Jin 2018
Jin 2018
Jin 2018
A R T I C L E I N F O A B S T R A C T
Article history:
Received 7 December 2017 Photocatalytic processes are attractive techniques in environmental waste treatment and renewable
Received in revised form 11 May 2018 energy generation. Herein, earth-abundant transition metal (Fe, Cu, or Ni)-impregnated one-dimensional
Accepted 29 May 2018 black TiO2 nanocomposites showed upgraded photocatalytic activities in vapor decomposition and
Available online xxx hydrogen production compared with reference samples. These results were ascribed to enhanced charge-
separation efficiencies, as demonstrated by photoluminescence emission spectroscopy and hydroxyl
Keywords: radical density measurements, and/or enhanced visible-light-absorption efficiencies. The photocatalytic
Earth-abundant metal activities depended on the initial concentration of pollutant and relative humidity in the case of pollutant
Nanostructure
decomposition, whereas they depended on the type and composition of the hole scavenger in the case of
Environmental degradation
hydrogen production.
Photocatalytic hydrogen production
Hole scavenger © 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.
https://doi.org/10.1016/j.jiec.2018.05.046
1226-086X/© 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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JIEC 4030 No. of Pages 7
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generation [15,16]. Upon doping with metal cations, an Metal-impregnated BTNT was prepared by impregnating the
intermediate electronic level is formed in the prohibited band BTNT sample with a metal (Fe, Cu, or Ni). Fe(NO3)39H2O (98%),
of TiO2, which narrows the band gap and thus allows this Cu(NO3) 3H2O (99%), and Ni(NO3)26H2O (99.99%) were utilized as
photocatalyst to effectively absorb visible light. In addition, the the Fe, Cu, and Ni sources, respectively. A specific weight of each
metal dopant impurities can serve as electron traps, which metal source (calculated to give metal-impregnated BTNT samples
suppress the recombination of charge carriers. Therefore, with a metal-to-BTNT loading of 0.01) was added to 10 mL of
impregnation of 1D black TiO2 nanostructures with metals deaerated water and stirred for 2 h, after which 1 g of BTNT powder
may generate unique photocatalysts with enhanced photo- was added and stirred for 2 h. This suspension was kept at 20–25 C
catalytic performance. To address this hypothesis, we investi- for 12 h, dried at 85 C for 10 h, and calcined at 300 C for 2 h. The
gated the photocatalytic activities of metal-impregnated 1D final product was cooled and ground to obtain the metal-
black TiO2 nanostructures for the decomposition of vaporous impregnated BTNT powder. Fe-, Cu-, and Ni-impregnated BTNT
pollutant (1,2,4-trimethyl benzene) under simulated-solar- samples were designated as FeBTNT, CuBTNT, and NiBTNT,
light illumination. Instead of utilizing expensive noble metals, respectively. In addition, NiBTNT samples with Ni-to-BTNT
three earth-abundant transition metals (Fe, Cu, and Ni) were loadings of 0.05, 0.10, and 0.20 were prepared and designated as
used. The target compound was chosen because of its high NiBTNT-0.05, NiBTNT-0.10, and NiBTNT-0.20, respectively.
detection frequency in indoor environments and its hazardous The fabricated materials were characterized using X-ray
properties [17]. diffraction (XRD, Rigaku D/max-2500 diffractometer), high-reso-
Hydrogen is a green energy resource, because its combustion lution transmission electron microscopy (HRTEM, FEI Titan G2
does not generate either CO2 or other toxic pollutants. However, ChemiSTEM Cs Probe TEM), UV-visible spectroscopy (Varian CARY
fossil fuels are generally used for the industrial hydrogen 5G), X-ray photoelectron spectroscopy (XPS, PHI Quantera SXM),
production, which is not environmentally favorable. Alternatively, and photoluminescence (PL) emission spectroscopy (Acton Re-
photocatalytic water splitting for hydrogen production with solar search SpectraPro 2150i). Detailed photocurrent measurement
energy has also received considerable interest as a sustainable procedures are provided in the supplementary content.
green process [18,19]. Photocatalytic hydrogen production can be
performed using a renewable solar energy source. This green Contaminant decomposition test
hydrogen energy can be utilized as a fuel for a variety of hydrogen-
energy systems, such as internal combustion engines in hydrogen- The photocatalytic decomposition of 1,2,4-trimethyl benzene
fueled cars, fuel cells, and thermal power generators. Although using the fabricated photocatalysts under simulated-solar-light
certain amounts of methanol are used for the photocatalytic irradiation was assessed in a continuous flow reactor (effective
hydrogen production, the photocatalytic process still provides volume, 0.21 L) (Supplementary Fig. S1) according to the procedure
more environmental as well as economic benefits than typical used in our previous study [20]. In brief, the interior surface of the
fossil-fuel-based industrial processes. Nevertheless, the use of reactor was covered with a nominal weight of each photocatalyst
expensive noble metals as co-catalysts in many metal oxide- (0.2 mg cm 2) and a daylight lamp was placed inside the reactor.
semiconductor-based photocatalysts has limited their practical The irradiance intensity was recorded as 1.7 mW cm 2 at the
application. Therefore, we investigated photocatalytic hydrogen photocatalyst surface. An ultra-pure air stream was supplied from
production using a low-cost transition metal-impregnated black a compressed gas cylinder and divided into dry and humidity-
TiO2 nanotubes (BTNT) sample under simulated solar irradiation. saturated air stream lines. The humidity was controlled by
For comparison, the photocatalytic activities of reference TiO2 adjusting the mixing ratio of humidity-saturated air to dry air.
particles, BTiO2, TiO2 nanotubes (TNT), and BTNT samples in The humidity-controlled air was delivered to a buffering bottle
pollutant decomposition and/or hydrogen production were also (1 L) to decrease any fluctuation in the air flow and then mixed
evaluated. with 1,2,4-trimethyl benzene in a mixing chamber. The mixed
standard gas, with an initial 1,2,4-trimethylbenzene concentration
Experimental of 10, 20, 40, or 50 ppm, was infused into the photocatalytic reactor.
The control procedures included system cleaning, continuous
Photocatalyst fabrication monitoring of the relative humidity and the adsorption equilibri-
um of 1,2,4-trimethyl benzene, and a photolysis test. The details of
TNT was fabricated from P25 TiO2 powder using a hydrothermal the sampling and analytical methods, along with hydroxyl radical
process. In brief, 1.0 g of P25 TiO2 powder (<20 nm) was added to density measurement methods, are provided in the supplementary
60 mL of deionized water and stirred to obtain a homogeneous material.
solution, after which 21 g of sodium hydroxide was added and
stirred for 20 min. The resulting suspension was transferred to a Hydrogen production test
Teflon bottle vessel, hydrothermally treated at 120 C for 48 h, and
cooled to 20–25 C. This mixture was centrifuged, and the obtained Photocatalytic water splitting for hydrogen evolution was
precipitates were added to 100 mL of 0.1 M hydrochloric acid, performed using a 70 mL Pyrex reactor with a quartz window. A
stirred for 12 h, and washed with distilled water. The washed mixture of Na2S (0.2 M, 15 mL)/sodium sulfite (Na2SO3, 0.2 M,
precipitate was filtered, dried at 85 C for 15 h, and annealed at 15 mL), methanol (30 mL)/distilled water (30 mL), ethanol (30 mL)/
350 C for 1 h to obtain the TNT powder. distilled water (30 mL), or lactic acid (30 mL)/deionized water
BTNT was fabricated by hydrogenating the as-synthesized TNT (30 mL) was transferred into the reactor, and then the synthesized
powder. Briefly, TNT powder was transferred into an alumina boat photocatalyst (30 mg) was added. These solutions were employed
and placed in a tubular electric furnace. Hydrogenation was carried to minimize the backward reaction of H2 and O2 to H2O on the
out by setting the H2 (5%)/Ar flow rate to 500 mL min 1, heating the catalyst surface [18,19]. Subsequently, the mixture was purged for
furnace to 350 C at a rate of 2 C min 1, and then maintaining these 30 min by bubbling pure nitrogen gas and then irradiated at an
conditions for 5 h. The hydrogenated TiO2 was washed with intensity of 1 Sun using a solar simulator with a 300 W xenon lamp.
distilled water, filtered, and dried at 85 C for 6 h to obtain the BTNT Gas samples were collected periodically using a gas-tight syringe
sample. BTiO2 was prepared by hydrogenating P25 TiO2 powder via (500 mL) and analyzed using a gas chromatograph (Shimadzu GC-
the procedure used for BTNT synthesis. 2010) equipped with a capillary column (Carboxen 1010 PLOT).
Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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JIEC 4030 No. of Pages 7
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Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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JIEC 4030 No. of Pages 7
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Fig. 3. (a) Valence-band XPS spectra and (b) band energy diagrams of TiO2, BTNT, FeBTNT, CuBTNT, and NiBTNT.
intensity vs binding energy curve (Fig. 3a), creating narrowed band The UV-visible absorption spectra of TiO2, BTiO2, TNT, BTNT,
gaps in the samples. CuBTNT, FeBTNT, and NiBTNT are displayed in Fig. 4. The
The metal-impregnated BTNT samples were synthesized using absorption spectra of TiO2 and TNT revealed low absorption
a metal doping process. Neither metals nor metal oxides were efficiencies in the visible region. By contrast, the hydrogenated
observed on the surfaces of the metal-impregnated BTNT samples samples exhibited enhanced absorption efficiencies in the visible-
(Fig. 1). The band gaps of the metal-impregnated BTNT samples light range, which were assigned to modified surface properties
were narrower than that of the unmodified BTNT sample (Fig. 3). and electronic structures [3,4,6]. Moreover, the visible-light-
These results were attributed to the formation of intermediate absorption efficiencies of two of the metal-impregnated hydroge-
electronic levels in the metal-impregnated BTNT samples between nated samples (FeBTNT and NiBTNT) were higher than that of the
the conduction and valence bands, likely owing to the presence of bare hydrogenated sample without metal impregnation (BTNT)
the metals as metal ion dopants in the bulk, which modifies the owing to the localized or delocalized electronic states produced by
BNT electronic structure. Consequently, the metals in the metal- the impregnated metals [23–26]. However, CuBTNT had a lower
impregnated BTNT samples are most likely ion dopants in the bulk. visible-light-absorption efficiency than BTNT, probably due to the
Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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JIEC 4030 No. of Pages 7
Y.-J. Jin, W.-K. Jo / Journal of Industrial and Engineering Chemistry xxx (2018) xxx–xxx 5
Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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Fig. 7. Fluorescence spectra of BTiO2, BTNT, and NiBTNT for 2HTPA for three different light illumination times (30, 45, and 60 min).
nanotube-incorporated TiO2 nanofibers under daylight illumina- time-series hydrogen evolution rates for NiBTNT-0.1 with different
tion decreased as the initial concentration increased [32]. types of hole scavengers under simulated-solar-light irradiation. For
Using an initial concentration of 50 ppm, the photocatalytic each hole scavenger (10 vol% in deionized water), the hydrogen
degradation efficiencies of NiBTNT samples with different Ni-to- evolution rate over NiBTNT-0.1 increased gradually as the irradiation
BTNT loadings were determined. The degradation efficiency of the time increased, but varied depending on the type of hole scavenger.
target pollutant increased as the Ni-to-BTNT loading increased In contrast, hydrogen production by BTNT was not detected over the
from 0.01 to 0.1, but decreased when the Ni-to-BTNT loading was 5-h photocatalytic period, regardless of the type of hole scavenger.
increased further to 0.2, indicating an optimal Ni composition for The 5-h average hydrogen evolution rates corresponding to the hole
NiBTNT photocatalysts (Supplementary Fig. S8). The decreased scavengers were in the order of: lactic acid (187 mmol g 1 h 1) >
degradation efficiency of the NiBTNT sample with a Ni-to-BTNT methanol (168 mmol g 1 h 1) > ethanol (128 mmol g 1 h 1) >
loading of 0.2 was ascribed to an increased charge-carrier glycerol (107 mmol g 1 h 1). Similarly, Lingampalli et al. reported
recombination rate owing to the formation of recombination sites that hydrogen yields with ZnO/Pt/CdS under visible-light irradia-
by excess Ni on the catalyst surface. tion depended on the type of hole scavenger. These results
demonstrated that the type of hole scavenger is an important
Photocatalytic hydrogen generation factor in photocatalytic hydrogen evolution processes [33].
Fig. 9 exhibits the time-series hydrogen evolution rates for
Photocatalytic hydrogen evolution procedures were carried out NiBTNT-0.1 according to the volume of lactic acid in deionized
using NiBTNT-0.1, as this sample exhibited the highest 1,2,4- water under simulated-solar-light irradiation. The 5-h average
trimethyl benzene decomposition efficiency. Fig. 8 displays the hydrogen evolution rates increased from 126 to 187 mmol g 1 h 1
Fig. 8. Time-series hydrogen evolution rates (mmol g-1) by BTNT and NiBTNT-0.1 Fig. 9. Time-series hydrogen evolution rates (mmol g-1) by NiBTNT-0.1 according to
according to the type of hole scavenger (methanol (10%), ethanol (10%), lactic acid volume percentage of lactic acid to deionized water (5, 10, 15, and 20%) under
(10%), and glycerol (10%) under simulated solar light irradiation. simulated solar light irradiation.
Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046
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JIEC 4030 No. of Pages 7
Y.-J. Jin, W.-K. Jo / Journal of Industrial and Engineering Chemistry xxx (2018) xxx–xxx 7
Acknowledgements
Disclosure statement
Fig. 10. Schematic band structures of TiO2 and NiBTNT, and the reduction–
oxidation. The author declares that no conflicting actual or potential
interests exist.
as the amount of lactic acid increased from 5 to 10 vol%; however,
the rates decreased to 145 and 50 mmol g 1 h 1 upon further Appendix A. Supplementary data
increasing the lactic acid amount to 15 and 20 vol%, respectively,
indicating the optimal amount of lactic acid for photocatalytic Supplementary data associated with this article can be found, in
hydrogen evolution over NiBTNT-0.1. Other research groups have the online version, at https://doi.org/10.1016/j.jiec.2018.05.046.
used lactic acid concentrations of 10–90 vol% for photocatalytic
hydrogen generation [34,35]. Specifically, Chen et al. [34] added a References
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Please cite this article in press as: Y.-J. Jin, W.-K. Jo, Upgraded organic vapor treatment and hydrogen generation using low-cost metal/1D black
titania nanocomposites under simulated solar irradiation, J. Ind. Eng. Chem. (2018), https://doi.org/10.1016/j.jiec.2018.05.046