1039/c3ee41272e.
González-Garay, A., Frei, M.S., Al-Qahtani, A., Mondelli, C., Guillén-Gosálbez, G., Pérez- Kong, T., Jiang, Y., Xiong, Y., 2020. Photocatalytic CO2 conversion: What can we learn
Ramírez, J., 2019. Plant-to-planet analysis of CO2 -based methanol processes. Energy from conventional COx hydrogenation? Chemical Society Reviews 49 (18), 6579–
& Environmental Science 12 (12), 3425–3436. doi:10.1039/c9ee01673b. 6591. doi:10.1039/c9cs00920e.
Gu, H., Gao, Y., Iftikhar, S., Li, F., 2022. Ce stabilized Ni–SrO as a catalytic phase transition Kosaka, F., Liu, Y., Chen, S.-Y., Mochizuki, T., Takagi, H., Urakawa, A., Kuramoto, K.,
sorbent for integrated CO2 capture and CH4 reforming. Journal of Materials Chemistry 2021. Enhanced Activity of Integrated CO2 Capture and Reduction to CH4 under Pres-
A 10 (6), 3077–3085. doi:10.1039/d1ta09967a. surized Conditions toward Atmospheric CO2 Utilization. ACS Sustainable Chemistry
Gul, A., Tezcan Un, U., 2022. Effect of Temperature and Gas Flow Rate on CO2 & Engineering 9 (9), 3452–3463. doi:10.1021/acssuschemeng.0c07162.
Capture. European Journal of Sustainable Development Research 6 (2), em0181. Li, L., Miyazaki, S., Yasumura, S., Ting, K.W., Toyao, T., Maeno, Z., Shimizu, K.-i.,
doi:10.21601/ejosdr/11727. 2022. Continuous CO2 Capture and Selective Hydrogenation to CO over Na-Promoted
Guo, Y., Sun, J., Wang, R., Li, W., Zhao, C., Li, C., Zhang, J., 2021. Recent advances in Pt Nanoparticles on Al2 O3 . ACS Catalysis 12 (4), 2639–2650. doi:10.1021/ac-
potassium-based adsorbents for CO2 capture and separation: a review. Carbon Capture scatal.1c05339.
Science & Technology 1, 100011. doi:10.1016/j.ccst.2021.100011. Lian, S., Song, C., Liu, Q., Duan, E., Ren, H., Kitamura, Y., 2021. Recent advances in ionic
He, X., Chen, D., Liang, Z., Yang, F., 2022. Insight and Comparison of Energy- liquids-based hybrid processes for CO2 capture and utilization. Journal of Environ-
efficient Membrane Processes for CO2 Capture from Flue Gases in Power mental Sciences 99, 281–295. doi:10.1016/j.jes.2020.06.034.
Plant and Energy-intensive Industry. Carbon Capture Science & Technology 2. Liang, F., Zhang, K., Zhang, L., Zhang, Y., Lei, Y., Sun, X., 2021. Recent Development
doi:10.1016/j.ccst.2021.100020. of Electrocatalytic CO2 Reduction Application to Energy Conversion. Small 17 (44),
Hong, W.Y., 2022. A techno-economic review on carbon capture, utilisation and storage e2100323. doi:10.1002/smll.202100323.
systems for achieving a net-zero CO2 emissions future. Carbon Capture Science & Liang, J., Wu, Q., Huang, Y.B., Cao, R., 2021. Reticular frameworks and their de-
Technology 3, 100044. doi:10.1016/j.ccst.2022.100044. rived materials for CO2 conversion by thermo−catalysis. EnergyChem 3 (6), 100064.
Hu, J., Hongmanorom, P., Chirawatkul, P., Kawi, S., 2021a. Efficient integration doi:10.1016/j.enchem.2021.100064.
of CO2 capture and conversion over a Ni supported CeO2 -modified CaO mi- Liu, L., Zhao, C., Xu, J., Li, Y., 2015. Integrated CO2 capture and photocatalytic conversion
crosphere at moderate temperature. Chemical Engineering Journal 426, 130864. by a hybrid adsorbent/photocatalyst material. Applied Catalysis B: Environmental
doi:10.1016/j.cej.2021.130864. 179, 489–499. doi:10.1016/j.apcatb.2015.06.006.
Hu, J., Hongmanorom, P., Galvita, V.V., Li, Z., Kawi, S., 2021b. Bifunctional Ni- Liu, W., Cai, Y., Luo, M., Yang, Y., Li, P., 2022. Potential Application of Alkaline Metal
Ca based material for integrated CO2 capture and conversion via calcium- Nitrate-Promoted Magnesium-Based Materials in the Integrated CO2 Capture and
looping dry reforming. Applied Catalysis B: Environmental 284, 119734. Methanation Process. Industrial & Engineering Chemistry Research 61 (7), 2882–
doi:10.1016/j.apcatb.2020.119734. 2893. doi:10.1021/acs.iecr.1c04615.
Hu, L., Urakawa, A., 2018. Continuous CO2 capture and reduction in one process: CO2 Liu, Z., Deng, Z., He, G., Wang, H., Zhang, X., Lin, J., Qi, Y., Liang, X., 2021. Challenges and
methanation over unpromoted and promoted Ni/ZrO2 . Journal of CO2 Utilization 25, opportunities for carbon neutrality in China. Nature Reviews Earth & Environment 3
323–329. doi:10.1016/j.jcou.2018.03.013. (2), 141–155. doi:10.1038/s43017-021-00244-x.
Huang, P., Guo, Y., Wang, G., Yu, J., Zhao, C., Wang, X., Wang, T., 2021. In- Lv, Z., Qin, C., Chen, S., Hanak, D.P., Wu, C., 2021. Efficient-and-stable CH4 reforming
sights into Nickel-Based Dual Function Materials for CO2 Sorption and Metha- with integrated CO2 capture and utilization using Li4 SiO4 sorbent. Separation and
nation: Effect of Reduction Temperature. Energy & Fuels 35 (24), 20185–20196. Purification Technology 277, 119476. doi:10.1016/j.seppur.2021.119476.
doi:10.1021/acs.energyfuels.1c03008. Ma, R., Sun, J., Li, D.H., Wei, J.J., 2020. Review of synergistic photo-thermo-catalysis:
Hyakutake, T., van Beek, W., Urakawa, A., 2016. Unravelling the nature, evolution and Mechanisms, materials and applications. International Journal of Hydrogen Energy
spatial gradients of active species and active sites in the catalyst bed of unpromoted 45 (55), 30288–30324. doi:10.1016/j.ijhydene.2020.08.127.
and K/Ba-promoted Cu/Al2 O3 during CO2 capture-reduction. Journal of Materials Ma, X., Li, X., Cui, H., Zhang, W., Cheng, Z., Zhou, Z., 2021. Metal oxide-doped Ni/CaO
Chemistry A 4 (18), 6878–6885. doi:10.1039/c5ta09461e. dual-function materials for integrated CO2 capture and conversion: Performance and
IEA, 2017. Energy Technology Perspectives 2017. https://www.iea.org/reports/energy- mechanism. AIChE Journal doi:10.1002/aic.17520.
technology-perspectives-2017. Masoudi Soltani, S., Lahiri, A., Bahzad, H., Clough, P., Gorbounov, M., Yan, Y., 2021.
IEA, 2019. World Energy Outlook 2019. https://www.iea.org/reports/world-energy- Sorption-enhanced Steam Methane Reforming for Combined CO2 Capture and Hy-
outlook-2019. drogen Production: A State-of-the-Art Review. Carbon Capture Science & Technology
IEA, 2021. World Energy Model. https://www.iea.org/reports/world-energy-model. 1. doi:10.1016/j.ccst.2021.100003.
Ikreedeegh, R.R., Tahir, M., 2021. A critical review in recent developments of Mazza, A., Bompard, E., Chicco, G., 2018. Applications of power to gas technologies in
metal-organic-frameworks (MOFs) with band engineering alteration for photo- emerging electrical systems. Renewable and Sustainable Energy Reviews 92, 794–806.
catalytic CO2 reduction to solar fuels. Journal of CO2 Utilization 43, 101381. doi:10.1016/j.rser.2018.04.072.
doi:10.1016/j.jcou.2020.101381. McCollum, D.L., Zhou, W., Bertram, C., de Boer, H.-S., Bosetti, V., Busch, S., Després, J.,
Institute, G.C., 2021. Global Status of CCS 2021. https://www.globalccsinstitute.com/ Drouet, L., Emmerling, J., Fay, M., Fricko, O., Fujimori, S., Gidden, M., Harmsen, M.,
wp-content/uploads/2021/11/Global-Status-of-CCS-2021-Global-CCS-Institute-1121. Huppmann, D., Iyer, G., Krey, V., Kriegler, E., Nicolas, C., Pachauri, S., Parkinson, S.,
pdf. Poblete-Cazenave, M., Rafaj, P., Rao, N., Rozenberg, J., Schmitz, A., Schoepp, W., van
Jeong-Potter, C., Abdallah, M., Sanderson, C., Goldman, M., Gupta, R., Farrauto, R., 2022. Vuuren, D., Riahi, K., 2018. Energy investment needs for fulfilling the Paris Agreement
Dual function materials (Ru+Na2 O/Al2 O3 ) for direct air capture of CO2 and in situ and achieving the Sustainable Development Goals. Nature Energy 3 (7), 589–599.
catalytic methanation: The impact of realistic ambient conditions. Applied Catalysis doi:10.1038/s41560-018-0179-z.
B: Environmental 307, 120990. doi:10.1016/j.apcatb.2021.120990. Miguel, C.V., Soria, M.A., Mendes, A., Madeira, L.M., 2017. A sorptive reactor for CO2
Jeong-Potter, C., Farrauto, R., 2021. Feasibility Study of Combining Direct Air Capture of capture and conversion to renewable methane. Chemical Engineering Journal 322,
CO2 and Methanation at Isothermal Conditions with Dual Function Materials. Applied 590–602. doi:10.1016/j.cej.2017.04.024.
Catalysis B: Environmental 282, 119416. doi:10.1016/j.apcatb.2020.119416. Molina-Ramírez, S., Cortés-Reyes, M., Herrera, C., Larrubia, M.A., Alemany, L.J., 2020.
Jiang, Y., Long, R., Xiong, Y., 2019. Regulating C-C coupling in thermocatalytic and CO2 -SR Cyclic Technology: CO2 Storage and in situ Regeneration with CH4 over a
electrocatalytic COx conversion based on surface science. Chemical Science 10 (31), new dual function NiBa unsupported catalyst. Journal of CO2 Utilization 40, 101201.
7310–7326. doi:10.1039/c9sc02014d. doi:10.1016/j.jcou.2020.101201.
Jo, S., Lee, J.H., Kim, T.Y., Woo, J.H., Ryu, H.-J., Hwang, B., Lee, S.C., Kim, J.C., Gilliard- Mountourakis, F., Papazi, A., Kotzabasis, K., 2021. The Microalga Chlorella vulgaris as a
AbdulAziz, K.L., 2022a. A fundamental study of CO2 capture and CH4 production in a Natural Bioenergetic System for Effective CO2 Mitigation—New Perspectives against
rapid cyclic system using nickel-lithium-silicate as a catal-sorbent. Fuel 311, 122602. Global Warming. Symmetry 13 (6), 997. doi:10.3390/sym13060997.
doi:10.1016/j.fuel.2021.122602. Nnabuife, S.G., Ugbeh-Johnson, J., Okeke, N.E., Ogbonnaya, C., 2022. Present and Pro-
Jo, S., Lee, J.H., Woo, J.H., Kim, T.-Y., Ryu, H.-J., Hwang, B., Kim, J.C., Lee, S.C., jected Developments in Hydrogen Production: A Technological Review∗. Carbon Cap-
Gilliard-AbdulAziz, K.L., 2022b. Coke-promoted Ni/CaO catal-sorbents in the pro- ture Science & Technology 3. doi:10.1016/j.ccst.2022.100042.
duction of cyclic CO and syngas. Sustainable Energy & Fuels 6 (1), 81–88. Omodolor, I.S., Otor, H.O., Andonegui, J.A., Allen, B.J., Alba-Rubio, A.C., 2020. Dual-
doi:10.1039/d1se01136g. Function Materials for CO2 Capture and Conversion: A Review. Industrial & Engi-
Jo, S.B., Woo, J.H., Lee, J.H., Kim, T.Y., Kang, H.I., Lee, S.C., Kim, J.C., 2020. A novel neering Chemistry Research 59 (40), 17612–17631. doi:10.1021/acs.iecr.0c02218.
integrated CO2 capture and direct methanation process using Ni/CaO catal-sorbents. Park, S.J., Bukhovko, M.P., Jones, C.W., 2021. Integrated capture and conversion of CO2
Sustainable Energy & Fuels 4 (9), 4679–4687. doi:10.1039/d0se00760a. into methane using NaNO3 /MgO + Ru/Al2 O3 as a catalytic sorbent. Chemical Engi-
Kamkeng, A.D.N., Wang, M., Hu, J., Du, W., Qian, F., 2021. Transformation technologies neering Journal 420, 130369. doi:10.1016/j.cej.2021.130369.
for CO2 utilisation: Current status, challenges and future prospects. Chemical Engi- Porta, A., Matarrese, R., Visconti, C.G., Castoldi, L., Lietti, L., 2021a. Storage Material
neering Journal 409, 128138. doi:10.1016/j.cej.2020.128138. Effects on the Performance of Ru-Based CO2 Capture and Methanation Dual Func-
Kim, S.M., Abdala, P.M., Broda, M., Hosseini, D., Copéret, C., Müller, C., 2018. Integrated tioning Materials. Industrial & Engineering Chemistry Research 60 (18), 6706–6718.
CO2 Capture and Conversion as an Efficient Process for Fuels from Greenhouse Gases. doi:10.1021/acs.iecr.0c05898.
ACS Catalysis 8 (4), 2815–2823. doi:10.1021/acscatal.7b03063.
25
Porta, A., Visconti, C.G., Castoldi, L., Matarrese, R., Jeong-Potter, C., Farrauto, R., Li- Tsiotsias, A.I., Charisiou, N.D., Yentekakis, I.V., Goula, M.A., 2020. The Role of Alkali and
etti, L., 2021b. Ru-Ba synergistic effect in dual functioning materials for cyclic Alkaline Earth Metals in the CO2 Methanation Reaction and the Combined Capture
CO2 capture and methanation. Applied Catalysis B: Environmental 283, 119654. and Methanation of CO2 . Catalysts 10 (7), 812. doi:10.3390/catal10070812.
doi:10.1016/j.apcatb.2020.119654. Veselovskaya, J.V., Lysikov, A.I., Netskina, O.V., Kuleshov, D.V., Okunev, A.G.,
Proaño, L., Arellano-Treviño, M.A., Farrauto, R.J., Figueredo, M., Jeong-Potter, C., 2020. K2 CO3 -Containing Composite Sorbents Based on Thermally Modified Alu-
Cobo, M., 2020. Mechanistic assessment of dual function materials, composed of Ru- mina: Synthesis, Properties, and Potential Application in a Direct Air Cap-
Ni, Na2 O/Al2 O3 and Pt-Ni, Na2 O/Al2 O3 , for CO2 capture and methanation by in-situ ture/Methanation Process. Industrial & Engineering Chemistry Research 59 (15),
DRIFTS. Applied Surface Science 533, 147469. doi:10.1016/j.apsusc.2020.147469. 7130–7139. doi:10.1021/acs.iecr.9b05457.
Proaño, L., Tello, E., Arellano-Trevino, M.A., Wang, S., Farrauto, R.J., Cobo, M., 2019. Veselovskaya, J.V., Parunin, P.D., Netskina, O.V., Kibis, L.S., Lysikov, A.I., Okunev, A.G.,
In-situ DRIFTS study of two-step CO2 capture and catalytic methanation over 2018a. Catalytic methanation of carbon dioxide captured from ambient air. Energy
Ru,“Na2 O”/Al2 O3 Dual Functional Material. Applied Surface Science 479, 25–30. 159, 766–773. doi:10.1016/j.energy.2018.06.180.
doi:10.1016/j.apsusc.2019.01.281. Veselovskaya, J.V., Parunin, P.D., Netskina, O.V., Okunev, A.G., 2018b. A Novel
Ran, J., Jaroniec, M., Qiao, S.Z., 2018. Cocatalysts in Semiconductor-based Photocatalytic Process for Renewable Methane Production: Combining Direct Air Capture by
CO2 Reduction: Achievements, Challenges, and Opportunities. Advanced Materials 30 K2 CO3 /Alumina Sorbent with CO2 Methanation over Ru/Alumina Catalyst. Topics
(7). doi:10.1002/adma.201704649. in Catalysis 61 (15-17), 1528–1536. doi:10.1007/s11244-018-0997-z.
Rogelj, J., den Elzen, M., Hohne, N., Fransen, T., Fekete, H., Winkler, H., Schaeffer, R., Wang, G., Guo, Y., Yu, J., Liu, F., Sun, J., Wang, X., Wang, T., Zhao, C., 2022.
Sha, F., Riahi, K., Meinshausen, M., 2016. Paris Agreement climate proposals need Ni-CaO dual function materials prepared by different synthetic modes for inte-
a boost to keep warming well below 2 degrees C. Nature 534 (7609), 631–639. grated CO2 capture and conversion. Chemical Engineering Journal 428, 132110.
doi:10.1038/nature18307. doi:10.1016/j.cej.2021.132110.
Shao, B., Hu, G., Alkebsi, K.A.M., Ye, G., Lin, X., Du, W., Hu, J., Wang, M., Liu, H., Qian, F., Wang, S., Farrauto, R.J., Karp, S., Jeon, J.H., Schrunk, E.T., 2018. Parametric, cyclic aging
2021a. Heterojunction-redox catalysts of Fex Coy Mg10 CaO for high-temperature CO2 and characterization studies for CO2 capture from flue gas and catalytic conversion
capture and in situ conversion in the context of green manufacturing. Energy & Envi- to synthetic natural gas using a dual functional material (DFM). Journal of CO2 Uti-
ronmental Science 14 (4), 2291–2301. doi:10.1039/d0ee03320k. lization 27, 390–397. doi:10.1016/j.jcou.2018.08.012.
Shao, B., Zhang, Y., Sun, Z., Li, J., Gao, Z., Xie, Z., Hu, J., Liu, H., 2021b. CO2 capture and Wang, S., Schrunk, E.T., Mahajan, H., Farrauto, a.R.J., 2017. The Role of Ruthenium in
in-situ conversion: recent progresses and perspectives. Green Chemical Engineering CO2 Capture and Catalytic Conversion to Fuel by Dual Function Materials (DFM).
doi:10.1016/j.gce.2021.11.009. Catalysts 7 (12), 88. doi:10.3390/catal7030088.
Sun, H., Wang, J., Zhao, J., Shen, B., Shi, J., Huang, J., Wu, C., 2019. Dual func- Wang, Y., Gao, X., Wu, M., Tsubaki, N., 2021. Thermocatalytic hydrogenation of CO2 into
tional catalytic materials of Ni over Ce-modified CaO sorbents for integrated aromatics by tailor-made catalysts: Recent advancements and perspectives. EcoMat 3
CO2 capture and conversion. Applied Catalysis B: Environmental 244, 63–75. (1), e12080. doi:10.1002/eom2.12080.
doi:10.1016/j.apcatb.2018.11.040. Wang, Y., Memon, M.Z., Xie, Q., Gao, Y., Li, A., Fu, W., Wu, Z., Dong, Y., Ji, G., 2022. Study
Sun, H., Wang, Y., Xu, S., Osman, A.I., Stenning, G., Han, J., Sun, S., Rooney, D., on CO2 sorption performance and sorption kinetics of Ce- and Zr-doped CaO-based
Williams, P.T., Wang, F., Wu, C., 2021. Understanding the interaction between ac- sorbents. Carbon Capture Science & Technology 2. doi:10.1016/j.ccst.2022.100033.
tive sites and sorbents during the integrated carbon capture and utilization process. Xu, Y., Shen, C., Lu, B., Luo, C., Wu, F., Li, X., Zhang, L., 2021. Study on the effect of NaBr
Fuel 286, 119308. doi:10.1016/j.fuel.2020.119308. modification on CaO-based sorbent for CO2 capture and SO2 capture. Carbon Capture
Sun, H., Wu, C., Shen, B., Zhang, X., Zhang, Y., Huang, J., 2018. Progress in the develop- Science & Technology 1. doi:10.1016/j.ccst.2021.100015.
ment and application of CaO-based adsorbents for CO2 capture—a review. Materials Yan, X., Li, Y., Ma, X., Zhao, J., Wang, Z., 2019. Performance of Li4 SiO4 Material for
Today Sustainability 1-2, 1-27. doi:10.1016/j.mtsust.2018.08.001. CO2 Capture: A Review. International Journal of Molecular Sciences 20 (4), 928.
Sun, H., Zhang, Y., Guan, S., Huang, J., Wu, C., 2020. Direct and highly selective con- doi:10.3390/ijms20040928.
version of captured CO2 into methane through integrated carbon capture and uti- Zhang, P., Tong, J., Huang, K., Zhu, X., Yang, W., 2021. The current status of high temper-
lization over dual functional materials. Journal of CO2 Utilization 38, 262–272. ature electrochemistry-based CO2 transport membranes and reactors for direct CO2
doi:10.1016/j.jcou.2020.02.001. capture and conversion. Progress in Energy and Combustion Science 82, 100888.
Sun, H., Zhang, Y., Wang, C., Isaacs, M.A., Osman, A.I., Wang, Y., Rooney, D., Wang, Y., doi:10.1016/j.pecs.2020.100888.
Yan, Z., Parlett, C.M.A., Wang, F., Wu, C., 2022. Integrated carbon capture and utiliza- Zhang, R.-Z., Wu, B.-Y., Li, Q., Lu, L.-L., Shi, W., Cheng, P., 2020. Design strategies and
tion: Synergistic catalysis between highly dispersed Ni clusters and ceria oxygen va- mechanism studies of CO2 electroreduction catalysts based on coordination chemistry.
cancies. Chemical Engineering Journal 437, 135394. doi:10.1016/j.cej.2022.135394. Coordination Chemistry Reviews 422, 213436. doi:10.1016/j.ccr.2020.213436.
Sun, S., Lv, Z., Qiao, Y., Qin, C., Xu, S., Wu, C., 2021a. Integrated CO2 capture and uti- Zhang, W., Hu, Y., Ma, L., Zhu, G., Wang, Y., Xue, X., Chen, R., Yang, S., Jin, Z.,
lization with CaO-alone for high purity syngas production. Carbon Capture Science & 2018. Progress and Perspective of Electrocatalytic CO2 Reduction for Renew-
Technology 1, 100001. doi:10.1016/j.ccst.2021.100001. able Carbonaceous Fuels and Chemicals. Advanced Science 5 (1), 1700275.
Sun, S., Sun, H., Guan, S., Xu, S., Wu, C., 2022. Integrated CO2 capture and methanation doi:10.1002/advs.201700275.
on Ru/CeO2 -MgO combined materials: Morphology effect from CeO2 support. Fuel Zhang, W., Ma, D., Pérez-Ramírez, J., Chen, Z., 2021. Recent Progress in Materials Explo-
317, 123420. doi:10.1016/j.fuel.2022.123420. ration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO2 -
Sun, S., Sun, H., Williams, P.T., Wu, C., 2021b. Recent advances in integrated CO2 to-Fuel Conversion. Advanced Energy and Sustainability Research 3 (2), 2100169.
capture and utilization: a review. Sustainable Energy & Fuels 5 (18), 4546–4559. doi:10.1002/aesr.202100169.
doi:10.1039/d1se00797a. Zhang, Y., Liang, C., Wu, J., Liu, H., Zhang, B., Jiang, Z., Li, S., Xu, P., 2020. Recent
Thema, M., Bauer, F., Sterner, M., 2019. Power-to-Gas: Electrolysis and methana- Advances in Magnetic Field-Enhanced Electrocatalysis. ACS Applied Energy Materials
tion status review. Renewable and Sustainable Energy Reviews 112, 775–787. 3 (11), 10303–10316. doi:10.1021/acsaem.0c02104.
doi:10.1016/j.rser.2019.06.030. Zheng, Q., Farrauto, R., Chau Nguyen, A., 2016. Adsorption and Methanation of Flue
Tian, S., Yan, F., Zhang, Z., Jiang, J., 2019. Calcium-looping reforming of methane real- Gas CO2 with Dual Functional Catalytic Materials: A Parametric Study. Industrial &
izes in situ CO2 utilization with improved energy efficiency. Science Advances 5 (4), Engineering Chemistry Research 55 (24), 6768–6776. doi:10.1021/acs.iecr.6b01275.
eaav5077. doi:10.1126/sciadv.aav5077. Zhou, Z., Sun, N., Wang, B., Han, Z., Cao, S., Hu, D., Zhu, T., Shen, Q., Wei, W., 2020. 2D-
Tollefson, J., Weiss, K.R., 2015. Nations adopt historic global climate accord: agreement Layered Ni-MgO-Al2 O3 Nanosheets for Integrated Capture and Methanation of CO2 .
commits world to holding warming ’well below’ 2[degrees]C. Nature 582, 315–317. ChemSusChem 13 (2), 360–368. doi:10.1002/cssc.201902828.
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Carbon Capture Science & Technology 4 (2022) 100052

Contents lists available at ScienceDirect

Carbon Capture Science & Technology

Full Length Article

Recent Progress in Integrated CO2 Capture and Conversion Process Using

Introduction Institute, 2021). According to the IEA, approximately 20% of anthro-

Fig. 1. Schematic diagram of the ICCC process.

DFMs Operation conditions

10%CO2 / 10%H2 O/N2 90% H2 /N2

Carbon Capture Science & Technology 4 (2022) 100052

DFMs Operation conditions CO2 uptake capacity CH4 yield

Al2 O3 TH100 0.17 87 0.2 –

Carbon Capture Science & Technology 4 (2022) 100052

K (5%) 0.19 100 0.18 94

Carbon Capture Science & Technology 4 (2022) 100052

shown in Fig. 6, Bobadilla et al. (Bobadilla et al., 2016) investigated

DFMs Operation conditions CO2 uptake capacity CO yield

CaO Ni Ce 650°C, 650°C, 14.1 52 7.3 100 (Sun et al.,

5.8%CO2 /5%O2 /4%H2 O/N2

Carbon Capture Science & Technology 4 (2022) 100052

Fig. 6. CO2 capture eﬃciency, conversion, and

DFMs Operation condition CO2 uptake capacity CO2 conv. Yield

MgO Ni (10%) K Al2 O3 650°C, 650°C, 0.2 14 (Al-

The development of DFMs is the cornerstone of the ICCC. DFMs are

Use of Ni-based DFMs for the ICCC-RWGS process

hance the reducibility and activity of Ni at low temperatures. Even in

Use of Ni-based DFMs for the ICCC-DR process

K species was supposed to be crucial to suppress the oxidation of Cu,

Fig. 19. Heterojunction redox mechanism of

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