Indium oxide(In_2O_3) has demonstrated to be an effective non-noble metal catalyst for methanol steam reforming reaction(MSR).However, the reaction mechanism of MSR and crucial structure-activity relations determining...Indium oxide(In_2O_3) has demonstrated to be an effective non-noble metal catalyst for methanol steam reforming reaction(MSR).However, the reaction mechanism of MSR and crucial structure-activity relations determining the catalytic performance of In_2O_3 are still not fully understood yet. Using density functional theory(DFT) calculation, we systematically investigate the MSR process over a high-index In_2O_3(211) and a favoured catalytic cycle of MSR is determined. The results show that In_2O_3(211) possesses excellent dehydrogenation and oxidizing ability, on which CH_3 OH can readily adsorb on the In4 c site and be easily activated by the reactive lattice oxygens, resulting in a total oxidation into CO_2 rather than CO, while the H_2 formation through surface H–H coupling limits the overall MSR activity because of the strong H adsorption on the two-coordinated lattice O(O_(2c)). Our analyses show that the relatively inert three-coordinated lattice O(O_(3c)) could play an important catalytic role. To uncover the influence of the local coordination of surface In atoms and lattice O on the catalytic activity, we evaluate the activity trend of several types of In_2O_3 surfaces including(211),(111), and(100) by examining the rate-limiting, which reveals the following activity order:(211)>(111)>(100). These findings provide an in-depth understanding on the MSR reaction mechanism over In_2O_3 catalysts and some basic structure-activity relations at the atomic scale, could facilitate the rational design of In_2O_3-based catalysts for MSR by controlling the local coordination environment of surface active sites.展开更多
基金supported by the National Natural Science Foundation of China(21333003,21622305)Young Elite Scientist Sponsorship Program by China Association for Science and Technology(YESS20150131)+1 种基金"Shu Guang"project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(13SG30)the Fundamental Research Funds for the Central Universities(WJ616007)
文摘Indium oxide(In_2O_3) has demonstrated to be an effective non-noble metal catalyst for methanol steam reforming reaction(MSR).However, the reaction mechanism of MSR and crucial structure-activity relations determining the catalytic performance of In_2O_3 are still not fully understood yet. Using density functional theory(DFT) calculation, we systematically investigate the MSR process over a high-index In_2O_3(211) and a favoured catalytic cycle of MSR is determined. The results show that In_2O_3(211) possesses excellent dehydrogenation and oxidizing ability, on which CH_3 OH can readily adsorb on the In4 c site and be easily activated by the reactive lattice oxygens, resulting in a total oxidation into CO_2 rather than CO, while the H_2 formation through surface H–H coupling limits the overall MSR activity because of the strong H adsorption on the two-coordinated lattice O(O_(2c)). Our analyses show that the relatively inert three-coordinated lattice O(O_(3c)) could play an important catalytic role. To uncover the influence of the local coordination of surface In atoms and lattice O on the catalytic activity, we evaluate the activity trend of several types of In_2O_3 surfaces including(211),(111), and(100) by examining the rate-limiting, which reveals the following activity order:(211)>(111)>(100). These findings provide an in-depth understanding on the MSR reaction mechanism over In_2O_3 catalysts and some basic structure-activity relations at the atomic scale, could facilitate the rational design of In_2O_3-based catalysts for MSR by controlling the local coordination environment of surface active sites.
