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Selective hydrogenation of acetylene on graphene-supported non-noble metal single-atom catalysts

石墨烯负载的非贵金属单原子催化剂的乙炔选择性加氢反应研究

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Abstract

Large-scale production of polyethylene in industry requires efficient elimination of the trace amount of acetylene impurity. Currently, zeolite adsorption or the conversion of acetylene to ethylene via selective semi-hydrogenation on Pd catalysts is the commonly used method. In this work, we investigate the reaction mechanisms of acetylene hydrogenation on defective graphene (DG) supported single-atom catalysts (SACs), M1/SV-G and M1/DV-G (M=Ni, Pd and Pt) using density functional theory (DFT), where SV-G and DV-G represent DG with single and double vacancies, respectively. It is shown that the metal single-atoms (SAs) as well as their different coordination numbers both affect the activity and selectivity of the hydrogenation process. M1/DV-G provides better H2 dissociation ability than M1/SV-G, which accounts for the poor acetylene hydrogenation activity of M1/SV-G. Based on the reaction barriers, Pt1/DV-G and Ni1/DV-G are better catalysts than other systems considered here, with Ni1/DV-G exhibiting high selectivity for the semi-hydrogenation product of acetylene. These results provide insights for the design of highly selective and noble-metal-free SACs for acetylene hydrogenation on carbon materials.

摘要

在工业上批量生产聚乙烯的过程中去除痕量乙炔杂质的常用方法是沸石吸附或钯基催化剂选择性半氢化乙炔生成乙烯. 本文通过密度泛函理论研究了乙炔在缺陷石墨烯负载的单原子催化剂M1/SV-G和M1/DV-G (其中M=Ni, Pd, Pt; SV-G, DV-G分别代表具有单碳缺陷和双碳缺陷的石墨烯)表面上加氢转化为乙烯的反应机理. 研究表明, 金属单原子及其配位环境均会影响加氢过程的活性和选择性. M1/DV-G催化剂比M1/SV-G具有更好的氢分子解离能力, 这是因为M1/DV-G具有较强的乙炔氢化能力. 基于计算得到的加氢能垒, Pt1/DV-G和Ni1/DV-G的催化活性明显优于其他催化剂, 其中Ni1/DV-G催化剂还具有高的乙炔半加氢选择性. 本研究结果为设计以碳材料为载体的、 具有高选择性的非贵金属单原子乙炔氢化催化剂提供了理论基础.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21573286, 21173269, 21576288, U1662104, 21590792 and 91645203), the Ministry of Science and Technology of China (2015AA034603), the Specialized Research Fund for the Doctoral Program of Higher Education (20130007110003), the Science Foundation of China University of Petroleum, Beijing (2462015YQ0304), and Guangdong Provincial Key Laboratory of Catalysis (2020B121201002). The calculations were performed using supercomputers at SUSTech Supercomputer Center and Tsinghua National Laboratory for Information Science and Technology.

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Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum, Beijing, 102249, China

    Hong-Ying Zhuo  (卓红英) & Xin Zhang  (张鑫)

  2. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China

    Hong-Ying Zhuo  (卓红英), Hai Xiao  (肖海) & Jun Li  (李隽)

  3. Shaanxi Key Laboratory of Catalysis, Shaanxi University of Technology, Hanzhong, 723000, China

    Xiaohu Yu  (于小虎) & Qi Yu  (于琦)

  4. Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China

    Jun Li  (李隽)

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  1. Hong-Ying Zhuo  (卓红英)
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Contributions

Author contributions Li J conceived the project; Zhuo HY and Yu X performed the calculations; Zhuo HY and Xiao H wrote the paper; Yu XH, Yu Q, Xiao H, Zhang X and Li J revised the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Hai Xiao  (肖海), Xin Zhang  (张鑫) or Jun Li  (李隽).

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Hong-Ying Zhuo is currently a PhD candidate in Prof. Xin Zhang’s group at China University of Petroleum-Beijing. She got her BSc degree in applied chemistry from Yantai University in 2011, and MSc degree in physical chemistry in 2015. Now, she is also a visiting student in Prof. Jun Li’s group, Tsinghua University (Beijing, China). Her current research interests focus on heterogeneous catalysis through theoretical methods.

Hai Xiao received his PhD degree from California Institute of Technology (Caltech) in 2015. He then continued to work at Caltech as a postdoctoral scholar and later a research scientist from 2015 to 2018. He is now an associate professor at Tsinghua University, and his research interest focuses on the fields of computational chemistry, catalysis and materials science.

Xin Zhang has received his PhD degree in 2006 from Tsinghua University. During 2007–2008, he joined Prof. Avelino Corma Canos’ group at the Instituto de Tecnología Química, Universidad Politécnica de Valencia in Spain (UPV-ITQ) as a postdoctoral fellow. In 2009, he started to work as a professor in the College of Chemical Engineering, China University of Petroleum, Beijing, China. His research focuses on the synthesis, characterization, and catalytic performance of catalysts with novel-structures.

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Zhuo, HY., Yu, X., Yu, Q. et al. Selective hydrogenation of acetylene on graphene-supported non-noble metal single-atom catalysts. Sci. China Mater. 63, 1741–1749 (2020). https://doi.org/10.1007/s40843-020-1426-0

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