MWCNT@MIL-53 (Cr) Nanoporous Composite: Synthesis, Characterization, and Methane Storage Property

Document Type : Original Paper


Research Laboratory of Nanoporous Materials, Faculty of Chemistry, Iran University of Science and Technology, Farjam Street, Narmak, Tehran 16846-13114, Iran


In this paper, porous metal−organic frameworks (MIL-53 [CrIII (OH).{O2C-C6H4-CO2}.{HO2C-C6H4-CO2H}x]) were hydrothermally synthesized and, then, a hybrid composite of these synthesized porous metal−organic frameworks (MOF) with acid-treated multi-walled carbon nanotubes (MWCNTs) was prepared. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmet–Teller (BET), and FT-IR analysis. The X-ray diffraction patterns showed that the structure of MWCNT@MIL-53-Cr nonoporous composite was not disturbed by incorporation of MWCNT in MIL-53-Cr. N2 adsorption – desorption analysis showed that the MIL-53-Cr and MWCNT@MIL-53-Cr nanoporous composite had BET surface areas of 1500m2.g-1 and 1347m2.g-1, respectively. These materials were developed as adsorbents for methane storage at room temperature. The analysis showed about 50% increase in methane storage capacity (from 7.1 to 10.8 mmol.g-1 at 298K and 35bar) for MWCNT@MIL-53-Cr composite. The increment in the CH4 adsorption capacity of MWCNT@MIL-53-Cr nanoporous composite is attributed to the increase in micropore volume of MIL-53-Cr by MWCNT incorporation.


[1] Lozano-Castelló, D., Alcaniz-Monge, J., De la Casa-Lillo, M. A., Cazorla-Amorós, D. and Linares-Solano, A . (2002). “Advances in the study of methane storage in porous carbonaceous materials.” Fuel, Vol. 81, pp.1777-1803.
[2] Yulong, W., Fei, W., Guohua, L., Guoqing, N. and Mingde, Y. (2008). “Methane storage in multi-walled carbon nanotubes at the quantity of 80 g.” Materials Research Bulletin, Vol. 43, pp.1431-1439.
[3] Celzard, A. and Fierro, V. (2005). “Preparing a Suitable Material Designed for Methane Storage: A Comprehensive Report.” Energy & Fuels, Vol. 19, pp. 573-583.
[4] ZareNezhad, B. (2009). “An investigation on the most important influencing parameters regarding the selection of the proper catalysts for Claus SRU converters.” Journal of Industrial and Engineering Chemistry, Vol. 15, pp. 143-147.
[5] Menon, V.C. and Komarneni, S. (1998). “Porous Adsorbents for Vehicular Natural Gas Storage: A Review.” Journal of Porous Materials, Vol. 5, pp. 43-58.
[6] Dong, J., Wang, X., Xu, H., Zhao, Q. and Li, J. (2007). "Hydrogen storage in several microporous zeolites.” International Journal of Hydrogen Energy, Vol. 32, pp. 4998-5004.
[7] Erdogan, F.O. and Kopac, T. (2007). “Dynamic analysis of sorption of hydrogen in activated carbon.” International Journal of Hydrogen Energy, Vol. 32, pp. 3448-3456.
[8] Anbia, M. and Lashgari, M. (2009). “Synthesis of amino-modified ordered mesoporous silica as a new nano sorbent for the removal of chlorophenols from aqueous media.” Chemical Engineering Journal, Vol. 150, pp. 555-560.
[9] Anbia, M. and Moradi, S.E. (2009). “Removal of naphthalene from petrochemical wastewater streams using carbon nanoporous adsorbent.” Applied Surface Science, Vol. 255, pp. 5041-5047.
[10] Anbia, M. and Moradi, S.E. (2009). "Adsorption of naphthalene-derived compounds from water by chemically oxidized nanoporous carbon.” Chemical Engineering Journal, Vol. 148, pp. 452-458.
[11] Anbia, M. and Hoseini, V. (2012). “Enhancement of CO 2 adsorption on nanoporous chromium terephthalate (MIL-101) by amine modification.” Journal of Natural Gas Chemistry, Vol. 21, pp. 339-343.
[12] Anbia, M., Hoseini, V. and Sheykhi, S. (2012). “Sorption of methane, hydrogen and carbon dioxide on metal-organic framework, iron terephthalate (MOF-235).” Journal of Industrial and Engineering Chemistry, Vol. 18, pp. 1149-1152.
[13] Anbia, M., Mohammadi, N. and Mohammadi, K. (2010). “Fast and efficient mesoporous adsorbents for the separation of toxic compounds from aqueous media.” Journal of hazardous materials, Vol. 176, pp. 965-972.
[14] Zhou, W. (2010). “Methane storage in porous metal − organic frameworks: current records and future perspectives.” The Chemical Record, Vol. 10, pp. 200-204.
[15] Klontzas, E., Mavrandonakis, A., Tylianakis, E. and Froudakis, G. E . (2008). “Improving hydrogen storage capacity of MOF by functionalization of the organic linker with lithium atoms.” Nano letters, Vol. 8, pp. 1572-1576.
[16] Kesanli, B., Cui, Y., Smith, M. R., Bittner, E. W., Bockrath, B. C. and Lin, W . (2005). “Highly interpenetrated metal – organic frameworks for hydrogen storage.” Angewandte Chemie International Edition, Vol. 44, pp. 72-75.
[17] Zhou, W., Wu, H., Hartman, M. R. and Yildirim, T . (2007). “Hydrogen and methane adsorption in metal-organic frameworks: a high-pressure volumetric study.” The Journal of Physical Chemistry C., Vol. 111, pp. 16131-16137.
18. Ma, S., Sun, D., Simmons, J. M., Collier, C. D., Yuan, D. and Zhou, H. C. (2008). “Metal-organic framework from an anthracene derivative containing nanoscopic cages exhibiting high methane uptake.” Journal of the American Chemical Society, Vol. 130, pp. 1012-1016.
[19] Wang, X.-S., Ma, S., Rauch, K., Simmons, J. M., Yuan, D., Wang, X . and Zhou, H. C . (2008). “Metal-Organic Frameworks Based on Double-Bond-Coupled Di-Isophthalate Linkers with High Hydrogen and Methane Uptakes.” Chemistry of Materials, Vol. 20, pp. 3145-3152.
[20] Wu, H., Zhou, W. and Yildirim, T. (2009). “High-capacity methane storage in metal-organic frameworks M2 (dhtp): The important role of open metal sites.” Journal of the American Chemical Society, Vol. 131, pp. 4995-5000.
[21] Lee, J.S., Jhung, S. H., Yoon, J. W., Hwang, Y. K. and Chang, J. S . (2009). “Adsorption of methane on porous metal carboxylates.” Journal of Industrial and Engineering Chemistry, Vol. 15, pp. 674-676.
[22] Rowsell, J.L. and Yaghi, O.M. (2005). “Strategies for hydrogen storage in metal-organic frameworks.” Angewandte Chemie International Edition, Vol. 44, pp. 4670-4679.
[23] Senkovska, I. and Kaskel, S. (2008). “High pressure methane adsorption in the metal-organic frameworks Cu 3 (btc) 2, Zn 2 (bdc) 2 dabco, and Cr 3 F (H 2 O) 2 O (bdc) 3.” Microporous and Mesoporous Materials, Vol. 112, pp. 108-115.
[24] Serre, C., Millange, F., Thouvenot, C., Noguès, M., Marsolier, G., Louër, D. and Férey, G . (2002). “Very Large Breathing Effect in the First Nanoporous Chromium (III)-Based Solids: MIL-53 or CrIII (OH)⊙{O2C-C6H4-CO2}⊙{HO2C-C6H4-CO2H} x⊙ H2O y.” Journal of the American Chemical Society, Vol. 124, pp. 13519-13526.
[25] Prestipino, C., Regli, L., Vitillo, J. G., Bonino, F., Damin, A., Lamberti, C. and Bordiga, S . (2006). “Local structure of framework Cu (II) in HKUST-1 metallorganic framework: spectroscopic characterization upon activation and interaction with adsorbates.” Chemistry of materials, Vol. 18, pp. 1337-1346.
Volume 51, Issue 1
June 2017
Pages 21-26
  • Receive Date: 10 June 2016
  • Revise Date: 14 May 2017
  • Accept Date: 14 May 2017
  • First Publish Date: 01 June 2017