Abstract
The reaction of ultrafine spherical β-MoO3 powders with CO or the mixed CO-CO2 gases by the temperature-programmed reaction (TPR) method is investigated in order to produce Mo2C. From the experimental results, it is concluded that the reaction process between MoO3 and CO is composed of two stages: the reduction of MoO3 to MoO2 and the carburization from MoO2 to Mo2C. Mo4O11 as an intermediate product is formed during the first reduction stage (from MoO3 to MoO2), which is similar to the reduction process of MoO3 to MoO2 by H2. The product Mo2C always keeps the same platelet-shaped morphology as that of MoO2. In addition, it is found that adding a certain proportion of CO2 into the reducing gases has a large inhibiting effect on the carbon deposition reaction of CO, which is beneficial for the preparation of pure Mo2C. However, if the proportion of CO2 is too high, Mo2C cannot be obtained and the product will turn to be MoO2 instead.
Similar content being viewed by others
References
Levy, R., Boudart, M.: Platinum-like behavior of tungsten carbide in surface catalysis. Science. 181, 547–549 (1973)
Torabi, O., Golabgir, M.H., Tajizadegan, H., Torabi, H.: A study on mechanochemical behavior of MoO3-Mg-C to synthesize molybdenum carbide. Int J Refract Met Hard Mater. 47, 18–24 (2014)
Volpe, L., Boudart, M.: Compounds of molybdenum and tungsten with high specific surface area: I. Nitrides J Solid State Chem. 59(3), 332–347 (1985)
Chaudhury, S., Mukerjee, S., Vaidya, V., Venugopal, V.: Kinetics and mechanism of carbothermic reduction of MoO3 to Mo2C. J Alloy Compd. 261, 105–113 (1997)
Dhandapani, B., Clair, T.S., Oyama, S.: Simultaneous hydrodesulfurization, hydrodeoxygenation, and hydrogenation with molybdenum carbide. Appl Catal. 168(2), 219–228 (1998)
Choi, J.G., Brenner, J.R., Thompson, L.T.: Pyridine hydrodenitrogenation over molybdenum carbide catalysts. J Catal. 154(1), 33–40 (1995)
Markel, E., Van, Z.J.: Catalytic hydrodesulfurization by molybdenum nitride. J Catal. 126(2), 643–657 (1990)
Ranhotra, G., Bell, A., Reimer, J.: Catalysis over molybdenum carbides and nitrides: II. Studies of CO hydrogenation and C2H6 hydrogenolysis. J Catal. 108(1), 40–49 (1987)
Vo, D.V.N., Adesina, A.A.: Fischer–Tropsch synthesis over alumina-supported molybdenum carbide catalyst. Appl Catal. 399(1), 221–232 (2011)
Park, K.Y., Seo, W.K., Lee, J.S.: Selective synthesis of light olefins from syngas over potassium-promoted molybdenum carbide catalysts. Catal Lett. 11(3), 349–356 (1991)
Keller, V., Wehrer, P., Garin, F., Ducros, R., Maire, G.: Catalytic activity of bulk tungsten carbides for alkane reforming: I. Characterization and catalytic activity for reforming of hexane isomers in the absence of oxygen. J Catal. 153(1), 9–16 (1995)
Brungs, A.J., York, A.P., Green, M.L.: Comparison of the group V and VI transition metal carbides for methane dry reforming and thermodynamic prediction of their relative stabilities. Catal Lett. 57(1), 65–69 (1999)
Brungs, A.J., York, A.P., Claridge, J.B., Márquez-Alvarez, C., Green, M.L.: Dry reforming of methane to synthesis gas over supported molybdenum carbide catalysts. Catal Lett. 70(3), 117–122 (2000)
LaMont, D.C., Thomson, W.J.: Dry reforming kinetics over a bulk molybdenum carbide catalyst. Chem Eng Sci. 60(13), 3553–3559 (2005)
York, A.E., Claridge, J., Brungs, A., Tsang, S., Green, M.H.: Molybdenum and tungsten carbides as catalysts for the conversion of methane to synthesis gas using stoichiometric feedstocks. Chem Commun. 1, 39–40 (1997)
Bouchy, C., SBD-A, H., Derouane, E.G.: A new route to the metastable FCC molybdenum carbide α-MoC1 − x. Chem Commun. 2, 125–126 (2000)
Volpe, L., Boudart, M.: Compounds of molybdenum and tungsten with high specific surface area: II. Carbides J Solid State Chem. 59(3), 348–356 (1985)
Xiao, T., York, A.P., Coleman, K.S., Claridge, J.B., Sloan, J., Charnock, J., Green, M.L.: Effect of carburising agent on the structure of molybdenum carbides. J Mater Chem. 11(12), 3094–3098 (2001)
Xiao, T.C., York, A.P., Williams, V.C., Al-Megren, H., Hanif, A., Zhou, X.Y., Green, M.L.: Preparation of molybdenum carbides using butane and their catalytic performance. Chem Mater. 12(12), 3896–3905 (2000)
Hanif, A., Xiao, T., York, A.P., Sloan, J., Green, M.L.: Study on the structure and formation mechanism of molybdenum carbides. Chem Mater. 14(3), 1009–1015 (2002)
Wang, X.H., Hao, H.L., Zhang, M.H., Li, W., Tao, K.Y.: Synthesis and characterization of molybdenum carbides using propane as carbon source. J Solid State Chem. 179(2), 538–543 (2006)
Liang, C., Ying, P., Li, C.: Nanostructured β-Mo2C prepared by carbothermal hydrogen reduction on ultrahigh surface area carbon material. Chem Mater. 14(7), 3148–3151 (2002)
Mordenti, D., Brodzki, D., Djéga, M.G.: New synthesis of Mo2C 14 nm in average size supported on a high specific surface area carbon material. J Solid State Chem. 141(1), 114–120 (1998)
Yang, Z., Cai, P., Shi, L., Gu, Y., Chen, L., Qian, Y.: A facile preparation of nanocrystalline Mo2C from graphite or carbon nanotubes. J Solid State Chem. 179(1), 29–32 (2006)
Patel, M., Subrahmanyam, J.: Synthesis of nanocrystalline molybdenum carbide (Mo2C) by solution route. Mater Res Bull. 43(8), 2036–2041 (2008)
Wang, H., Wang, Z., Chen, S.: Preparation of molybdenum carbides with multiple morphologies using surfactants as carbon sources. J Solid State Chem. 194, 19–22 (2012)
Khabbaz, S., Honarbakhsh, R.A., Ataie, A., Saghafi, M.: Effect of processing parameters on the mechanochemical synthesis of nanocrystalline molybdenum carbide. Int J Refract Met Hard Mater. 41, 402–407 (2013)
Hoseinpur, A., Jalaly, M., Bafghi, M.S., Khaki, J.V.: On the formation of Mo2C nanocrystals by a novel system through microwave assisted combustion synthesis. Mater Charact. 108, 79–84 (2015)
Vitale, G., Guzmán, H., Frauwallner, M.L., Scott, C.E., Pereira, A.P.: Synthesis of nanocrystalline molybdenum carbide materials and their characterization. Cataly Today. 250, 123–133 (2015)
Dang, J., Zhang, G.H., Wang, L., Chou, K.C., Pistorius, P.C.: Study on reduction of MoO2 powders with CO to produce Mo2C. J Am Ceram Soc. 99(3), 819–824 (2016)
Wang, Z.Q., Zhang, Z.B., Zhang, M.H.: The efficient synthesis of a molybdenum carbide catalyst via H2-thermal treatment of a Mo(vi)-hexamethylenetetramine complex. Dalton Trans. 40(5), 1098–1104 (2011)
Lemaître, J., Vidick, B., Delmon, B.: Control of the catalytic activity of tungsten carbides: I. Preparation of highly dispersed tungsten carbides. J Catal. 99(2), 415–427 (1986)
Alonso, F.N., Morales, M.Z., Salas, A.U., Becerril, J.B.: Tungsten trioxide reduction-carburization with carbon monoxide-carbon dioxide mixtures: kinetics and thermodynamics. Int J Miner Process. 20, 137–151 (1987)
Valendar, H.M., Yu, D., Barati, M., Rezaie, H.: Isothermal kinetics of reduction and carburization of WO3–NiO nanocomposite powder by CO/CO2. J Therm Anal Calorim. 128(1), 553–566 (2017)
Wang, L., Zhang, G.H., Sun, Y.J., Zhou, X.W., Chou, K.C.: Preparation of ultrafine β-MoO3 from industrial grade MoO3 powder by the method of sublimation. J Phys Chem C. 120(35), 19821–19829 (2016)
Wang, L., Zhang, G.H., Chou, K.C.: Preparation of single-crystal spherical γ-Mo2N by temperature-programmed reaction between β-MoO3 and NH3. J Solid State Chem. 254, 96–102 (2017)
McCarron, E.: β-MoO3: a metastable analogue of WO3. J Chem Soc Chem Commun. 4(4), 336–338 (1986)
Sayede, A., Amriou, T., Pernisek, M., Khelifa, B., Mathieu, C.: An ab initio LAPW study of the α and β phases of bulk molybdenum trioxide, MoO3. Chem Phys. 316(1), 72–82 (2005)
Phuc, N.H.H., Ohkita, H., Mizushima, T., Kakuta, N.: Simple method to prepare new structure of metastable molybdenum (VI) oxide. Mater Lett. 76, 173–176 (2012)
Dang, J., Zhang, G.H., Chou, K.C.: Phase transitions and morphology evolutions during hydrogen reduction of MoO3 to MoO2. High Temp Mater Process. 51, 275–281 (2014)
Wang, L., Zhang, G.H., Chou, K.C.: Mechanism and kinetic study of hydrogen reduction of ultra-fine spherical MoO3 to MoO2. Int J Refract Met Hard Mater. 54, 342–350 (2016)
Ma, L., Ting, L.R.L., Molinari, V., Giordano, C., Yeo, B.S.: Efficient hydrogen evolution reaction catalyzed by molybdenum carbide and molybdenum nitride nanocatalysts synthesized via the urea glass route. J Mater Chem A. 3(16), 8361–8368 (2015)
Dang, J., Zhang, G.H., Chou, K.C., Reddy, R.G., He, Y., Sun, Y.J.: Kinetics and mechanism of hydrogen reduction of MoO3 to MoO2. Int J Refract Met Hard Mater. 41, 216–223 (2013)
Schulmeyer, W.V., Ortner, H.M.: Mechanisms of the hydrogen reduction of molybdenum oxides. Int J Refract Met Hard Mater. 20(4), 261–269 (2002)
Bale, C., Chartrand, P., Degterov, S., Eriksson, G., Hack, K., Mahfoud, R.B., Melançon, J., Pelton, A., Petersen, S.: FactSage thermochemical software and databases. Calphad. 26(2), 189–228 (2002)
Utigard, T.: Oxidation mechanism of molybdenite concentrate. Metall Mater Trans B Process Metall Mater Process Sci. 40(4), 490–496 (2009)
Wang, L., Zhang, G.H., Chou, K.C.: Study on oxidation mechanism and kinetics of MoO2 to MoO3 in air atmosphere. Int J Refract Met Hard Mater. 57, 115–124 (2016)
Acknowledgements
The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (U1460201).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wang, L., Zhang, GH. & Chou, KC. Preparation of Mo2C by reducing ultrafine spherical β-MoO3 powders with CO or CO-CO2 gases. J Aust Ceram Soc 54, 97–107 (2018). https://doi.org/10.1007/s41779-017-0131-x
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s41779-017-0131-x