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Density Functional Study of Catalytic Activity of Cu12TM for Water Gas Shift Reaction

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Abstract

Based on density functional theory calculations, we have systematically studied the WGS reaction on various nanosized Cu12TM of Co, Ni, Cu (from the 3d row), Rh, Pd, Ag (from the 4d row), Ir, Pt, Au (from the 5d row). The reaction mechanism proposed by Langmuir–Hinshelwood has been followed, which corresponds to \({\text{CO* + OH* }} \to {\text{COOH*}} \to {\text{CO}}_{2} {\text{ + H*}}\). The comparison of the Gibbs free energy profiles of carboxyl mechanism on different Cu12TM systems concludes that WGS reaction is determined by the steps of H2 forming and OH* reacting with CO* to form COOH*. BEP relationship between activation barriers (Ea) and reaction energies (ΔH) on a series of Cu12TM clusters is very good. What’s more, the activation barrier of rate-determining step of Cu12Au is the smallest. TOF, with the aid of An Energetic Span Model (ESM), is used to estimate the efficiency of the different Cu12TM clusters. The results show that the values of TOFs in doping Cu12Rh, Cu12Ir and Cu12Pt are smaller than that in pure Cu. Moreover, the values of TOFs in doping Cu12Co, Cu12Ni, Cu12Pd, Cu12Ag, and Cu12Au are higher than that in Cu13. The higher value of TOF, the more favorable catalysts they are. This results shoud be helpful in developing efficient catalysts for WGS reaction. Finally, d-band center is used to explain the binding energy of CO and H2O. It shows that there is a good liner relationship between d-band center and binding energy of CO but not for H2O.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant No. 20603021), the Natural Science Foundation of Shanxi (Grant No. 2013011009-6), the High School 131 Leading Talent Project of Shanxi, Undergraduate Training Programs for Innovation and Entrepreneurship of Shanxi Province (Grant Nos. 2013145 and 2015537) and Shanxi Normal University (SD2015CXXM-80).

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Authors and Affiliations

  1. School of Chemistry and Material Science, School of Modern Arts and Sciences, Shanxi Normal University, Linfen, 041004, China

    Zhaoru Cao, Ling Guo, Naying Liu, Xiaoyu An & Aixia Li

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  1. Zhaoru Cao
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  2. Ling Guo
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  3. Naying Liu
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  4. Xiaoyu An
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  5. Aixia Li
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Correspondence to Ling Guo.

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Cao, Z., Guo, L., Liu, N. et al. Density Functional Study of Catalytic Activity of Cu12TM for Water Gas Shift Reaction. Catal Surv Asia 20, 63–73 (2016). https://doi.org/10.1007/s10563-015-9207-1

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