Regulating coordination number in atomically dispersed Pt species on defect-rich graphene for n-butane dehydrogenation reaction

Xiaowen Chen; Mi Peng; Xiangbin Cai; Yunlei Chen; Zhimin Jia; Yuchen Deng; Bingbao Mei; Zheng Jiang; Dequan Xiao; Xiaodong Wen; Ning Wang; Hongyang Liu; Ding Ma

doi:10.1038/s41467-021-22948-w

Regulating coordination number in atomically dispersed Pt species on defect-rich graphene for n-butane dehydrogenation reaction

Nat Commun. 2021 May 11;12(1):2664. doi: 10.1038/s41467-021-22948-w.

Authors

Xiaowen Chen^#^{1

2}, Mi Peng^#³, Xiangbin Cai^#⁴, Yunlei Chen^#^{5

6}, Zhimin Jia^{1

2}, Yuchen Deng³, Bingbao Mei⁷, Zheng Jiang⁷, Dequan Xiao⁸, Xiaodong Wen^{5

6}, Ning Wang⁹, Hongyang Liu^{10

11}, Ding Ma¹²

Affiliations

¹ Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, P. R. China.
² School of Materials Science and Engineering, University of Science and Technology of China, Shenyang, P. R. China.
³ Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering and College of Engineering, and BIC-ESAT, Peking University, Beijing, P. R. China.
⁴ Department of Physics and Center for Quantum Materials, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, P. R. China.
⁵ State Key Laboratory of Coal Conversion, Institute Coal Chemistry, Chinese Academy of Sciences, Taiyuan, P. R. China.
⁶ University of Chinese Academy of Science, Beijing, P. R. China.
⁷ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, P. R. China.
⁸ Center for Integrative Materials Discovery, Department of Chemistry and Chemical Engineering, University of New Haven, West Haven, CT, USA.
⁹ Department of Physics and Center for Quantum Materials, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, P. R. China. [email protected].
¹⁰ Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, P. R. China. [email protected].
¹¹ School of Materials Science and Engineering, University of Science and Technology of China, Shenyang, P. R. China. [email protected].
¹² Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering and College of Engineering, and BIC-ESAT, Peking University, Beijing, P. R. China. [email protected].

^# Contributed equally.

Abstract

Metal nanoparticle (NP), cluster and isolated metal atom (or single atom, SA) exhibit different catalytic performance in heterogeneous catalysis originating from their distinct nanostructures. To maximize atom efficiency and boost activity for catalysis, the construction of structure-performance relationship provides an effective way at the atomic level. Here, we successfully fabricate fully exposed Pt₃ clusters on the defective nanodiamond@graphene (ND@G) by the assistance of atomically dispersed Sn promoters, and correlated the n-butane direct dehydrogenation (DDH) activity with the average coordination number (CN) of Pt-Pt bond in Pt NP, Pt₃ cluster and Pt SA for fundamentally understanding structure (especially the sub-nano structure) effects on n-butane DDH reaction at the atomic level. The as-prepared fully exposed Pt₃ cluster catalyst shows higher conversion (35.4%) and remarkable alkene selectivity (99.0%) for n-butane direct DDH reaction at 450 °C, compared to typical Pt NP and Pt SA catalysts supported on ND@G. Density functional theory calculation (DFT) reveal that the fully exposed Pt₃ clusters possess favorable dehydrogenation activation barrier of n-butane and reasonable desorption barrier of butene in the DDH reaction.