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Non-noble metal single-atom catalysts with phosphotungstic acid (PTA) support: A theoretical study of ethylene epoxidation

磷钨酸负载的非贵金属单原子催化剂: 乙烯环氧化的理论研究

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Abstract

Geometric and electronic structures of phosphotungstic acid (PTA) supported single transition metal atom (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt) catalysts have been systematically investigated by using the first-principles theoretical methods. Possible reaction mechanism for ethylene epoxidation was explored. The most possible anchoring site for the single transition metal atom is the fourfold hollow site on PTA. As the non-noble metal Fe1-PTA system possesses considerable adsorption energies towards both O2 and C2H4, the strong bonding interaction between Fe1 and PTA cluster was analyzed. It is found that the electron transfers from Fe atom to PTA cluster and strong covalent metal-support interactions (CMSI) between the Fe 3d orbitals and O 2p orbitals of PTA lay the foundation of high stability. The proposed catalytic reaction mechanism for ethylene epoxidation on Fe1- PTA single-atom catalyst (SAC) includes three steps: the O2 adsorbs on Fe1-PTA via electron transfer; the first ethylene attacks the adsorbed O2 molecule on Fe1-PTA followed by the formation of C2H4O; finally, the O atom remained on Fe1-PTA reacts with a second ethylene to form the product and accomplish the catalytic cycle. The Fe1-PTA has high selectivity and catalytic activity for ethylene epoxidation via an Eley–Rideal mechanism with low energy barriers. A potentially competitive pathway for the formation of acetaldehyde is not kinetically favorable. These results provide insights for the development of highly efficient heterogeneous SACs for ethylene epoxidation with non-noble metals.

摘要

基于第一性原理, 本文系统研究了过渡金属单原子(铁, 钴, 镍, 钌, 铑, 钯, 锇, 铱, 铂)负载在磷钨酸(PTA)催化剂上的几何和电子结构, 并进一步研究了乙烯环氧化在铁单原子催化剂上的可能反应机理. 我们发现PTA最可能结合过渡金属单原子的位置是四配位中空位. 乙烯环氧化催化活性的理论计算表明, 非贵金属Fe1-PTA具有可观的吸附能, 这是引发此催化循环的关键物理量. 我们进一步进行了铁单原子和PTA结合的成键分析, 发现电荷从铁单原子转移到PTA团簇, 并且强烈的Fe–O共价金属-载体相互作用(CMSI)是其高稳定性的基础. 在催化剂Fe1-PTA上可能的乙烯环氧化催化机理共包括三步: 1) 氧气分子通过电荷转移吸附在Fe1-PTA 上; 2) 第一个乙烯分子攻击吸附在Fe1-PTA上的氧气分子, 随后形成C2H4O; 3) 表面吸附的氧原子和第二个乙烯分子生成C2H4O, 完成催化循环. 本研究发现, Fe1-PTA对于乙烯环氧化主要通过Eley-Rideal 机理进行. 本工作为发展高效多相非贵金属单原子乙烯环氧化催化剂提供了理论依据.

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Acknowledgements

This work was financially supported by the Na Acknowledgements This work was financially supported by the National Natural Science Foundation of China (21590792, 91426302 and 21433005) to Li J. The support from Guangdong Provincial Key Laboratory of Catalysis (2020B121201002) is also acknowledged. The calculations were performed using supercomputers at Tsinghua National Laboratory for Information Science and Technology. Yu X thanks for the Special Funding for Transformation of Scientific and Technological Achievements in Qinghai Province (2018-GX-101), and the Natural Science Basic Research Program of Shaanxi Province (2019JM-226).

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Authors and Affiliations

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

    Shamraiz Hussain Talib & Jun Li  (李隽)

  2. Shaanxi Key Laboratory of Catalysis and School of Chemical & Environment Sciences, Shaanxi University of Technology, Hanzhong, 723000, China

    Xiaohu Yu  (于小虎)

  3. School of Materials Science and Engineering and Institute of Graphene at Shaanxi Key Laboratory of Catalysis, Shaanxi University of Technology, Hanzhong, 723001, China

    Qi Yu  (于琦)

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

    Sambath Baskaran & Jun Li  (李隽)

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  1. Shamraiz Hussain Talib
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  2. Xiaohu Yu  (于小虎)
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  3. Qi Yu  (于琦)
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  5. Jun Li  (李隽)
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Contributions

Li J designed the research. Talib SH and Yu X performed the calculations. Talib SH, Yu X, Yu Q, Baskaran S, and Li J interpreted the data. Talib SH, Yu X, Yu Q and Li J co-wrote and revised the manuscript.

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Correspondence to Xiaohu Yu  (于小虎) or Jun Li  (李隽).

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The authors declare no conflict of interest.

Shamraiz Hussain Talib is currently a PhD candidate at the Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering, Tsinghua University, under the supervision of Prof. Jun Li. He received his M. Phil degree (majored in chemistry) from the Department of Chemistry, Mohi-Ud-Din Islamic University, AJ&K, Pakistan in 2016. His PhD research focuses on the theoretical investigations on heterogeneous single-atom catalysts.

Xiaohu Yu received his PhD degree from the Institute of Coal Chemistry, Chinese Academy of Sciences in 2013. He did postdoctoral research at Moscow Institute of Physics and Technology from 2013 to 2015. He worked as a visiting scholar in Prof. Jun Li’s group at Tsinghua University from 2019 to 2020. He is now an associative professor at Shaanxi University of Technology. His research interests focus on theoretical inorganic chemistry and computational cataysis science.

Jun Li received his PhD degree from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences in 1992. He did postdoctoral research at the University of Siegen and Ohio State University from 1994 to 1997. He worked as a research scientist at Ohio State University and senior research scientist at the Pacific Northwest National Laboratory from 1997 to 2009. He is now a full professor at Tsinghua University. His research involves theoretical chemistry, heavy-element chemistry, and computational catalysis science.

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Non-noble metal single-atom catalysts with phosphotungstic acid (PTA) support: A theoretical study of ethylene epoxidation

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Talib, S.H., Yu, X., Yu, Q. et al. Non-noble metal single-atom catalysts with phosphotungstic acid (PTA) support: A theoretical study of ethylene epoxidation. Sci. China Mater. 63, 1003–1014 (2020). https://doi.org/10.1007/s40843-020-1399-y

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