A novel synthesis route to obtain highly dispersed molybdenum carbides in porous silica is described. The synthesis was carried out by a single-step heat treatment of molybdenum-containing and methyl-modified silica ...A novel synthesis route to obtain highly dispersed molybdenum carbides in porous silica is described. The synthesis was carried out by a single-step heat treatment of molybdenum-containing and methyl-modified silica （Mo-M-SiO2） in argon atmosphere at 973 K. Mo-M-SiO2 precursor was facilely obtained via a one-pot synthesis route, using （NH4）6Mo7O24 4H2O （AHM） as molybdenum sources and polymethylhydrosiloxane （PMHS） as silica sources at the initial synthetic step. The optimal C/Mo molar ratio in reaction system for complete carburization of molybdenum species was 7. The carburization process of molybdenum species followed a nontopotactic route involving a MoO2 intermediate phase, which was evidenced by XRD, N2 adsorption-desorption and in situ XPS. Formation mechanism of Mo-M-SiO2 precursor was also proposed by observation of the reaction between AHM and PMHS with TEM. Furthermore, by adding TEOS into silica sources and adjusting TEOS/PMHS mass ratio, crystal phase of molybdenum carbides transferred from β-Mo2C to α-MoC1-x, and SiO2 structure changed from microporous to micro/mesoporous. Catalytic performances of samples were tested using CO hydrogenation as a probe reaction. The supported molybdenum carbides exhibited high selectivity for higher alcohol synthesis compared with bulk β-Mo2C and α-MoC1-x.展开更多
基金supported by the National Natural Science Foundation of China (No. 200573128)the Natural Science Foundation of Shanxi Province, China (No. 20051025)the Natural Science Foundation for Young Scientists of Shanxi Province, China (No. 2006021031)
文摘A novel synthesis route to obtain highly dispersed molybdenum carbides in porous silica is described. The synthesis was carried out by a single-step heat treatment of molybdenum-containing and methyl-modified silica （Mo-M-SiO2） in argon atmosphere at 973 K. Mo-M-SiO2 precursor was facilely obtained via a one-pot synthesis route, using （NH4）6Mo7O24 4H2O （AHM） as molybdenum sources and polymethylhydrosiloxane （PMHS） as silica sources at the initial synthetic step. The optimal C/Mo molar ratio in reaction system for complete carburization of molybdenum species was 7. The carburization process of molybdenum species followed a nontopotactic route involving a MoO2 intermediate phase, which was evidenced by XRD, N2 adsorption-desorption and in situ XPS. Formation mechanism of Mo-M-SiO2 precursor was also proposed by observation of the reaction between AHM and PMHS with TEM. Furthermore, by adding TEOS into silica sources and adjusting TEOS/PMHS mass ratio, crystal phase of molybdenum carbides transferred from β-Mo2C to α-MoC1-x, and SiO2 structure changed from microporous to micro/mesoporous. Catalytic performances of samples were tested using CO hydrogenation as a probe reaction. The supported molybdenum carbides exhibited high selectivity for higher alcohol synthesis compared with bulk β-Mo2C and α-MoC1-x.
