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 AJAC  Vol.5 No.8 , June 2014
Production of Hydrogen: Photocatalytic Decomposition of Dimethyl Ether over Metal-Promoted TiO2 Catalysts
Abstract: The photo-induced vapor-phase decomposition of dimethyl ether was investigated on Pt metals deposited on pure and N-doped TiO2. Infrared spectroscopic measurements revealed that adsorption of dimethyl ether on TiO2 samples underwent partial dissociation to methoxy species. Illumination of the (CH3)2O-TiO2 and (CH3)2O-M/TiO2 systems led to the conversion of methoxy into adsorbed formate. In the case of metal-promoted TiO2 catalysts, CO bonded to the metals was also detected. Pure titania exhibited a very little photoactivity. Deposition of Pt metals on TiO2 markedly enhanced the extent of photocatalytic decomposition of dimethyl ether to give H2 and CO2 as the major products. A small amount of CO and methyl formate was also identified in the products. The most active metal was the Rh followed by Pd, Ir, Pt and Ru. When the bandgap of TiO2 was lowered by N-doping, the photocatalytic activity of metal/TiO2 catalysts appreciably increased. The effect of metals was explained by a better separation of charge carriers induced by illumination and by enhanced electronic interaction between metal nanoparticles and TiO2.
Cite this paper: Halasi, G. , Schubert, G. and Solymosi, F. (2014) Production of Hydrogen: Photocatalytic Decomposition of Dimethyl Ether over Metal-Promoted TiO2 Catalysts. American Journal of Analytical Chemistry, 5, 455-466. doi: 10.4236/ajac.2014.58054.
References

[1]   Sandstede, G. (1992) Decomposition of Hydrocarbons into Hydrogen and Carbon for the CO2-Free Production of Hydrogen. 9th World Hydrogen Energy Conference, Paris, 22-25 June 1992, 1745.

[2]   Haryanto, A., Fernando, S., Murali, N. and Adhikari, S. (2005) Current Status of Hydrogen Production Techniques by steam Reforming of Ethanol: A Review. Energy Fuels, 19, 2098-2106.
http://dx.doi.org/10.1021/ef0500538

[3]   Muradov, N. (2001) Catalysis of Methane Decomposition over Elemental Carbon. Catalysis Communications, 2, 89-94.
http://dx.doi.org/10.1016/S1566-7367(01)00013-9

[4]   Mariňo, F., Boveri, M., Baronetti, G. and Laborde, M. (2001) Hydrogen Production from Steam Reforming of Bio-ethanol Using Cu/Ni/K/γ-Al2O3 Catalysts. Effect of Ni. International Journal of Hydrogen Energy, 26, 665-668.
http://dx.doi.org/10.1016/S0360-3199(01)00002-7

[5]   Diagne, C., Idriss, H. and Kiennemann, A. (2002) Hydrogen Production by Ethanol Reforming over Rh/CeO2-ZrO2 Catalysts. Catalysis Communications, 3, 565-571.
http://dx.doi.org/10.1016/S1566-7367(02)00226-1

[6]   Ojeda, M. and Iglesia, E. (2009) Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures. Angewandte Chemie International Edition, 48, 4800-4803.
http://dx.doi.org/10.1002/anie.200805723

[7]   Koós, á. and Solymosi, F. (2010) Production of CO-free H2 by Formic Acid Decomposition over MO2C/Carbon Catalysts. Catalysis Letters, 138, 23-27.
http://dx.doi.org/10.1007/s10562-010-0375-3

[8]   Bulushev, D.A., Beloshapkin, S. and Ross, J.R.H. (2010) Hydrogen from Formic Acid Decomposition over Pd and Au Catalysts. Catalysis Today, 154, 7-12.
http://dx.doi.org/10.1016/j.cattod.2010.03.050

[9]   Zhou, X., Huang, Y., Xing, W., Liu, C., Liao, J. and Lu, T. (2008) High-Quality Hydrogen from the Catalyzed Decomposition of Formic Acid by Pd-Au/C and Pd-Ag/C. Chemical Communications, 3540-3542.
http://dx.doi.org/10.1039/b803661f

[10]   Solymosi, F., Koós, á., Liliom, N. and Ugrai, I. (2011) Production of CO-free H2 from Formic Acid. A Comparative Study of the Catalytic Behaviour of Pt Metals on a Carbon Support. Journal of Catalysis, 279, 213-219.
http://dx.doi.org/10.1016/j.jcat.2011.01.023

[11]   Gazsi, A., Bánsági, T. and Solymosi, F. (2011) Decomposition and Reforming of Formic Acid on Supported Au Catalysts: Production of CO-Free H2. Journal of Physical Chemistry C, 115, 15459-15466.
http://dx.doi.org/10.1021/jp203751w

[12]   Linsebigler, A., Lu, G. and Yates, Jr., J.T. (1995) Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results. Chemical Reviews, 95, 735-758.
http://dx.doi.org/10.1021/cr00035a013

[13]   Hoffmann, M.R., Martin, S.T., Choi, W. and Bahnemann, D.W. (1995) Environmental Applications of Semiconductor Photocatalysis. Chemical Reviews, 95, 69-96.
http://dx.doi.org/10.1021/cr00033a004

[14]   Halasi, Gy., Schubert, G. and Solymosi, F. (2012) Photodecomposition of Formic Acid on N-Doped and Metal-Promoted TiO2. Production of CO-Free H2. Journal of Physical Chemistry C, 116, 15396-15405.
http://dx.doi.org/10.1021/jp3030478

[15]   Galvita, V.V., Semin, G.L., Belyaev, V.D., Yurieva, T.M. and Sobyanin, V.A. (2001) Production of Hydrogen from Dimethyl Ether. Applied Catalysis A: General, 216, 85-90.
http://dx.doi.org/10.1016/S0926-860X(01)00540-3

[16]   Takeishi, K. and Suzuki, H. (2004) Steam Reforming of Dimethyl Ether. Applied Catalysis A: General, 260, 111-117.
http://dx.doi.org/10.1016/j.apcata.2003.10.006

[17]   Nishiguchi, T., Oka, K., Matsumoto, T., Kanai, H., Utani, K. and Imamura, S. (2004) Durability of WO3/ZrO2- CuO/CeO2 Catalysts for Steam Reforming of Dimethyl Ether. Applied Catalysis A: General, 301, 66-74.
http://dx.doi.org/10.1016/j.apcata.2005.11.011

[18]   Faungnawakij, K., Tanaka, Y., Shimoda, N., Fukunaga, T., Kawashima, S., Kikuchi, R. and Eguchi, K. (2006) Influence of Solid-Acid Catalysts on Steam Reforming and Hydrolysis of Dimethyl Ether for Hydrogen Production. Applied Catalysis A: General, 304, 40-48.
http://dx.doi.org/10.1016/j.apcata.2006.02.021

[19]   Kawabata, T., Matsuoka, H., Shishido, T., Li, D., Tian, Y., Sano, T. and Takehira, K. (2006) Steam Reforming of Dimethyl Ether over ZSM-5 Coupled with Cu/ZnO/Al2O3 Catalyst Prepared by Homogeneous Precipitation. Applied Catalysis A: General, 308, 82-90.
http://dx.doi.org/10.1016/j.apcata.2006.04.032

[20]   Semelsberger, T.A., Ott, K.C., Borup, R.L. and Greene, H.L. (2005) Generating Hydrogen-Rich Fuel-Cell Feeds from Dimethyl Ether (DME) Using Physical Mixtures of a Commercial Cu/Zn/Al2O3 Catalyst and Several Solid-Acid Catalysts. Applied Catalysis B: Environmental, 65, 291-300.
http://dx.doi.org/10.1016/j.apcatb.2006.02.015

[21]   Fukunaga, T., Ryomon, N. and Shimazo, S. (2008) The Influence of Metals and Acidic Oxide Species on the Steam Reforming of Dimethyl Ether (DME). Applied Catalysis A: General, 348, 193-200.
http://dx.doi.org/10.1016/j.apcata.2008.06.031

[22]   Solymosi, F., Barthos, R. and Kecs-keméti, A. (2008) The Decomposition and Steam Reforming of Dimethyl Ether on Supported Mo2C Catalysts. Applied Catalysis A: General, 350, 30-37.
http://dx.doi.org/10.1016/j.apcata.2008.07.037

[23]   Halasi, Gy., Bánsági, T. and Solymosi, F. (2009) Production of Hydrogen from Dimethyl Ether over Supported Rhodium Catalysts. ChemCatChem, 1, 311-317.
http://dx.doi.org/10.1002/cctc.200900113

[24]   Faungnawakij, K., Shimoda, N., Fukunaga, T., Kikuchi, R. and Eguchi, K. (2009) Crystal Structure and Surface Species of CuFe2O4 Spinel Catalysts in Steam Reforming of Dimethyl Ether. Applied Catalysis B: Environmental, 92, 341-350.
http://dx.doi.org/10.1016/j.apcatb.2009.08.013

[25]   Gazsi, A., Ugrai, I. and Solymosi, F. (2011) Production of Hydrogen from Dimethyl Ether on Supported Au Catalysts. Applied Catalysis A: General, 391, 360-366.
http://dx.doi.org/10.1016/j.apcata.2010.04.054

[26]   Rouhi, A.M. (1995) Underwater Chemistry Creates Massive Sea-Floor Mineral Deposits. Chemical & Engineering News, 73, 37-39.
http://dx.doi.org/10.1021/cen-v073n050.p037

[27]   Fleish, T.H., Basu, A., Gradassi, M.J. and Masin, J.G. (1997) Dimethyl Ether: A Fuel For The 21st Century. Studies in Surface Science and Catalysis, 107, 117-125.
http://dx.doi.org/10.1016/S0167-2991(97)80323-0

[28]   Olah, G.A. and Molnár, á. (2003) Hydrocarbon Chemistry. Wiley, New York.
http://dx.doi.org/10.1002/0471433489

[29]   Kecskeméti, A., Barthos, R. and Solymosi, F. (2008) Aromatization of Dimethyl Ether and Diethyl Ether on Mo2C-Promoted ZSM-5 Catalysts. Journal of Catalysis, 258, 111-120.

[30]   Wu, M.C., Tóth, G., Sápi, A., Leino, A.R., Kónya, Z., Kukovecz, á., Su, W.F. and Kordás, K. (2012) Synthesis and Photocatalytic Performance of Titanium Dioxide Nanofibers and the Fabrication of Flexible Composite Films from Nanofibers. Journal of Nanoscience and Nanotecnology, 12, 1421-1424.
http://dx.doi.org/10.1166/jnn.2012.4655

[31]   Xu, J.H., Dai, W.L., Li, J., Cao, Y., Li, H., He, H. and Fan, K. (2008) Simple Fabrication of Thermally Stable Apertured N-doped TiO2 Microtubes as a Highly Efficient Photocatalyst under Visible Light Irradiation. Catalysis Communications, 9, 146-152.
http://dx.doi.org/10.1016/j.catcom.2007.05.043

[32]   Schubert, G., Bánsági, T. and Solymosi, F. (2013) Photocatalytic Decomposition of Methyl Formate over TiO2-Supported Pt Metals. Journal of Physical Chemistry C, 117, 22797-22804.
http://dx.doi.org/10.1021/jp406840n

[33]   Beebe Jr., T.P., Crowell, J.E. and Yates Jr., J.T. (1988) Reaction of Methyl Chloride with Alumina Surfaces: A Study of the Methoxy Surface Species by Transmission Infrared Spectroscopy. Journal of Physical Chemistry, 92, 1296-1301.
http://dx.doi.org/10.1021/j100316a056

[34]   Chen, J.G., Basu, P., Ballinger, T.H. and Yates Jr., J.T. (1989) A Transmission Infrared Spectroscopic Investigation of the Reaction of Dimethyl Ether with Alumina Surfaces. Langmuir, 5, 352-356.
http://dx.doi.org/10.1021/la00086a011

[35]   Busca, G., Elmi, A.S. and Forzatti, P. (1987) Mechanism of Selective Methanol Oxidation over Vanadium Oxide-Titanium Oxide Catalysts: A FT-IR and Flow Reactor Study. Journal of Physical Chemistry, 91, 5263-5269.
http://dx.doi.org/10.1021/j100304a026

[36]   Solymosi, F. and Pásztor, M. (1986) Infrared Study of the Effect of H2 on CO-Induced Structural Changes in Supported Rh. Journal of Physical Chemistry, 90, 5312-5317.
http://dx.doi.org/10.1021/j100412a081

[37]   Solymosi, F. and Klivényi, G. (1993) HREELS Study of CH3I and CH3 Adsorbed on Rh(111) Surface. Journal of Electron Spectroscopy and Related Phenomena, 64-65, 499-506.
http://dx.doi.org/10.1016/0368-2048(93)80115-3

[38]   Jenner, G. (1995) Homogeneous Catalytic Reactions Involving Methyl Formate. Applied Catalysis A: General, 121, 25-44.
http://dx.doi.org/10.1016/0926-860X(95)85008-2

[39]   Kominami, H., Sugahara, H. and Hashimoto, K. (2010) Photocatalytic Selective Oxidation of Methanol to Methyl Formate in Gas Phase over Titanium(Iv) Oxide in a Flow-Type Reactor. Catalysis Communications, 11, 426-429.
http://dx.doi.org/10.1016/j.catcom.2009.11.014

[40]   Halasi, G., Schubert, G. and Solymosi, F. (2012) Comparative Study on the Photocatalytic Decomposition of Methanol on TiO2 Modified by N and Promoted by Metals. Journal of Catalysis, 294, 199-206.
http://dx.doi.org/10.1016/j.jcat.2012.07.020

[41]   Phillips, K.R., Jensen, S.C., Baron, M., Li, S.C. and Friend, C.M. (2013) Sequential Photo-Oxidation of Methanol to Methyl Formate on TiO2(110). Journal of American Chemical Society, 135, 574-577.
http://dx.doi.org/10.1021/ja3106797

[42]   Connelly, K., Wahab, A.K. and Idriss, H. (2012) Photoreaction of Au/TiO2 for Hydrogen Production from Renewables: A Review on the Synergistic Effect between Anatase and Rutile Phases of TiO2. Materials for Renewable and Sustainable Energy, 1, 3.

[43]   Szabó, Z.G. and Solymosi, F. (1961) Influence of the Defect Structure of Support on the Activity of Catalyst. Actes Du Deuxieme Congres International De Catalyse, Paris, July 1960, 1627-1651.

[44]   Solymosi, F. (1968) Importance of the Electric Properties of Supports in the Carrier Effect. Catalysis Reviews, 1, 233-255.
http://dx.doi.org/10.1080/01614946808064705

 
 
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