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Theoretical insight into methanol steam reforming on indium oxide with different coordination environments

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Abstract

Indium oxide (In2O3) 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 In2O3 are still not fully understood yet. Using density functional theory (DFT) calculation, we systematically investigate the MSR process over a high-index In2O3(211) and a favoured catalytic cycle of MSR is determined. The results show that In2O3(211) possesses excellent dehydrogenation and oxidizing ability, on which CH3OH can readily adsorb on the In4c site and be easily activated by the reactive lattice oxygens, resulting in a total oxidation into CO2 rather than CO, while the H2 formation through surface H–H coupling limits the overall MSR activity because of the strong H adsorption on the two-coordinated lattice O (O2c). Our analyses show that the relatively inert three-coordinated lattice O (O3c) 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 In2O3 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 In2O3 catalysts and some basic structure-activity relations at the atomic scale, could facilitate the rational design of In2O3-based catalysts for MSR by controlling the local coordination environment of surface active sites.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (21333003, 21622305), Young Elite Scientist Sponsorship Program by China Association for Science and Technology (YESS20150131), “Shu Guang” project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation (13SG30), and the Fundamental Research Funds for the Central Universities (WJ616007). We also cordially thank Prof. Huagui Yang and Dr. Xiaohui Liu of East China University of Science and Technology for helpful discussions on the MSR experiment.

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Authors and Affiliations

  1. Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis and Centre for Computational Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Jinglin Wang, Haifeng Wang & P. Hu

  2. School of Chemistry and Chemical Engineering, The Queen’s University of Belfast, Belfast, BT9 5AG, UK

    P. Hu

Authors
  1. Jinglin Wang
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  2. Haifeng Wang
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  3. P. Hu
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Correspondence to Haifeng Wang or P. Hu.

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Wang, J., Wang, H. & Hu, P. Theoretical insight into methanol steam reforming on indium oxide with different coordination environments. Sci. China Chem. 61, 336–343 (2018). https://doi.org/10.1007/s11426-017-9139-x

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  • DOI: https://doi.org/10.1007/s11426-017-9139-x

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