High-Density Coordinatively Unsaturated Zn Catalyst for Efficient Alkane Dehydrogenation

Linlin Wang; Hui Wang; Renfei Cheng; Maolin Wang; Xiangbin Cai; Pengju Ren; Dequan Xiao; Ning Wang; Xiao-Dong Wen; Jiangyong Diao; Xiaohui Wang; Ding Ma; Hongyang Liu

doi:10.1021/jacs.3c06311

High-Density Coordinatively Unsaturated Zn Catalyst for Efficient Alkane Dehydrogenation

J Am Chem Soc. 2023 Sep 27;145(38):20936-20942. doi: 10.1021/jacs.3c06311. Epub 2023 Sep 13.

Authors

Linlin Wang¹, Hui Wang^{2

3

4}, Renfei Cheng¹, Maolin Wang⁵, Xiangbin Cai⁶, Pengju Ren^{2

4}, Dequan Xiao⁷, Ning Wang⁶, Xiao-Dong Wen², Jiangyong Diao^{1

8}, Xiaohui Wang^{1

8}, Ding Ma⁵, Hongyang Liu^{1

8}

Affiliations

¹ Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, P. R. China.
² State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan030001, P. R. China.
³ University of Chinese Academy of Sciences, No. 19A Yuquan Road, Beijing 100049, P. R. China.
⁴ National Energy Center for Coal to Liquids, Synfuels China Co., Ltd, Huairou District, Beijing 101400, P. R. China.
⁵ Beijing National Laboratory for Molecular Sciences, New Cornerstone Science Laboratory, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China.
⁶ Department of Physics, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, 999077P. R. China.
⁷ Center for Integrative Materials Discovery, Department of Chemistry and Chemical Engineering, University of New Haven, 300 Boston Post Road, West Haven, Connecticut 06516, United States.
⁸ School of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, P. R. China.

PMID: 37703050
DOI: 10.1021/jacs.3c06311

Abstract

The exploration of non-noble metal catalysts for alkane dehydrogenation and their catalytic mechanisms is the priority in catalysis research. Here, we report a high-density coordinatively unsaturated Zn cation (Zn_cus) catalyst for the direct dehydrogenation (DDH) of ethylbenzene (EB) to styrene (ST). The catalyst demonstrated good catalytic performance (∼40% initial EB conversion rate and >98% ST selectivity) and excellent regeneration ability in the reaction, which is attributed to the high-density (HD) distribution and high-stability structure of Zn_cus active sites on the surface of zinc silicate (HD-Zn_cus@ZS). Density functional theory (DFT) calculations further illustrated the reaction pathway and intermediates, supporting that the Zn_cus sites can efficiently activate the C-H bond of ethyl on ethylbenzene. Developing the high-density Zn_cus catalyst and exploring the catalytic mechanism laid a good foundation for designing practical non-noble metal catalysts.