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Methane activation on nickel oxide clusters with a concerted mechanism: a density functional theory study of the effect of silica support

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Abstract

The support effect is an important issue in heterogeneous catalysis. A systematic density functional theory (DFT) study was performed to investigate the support effect of a silica model on the initial step of methane activation on NixOx (x =2,3) clusters with a concerted mechanism. Four reactions were examined by exploring their potential energy surfaces (PES): CH4 reacting with unsupported Ni2O2, with silica-supported Ni2O2, with unsupported Ni3O3, and with silica-supported Ni3O3. For each reaction, PES with different spin states were explored. For CH4 activation taking place via a concerted mechanism, the reaction barriers in terms of free energy and reaction free energy increased with the involvement of the model silica support. Only one PES made a major contribution to the overall reaction rate of all four reactions examined. No spin transition process was required for the reactions to undergo their most-favorable pathway from their starting reactants. These results provide a deeper insight into the support effect on C–H bond activation of small alkanes in general, and of methane in particular, on supported transition metal catalysts.

Different reaction behaviors of CH4 on nickel oxide clusters at the absence and presence of silica support

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Notes

  1. \( \frac{k_{\mathrm{supported}}}{k_{\mathrm{unsupported}}}= \exp \left(\frac{G_{\mathrm{unsupported}}-{G}_{\mathrm{supported}}}{\mathrm{RT}}\right) \), where R = 8.314 J mol−1 K−1 and T = 873.15 K. For Reactions A and B, G unsupported − G supported = 12.7 kcal mol−1 (see Figs. 2, 3). For Reactions C and D, G unsupported − G supported = 7.1 kcal mol−1 (see Figs. 4, 5).

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Acknowledgments

Support from the National Natural Science Foundation of China (21306230, 21203250, 21203251), Shandong Province Natural Science Foundation (ZR2014BM002, ZR2012BQ020), and the Fundamental Research Funds for the Central Universities to XFL (15CX08010A) are gratefully acknowledged. Prof. Guo (Taiyuan University of Technology) provided much appreciated help with calculations related to GD3 corrections.

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Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao, 266580, People’s Republic of China

    Yanyan Xi, Xufeng Lin, Chuangye Wang & Hui Fu

  2. College of Chemical Engineering, China University of Petroleum (East China), Qingdao, 266580, People’s Republic of China

    Yanyan Xi

  3. College of Science, China University of Petroleum (East China), Qingdao, 266580, People’s Republic of China

    Bili Chen, Xufeng Lin, Chuangye Wang & Hui Fu

  4. Key Laboratory of Catalysis of China National Petroleum Corporation, China University of Petroleum (East China), Qingdao, 266580, People’s Republic of China

    Xufeng Lin

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Correspondence to Xufeng Lin.

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Xi, Y., Chen, B., Lin, X. et al. Methane activation on nickel oxide clusters with a concerted mechanism: a density functional theory study of the effect of silica support. J Mol Model 22, 79 (2016). https://doi.org/10.1007/s00894-016-2947-7

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