Porous carbon materials synthesized using IRMOF-3 and furfuryl alcohol as precursor

Pemta Tia Deka and Ratna Ediati

Citation: AIP Conference Proceedings 1718, 100002 (2016); doi: 10.1063/1.4943346

View online: http://dx.doi.org/10.1063/1.4943346
View Table of Contents: http://aip.scitation.org/toc/apc/1718/1
Published by the American Institute of Physics
 Porous Carbon Materials Synthesized Using IRMOF-3
and Furfuryl Alcohol as Precursor
Pemta Tia Deka, Ratna Ediati

Department of Chemistry Institut Teknologi Sepuluh Nopember, Surabaya 60115 Indonesia

*Email: tia.deka12@gmail.com, ratna.ediati@gmail.com

Abstract.: IRMOF-3 crystals have been synthesized using solvothermal method by adding zinc nitrate
hexahydrate with 2-amino-1,4-benzenedicarboxylic acid in N'N-dimethylformamide (DMF) at 100°C
for 24 (note as IR-24) and 72 h (note as IR-72). The obtained crystals were characterized using X-ray
Diffraction (XRD), SEM (Scanning Electron Microscopy) and Scanning Electron Microscopy-Energy
Dispersive X-ray (SEM-EDX), FTIR and Isothermal adsorption-desorption N2. The diffractogram
solids synthesized show characteristic peak at 2θ 6.8, 9.6 and 13.7°. SEM micrograph show cubic shape
of IRMOF-3 crystal. Based on FTIR characterization, IRMOF-3 appear at wavelength (1691,46; 1425,3;
1238,21; 1319,22 dan 3504,42)cm-1. The Isotherm of crystal IRMOF-3 at heating time 24 h and 72 h
are type IV. The surface area of IR-24 and IR-72 are respectively 24,758 m2/g and 29,139 m2/g with its
dominant mesopores. Carbonaceous materials has been successfully synthesized using IR-24, IR-72 and
furfuryl alcohol (FA) as second carbon precursor with variation of carbonation temperature 550, 700
and 850oC. The XRD result from both carbonaceous materials show formation of amorphous carbon
and caharacteristic peak of ZnO oxide. Micrograph SEM show that carbonaceous materials have cubic
shape as IRMOF-3 and SEM-EDX result indicate Zn and nitrogen content of these materials has
decrease until temperature 850oC. Porous carbon using IR-24 and FA (notes as C-24) has increased
surface area with higher carbonation temperature. The highest surface area is 1495,023 m2/g. Total pore
volume and pore size of C-24 from low to high temperature respectively as (0,338;0,539 and 1,598) cc/g
; (0,107; 0,152 and 0,610) cc/g. Porous carbon using IR-72 and FA (notes as C-72) has smaller surface
area than C-24 but its also increased during higher carbonation heating. The highest surface area is
1029,668 m2/g.The total pore volume and pore size of these carbon materials from low to high
temperature respectively as (0,390; 0,727 and 1,345) cc/g and (0,065; 0,157 and 0,381) cc/g.
Carbonaceous materials with high porosity and nitrogen content will be expected increase mechanical
properties and hydrogen storage from these materials.

Keywords: IRMOF-3, furfuryl alcohol, porous carbon materials, carbonation temperature.

INTRODUCTION

Metal organic framework (MOF) is a porous material which consist of organic ligand linked
with metal ion (Zhao [13]). This combination in MOF structure will form variation of crystalline
structures with unique geometry structure, many kind of pore size. MOF have many application such
as catalyst, gas storage, drug delivery and currently is used for template porous carbon materials. The
different type and variation pore size of MOF can facilitates them as carbon precursor materials. MOF
also have large area compare with another porous materials such zeolite, aerogel resolsinol-
formaldehida (RF) and melamin formaldehida. Some MOF that already use as carbon precursor like
composite MOF-5-furfuryl alcohol (Liu et al.,2010 [8]); ZIF-8-furfuryl alcohol (Jiang et.al.,2011
[6]); HKUST-1 (Petit et al.,2011 [8]);IRMOF-3 without furfuryl alcohol (Yang et al.,2011 [15]).
Based on previous experiment, using MOF as carbon precursor is able to produce large surface area
and carbonation temperature can affect to carbon characteristic.
IRMOF-3 or Isoreticular Metal Organic Framework-3 (Zn4O(BDC-NH2)3) is one type of
MOF consisting metal ions Zn as central atom and benzene dicarboxylic (BDC) which has a group-
NH2 as organic ligand. Both of them made linker like a framework formation. The presence of N
atoms in IRMOF-3 can act as active centers of the hydrogen thus increasing the energy storage

5th International Conference and Workshop on Basic and Applied Sciences (ICOWOBAS 2015)
AIP Conf. Proc. 1718, 100002-1–100002-10; doi: 10.1063/1.4943346
© 2016 AIP Publishing LLC 978-0-7354-1364-1/$30.00

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properties associated with its application as a hydrogen storage material (Sankaran and
Viswanathan,2001[12]). Yang et al (2000)[14] done an experiment to increase carbon materials
properties through modified carbon surface with adding metal or metal oxide.
IRMOF-3 already synthesized using solvothermal method by adding reagent Zn(NO3)2.4H2O
and 2-amino-1,4-benzendicarboxylic acid in media dietilformamida (DEF) or dimethyl formamida
(DMF) at 100oC. Heating time that used in some experiment are 15h;18h;24h;48h (Rowsell et al.,
2006 [13]; Sumida et al., 2012 [13]; Gascon et al., 2009 [5]; Yang et al., 2012 [15]; Cao et al.,2011[3];
Phan et al 2012)[10]. In this research, porous carbon materials was prepared using IRMOF-3 and
furfuryl alcohol as precursor. Preparation of porous carbon materials was conduct by Yang et.al
(2012) [15] by calcinate directly IRMOF-3 until temperature 900oC (note as MDC-3). This porous
carbon have hierarchy pore, high porosity and applicated as hydrogen storage materials but it has
some problems like decreasing surface area from IRMOF-3 to MDC-3 (2351 m2/g to 1678 m2/g).
Therefore its important to find another method to increase surface area of carbon template IRMOF-3
by adding second carbon precursor as furfuryl alcohol. In this experiment, IRMOF-3 was synthesized
by adding NH2(BDC) ligand with Zn(NO3)2.6H2O at 100oC for 24h and 72h. After that, porous carbon
materials was synthesized using IRMOF-3 and furfuryl alcohol with variation of carbonation
temperature. All of IRMOF-3 and carbon materials were characterized using XRD, FTIR, SEM and
adsorption-desorption N2.

METHOD

Synthesis of IRMOF-3

IRMOF-3 crystals synthesized using solvothermal method by reacting 0.9683 g Zn (NO3)

.4H2O (Sigma-Aldrich, 99.0%), 0.2293 g of 2-amino-1,4-benzenedicarbocylic acid (Sigma-Aldrich
, 99.0%), and 30 mL of solvent N'N-dimethyl formamide (DMF, Merck, 99.8%) in a sealed reaction
bottle. After that, the mixture was heated at 100°C for 24 and 72 hours. The next step is followed
by cooling and decantation process. Filtrate mixture into the bottle vial accommodated while solid
results during the decantation washed once a day using 30 mL DMF. Subsequently, 50 ml of
chloroform (Merck, 99.9%) was added to previous solution and the mixture allowed to remain joined
crystal solvent for almost 1 day. After that, decant the solution and crystalline solids were washed
again using chloroform once daily for 3 days. Solvent chloroform was removed using vacuum for 3-
4 hours. IRMOF-3 solids are stored in small vials bottles in a nitrogen atmosphere (Sumida et al.,
2010).

Prepare Templated Porous Carbon Materials Using IRMOF-3

Porous carbon materials was synthesized by adding 1 gram IRMOF-3 crystals as first carbon
precursor with 5 ml furfuryl alcohol as second precursor then shake vigorously. After soaked for one
day, solid phase was separated and wash with ethanol. Transfer these materials into quartz boat then
heat it using furnace at 80oC for 24h. Increase the temperature until 150oC 6h and calcinate at 550oC
under nitrogen atmosphere for 4h. This experiment use variation carbonation temperature at (550,700,
and 850) oC. All carbon materials was characterized using XRD, FTIR, SEM, SEM-EDX, and Gas
Sorption Analysis (Almasoudi et al., 2012).

Characterization

XRD patterns of the samples obtained from the XRD-JEOL using Cu Kα radiation (l = 1.5405
Å) at 40 kV and 30 mA, and recorded on a scale of 5-50o 2θ , a scan speed of 0.04 ° / sec. Data
obtained in the form of price 2θ, d spacing and intensity of the diffraction peaks. Identifying
characteristic peak of materials based on molecule vibration using 8400S Shimadzu FTIR. Zeiss
Scanning Electron Microscopy (EVO MA10) equipped with Energy Dispersive X-ray (SEM-EDX)
was used to determine the morphology and elemental content of the surface of the product. Quanta

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chrome gas sorption analyzer, BET and BJH equation was used to measure surface area and pore
characteristic of materials.

RESULTS AND DISCUSSION

Synthesis and Characterization of Crystal IRMOF-3

IRMOF-3 crystal resulted from heating time 24h (Note as IR-24) and 72h (note as IR-72)
have amber color as shown in Figure 1. The crystals stick to the walls and bottom of the bottle
reaction. When the solvent DMF was replaced with chloroform, the resulting filtrate was clear
colored. IR-24 has much crystal weight than IR-72 because increasing heating time, the cyrstal
growth of IRMOF-3 went faster.

Figure 1. Crystal IRMOF-3 Synthesized

Characterization using XRD to determine the crystallinity of synthesized IRMOF-3. 2θ angle used is
5-50o. The resulting XRD pattern of the crystal IRMOF-3 24 and 72 h show the characteristic peak
at 2θ (6.8o, 9.6o and 13.7o). The pattern is suitable with the simulated diffractogram IRMOF-3 (Yim
et al., 2012). The diffractogram of IR-24 and IR-72 are shown in Figure 2.

Figure 2. Diffractogram Pattern of IR-24

FTIR spectra of IR-24 and IR-72 show characteristic peak at wavelength 1595 cm-1 as
stretching vibration C-O, 1369 cm-1 as stretching vibration C-O symmetric, 1500 cm-1 as stretching
vibration C-C aromatic, 3270 cm-1 as stretching vibration N-H, 1200 cm-1 as C-N vibration.
Characterization using SEM to determine the surface morphology of the crystal IRMOF-3. SEM-
EDX can be used to determine the elemental information on the particle surface. Micrograph SEM
showed that the IR-24 and IR-72 crystal has a cubic shape with the largest particle size of 500 nm. In
addition, the surface of the crystal IRMOF-3 from 72h look rough, cracks and no uniform size,

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whereas the surface of IR-24 are smooth and it have uniform size. This is possible because the longer
the time solvothermal, the IRMOF-3 crystals growing imperfect.
SEM results are consistent with studies that have been conducted by Phan et.al., (2012)[10]
on the experiment of synthesis of IRMOF-3 using solvothermal method then applied as a catalyst for
the reaction of Pall-Knor. IRMOF-3 crystal form produced is a cube with crystal size between 400
and 500 nm. Micrograph SEM of IR-24 and IR-72 shown at Figure 3.

Figure 3. Micrograph SEM of IR-24 and IR-72

SEM-EDX characterization showed that both of IRMOF-3 crystal have variation amount of
element such as nitrogen, carbon, oxygen and Zn as shown in Table 1. the longer heating time, the
amount of nitrogen contained IRMOF-3 has decrease. IR-72 have nitrogen 5.35 wt% and IR-24 are
4.27 wt%. This result is similar with experiment report by Roswell et al (2006).[11] IRMOF-3 has
empiric formula Zn4O (C8H5NO4)3 with molecule weight 814,2 g/mol.
Table 1. Percentage Element of IR-24 and IR-72
Element Content (%)
No Sample
C N O Zn
1 IR-24 37,17 04,27 21,95 36,71

2 IR-72 42,46 05,35 25,58 18,82

Gas sorption analyzer was used to measure surface area and pore characteristic of materials.
Based on this characterization, IR-24 and IR-72 subsequently has isothermal adsorption type I and
IV as shown at Figure 4. Adsorption of nitrogen begin at P/Po 0-0.8 indicate microspore and it made
monolayer filled until P/Po 0.8. The sharp curve at P/Po 1 showed many nitrogen adsorb in IRMOF-
3 pore. IR-24 and IR-72 has hysteresis loop at low pressure in desorption process. This phenomenon
indicate both materials has different amount of nitrogen adsorption and desorption lead to mesopore.
Surface ares and pore characteristic was presented in Figure 4 and Table 2. Overall IRMOF-3 has
mesopore and isotherm type I as Rostamnia and Ali (2014); Gascon et al (2009); Britt et al (2010);
Phan et al (2012).

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Figure 4. Isotherm Adsorption-Desorption N2 (a) IR-24 (b) IR-72 Pore Characteristic of IR-24 and
IR-72
Table 2. Pore characteristic
Total Pore Pore radius
Total surface
No Sample Volume (Å)
area (m2/g)
(cc/g)
1 IR-24 24,758 0,212 0,0171
2 IR-72 29, 139 0,184 0,0126

Synthesized Porous Carbon Materials

Synthesized carbon using IR-24 and IR-72 as precursor noted as C-24 and C-72. As describe
in method section, porous carbon materials were prepared using furfuryl alcohol (FA). Impregnation
FA into IR-24 and IR-72 then heating at 80 and 150oC under nitrogen atmosphere to produce
composite followed by carbonaton at 550,700,and 850oC. The carbon materials has weight decrease
from 1 g to 0.447 g. Moiety of organic ligand was converted into carbon and formed CO2, CO and
benzene. At higher carbonation temperature 750oC indicate evaporation of CO2,CO, and Zn.

Characterization of Carbon template IRMOF-3 (C-24 and C-72)

Diffractogram of C-24 an C-72 at various carbonation temperature are shown at Figure 5 and
6. Characteristic peak of IRMOF-3 was dismiss The pattern indicate two broad peak at 2θ = 28° and
44°. These broad peak is related to diffraction peak of graphite carbon. In this experiment, carbonation
temperature gave effect for carbon materials. The intensity of graphite diffraction peak was increased
during higher heating temperature. This condition implies FA were deposited into IRMOF-3 pore
(Jiang et al.,2011). ZnO characteristic peak appear at 2θ = (31,4 ; 34,3; 36,2 and 47,0)o. The highest
carbonation temperature lead to decreasing amount of Zn as showed in diffractogram pattern C-24
and C-72. Zn was evaporate during it’s boiling point is 908oC.

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 Figure 5. Diffractogram Pattern of C-24 at various carbonation

Figure 6. Diffractogram Pattern of C-24 at various carbonation temperature

FTIR spectra of C-24 and C-72 show structure change from precursor then carbon porous
materials. Characteristic peak of IRMOF-3 and furfuryl alcohol was dismiss. Vibration for O-H at
wavelength 3300 cm-1 and 3100 cm-1 indicate C-H vibration from carbon materials. Micrograph SEM
of C-24 and C-72 are show in Figure 7 and 8. This micrograph compared with IRMOF-3 morphology
as precursor. Based on SEM characterization, C-72 has cubic shape similar with C-24 with size 500
μm. Carbon materials indicate preserved cubic shape although following by high carbonation
temperature. This result is consistent with experiment about porous carbon materials using IRMOF-
1 (Yang et al.,2012)[15]. SEM-EDX give result that ZnO oxide still remains in C-24 and C-72. Zn
atom was decrease at the highest temperature. Carbon (C) contained this materials was rising during
increased carbonation temperature. Beside that, nitrogen content from this materials is 5.66%. The
remains nitrogen can help increasing application of C-24 and C-72 as hydrogen storage materials.

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Figure 7. Micrograph of C-24 at various carbonation temperature

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 Figure 8. Micrograph of C-72 at various carbonation temperature

Figure 9 and 10 show the isotherm adsorption-desorption for C-24 and C-72. The isotherm
are all type IV H4. The type IV nature indicate microspore on monolayer at P/Po < 0.4. Increasing
pressure result not sharp curve at P/Po 0.4-1. All carbon material curve show hysteresis as implied
mesopore. Surface area of C-24 higher than C-72 during decreasing number of ZnO. The higher
carbonation temperature also give larger surface area of carbon materials (Xia et al,2011). The
isotherm analysis indicate variation porosity with surface area in the range of 270-1029 m2/g and pore
volume between 0.3-1.3 cc/g as shown in Table 2. The highest surface area reach at 850oC following
with sharp curve.

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 Figure 9. Isothermal adsorption-desorption C-24

Figure 10. Isothermal adsorption-desorption C-72

CONCLUSION

Cyrstal IRMOF-3 successfully synthesized using solvothermal method (note as IR-24 and
IR-72). In summary, this experiment describe an easy method for preparing porous carbon materials
using IRMOF-3 as carbon precursor and furfuryl alcohol as second precursor via liquid
impregnation, polymeration and variation carbonation temperature (550,700 and 850) oC (noted as
C-24 and C-72). Diffractogram pattern showed formation of amorphous carbon and characteristic
peak for ZnO. Micrograph SEM indicate that C-24 and C-72 has cubic shape and SEM-EDX
represent decreasing Zn during higher temperature and nitrogen still remains in carbon materials.
Based on gas sorption analyzer, C-24 850oC reach the highest surface area with microspore dominant.

ACKNOWLEDGEMENTS

This research was supported by Direktorat Jendral Pendidikan tinggi (Dirjen DIKTI) and
chemistry laboratory Tenth Nopember Institute of Technology

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