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Coordination structure dominated performance of single-atomic Pt catalyst for anti-Markovnikov hydroboration of alkenes

配位结构主导单原子Pt的烯烃反马氏硼氢化催化 性能

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Abstract

The rational design of efficient single-atomic (SA) catalysts is essential and highly desirable but impeded by the lack of sufficient acknowledge between structure and property. To this end, it is critical to clarify the effect of the coordination structure of active metal centers on the catalytic activities for the design of such catalysts. Here, we report that different coordination structures of SA Pt catalysts can dramatically influence their activities for anti-Markovnikov hydroboration of alkenes. Compared with the other two coordination structures (Pt-N4 and Pt-O2), the SA Pt species coordinated with three O atoms (Pt-O3) display the highest turnover number value of 3288 for the hydroboration reaction to access the important alkylboronic esters. Density functional theory calculations reveal that a superior catalytic activity can be expected for alkene hydroboration over the three O coordinated Pt species due to the lowest reaction energy (ΔG) limiting step from the reaction phase diagram.

摘要

单原子催化剂的高效合理设计具有十分重要的意义, 但是目 前对于结构和性能之间的关联关系认知不足, 严重阻碍了催化剂 的发展进程. 因此, 清晰阐释金属活性中心的配位结构对于其催化 性能的影响将有利于单原子催化剂的高效设计. 本文研究报道了 单原子Pt催化剂的活性中心配位结构显著影响其在烯烃反马氏硼 氢化反应中的性能表现. 三个O原子配位的Pt单原子催化剂(Pt-O3) 与另外两种配位结构(Pt-N4和Pt-O2)相比, 表现出了更高的催化活 性, 在烯烃反马氏硼氢化反应中的转化数可达到3288. 密度泛函理 论计算表明, Pt-O3催化剂具有超高活性的主要原因是其在反应相 图中具有最低的决速步能垒.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2018YFA0702003) and the National Natural Science Foundation of China (21890383, 21671117, 21871159 and 21901135). We thank the BL14W1 station in Shanghai Synchrotron Radiation Facility (SSRF) and 1W1B station for XAFS measurement in Beijing Synchrotron Radiation Facility (BSRF).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Qi Xu  (徐琪), Shubo Tian  (田书博), Jian Zhang  (张剑), Weng-Chon Cheong  (张永臻), Qiang Liu  (刘强), Bijie Li  (李必杰), Dingsheng Wang  (王定胜) & Yadong Li  (李亚栋)

  2. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    ChenXi Guo  (郭辰曦) & Jianping Xiao  (肖建平)

  3. Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Wenxing Chen  (陈文星)

  4. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China

    Lin Gu  (谷林)

  5. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China

    Lirong Zheng  (郑黎荣)

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  1. Qi Xu  (徐琪)
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Contributions

Xu Q designed and performed the experiments, analyzed the data, and wrote the paper. Guo C and Xiao J conducted the density functional theory calculations and contributed to the writing of the paper. Tian S and Zhang J assisted to carry out the experiments. Chen W and Zheng L helped with XAFS characterization and corresponding data analysis. Cheong WC assisted in HAADF-STEM and EDX elemental mapping characterizations. Gu L helped with the AC HAADF-STEM characterization. Liu Q and Li B helped analyze the data. Wang D and Li Y conceived the research project, analyzed the results and wrote the paper. All authors contributed to the general discussion.

Corresponding author

Correspondence to Dingsheng Wang  (王定胜).

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The authors declare that they have no conflict of interest.

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Supporting data are available in the online version of the paper.

Qi Xu received his BSc degree from the University of Science and Technology of China in 2017. Now, he is a PhD student under the supervision of Prof. Dingsheng Wang at Tsinghua University. His research interests mainly focus on the design and fabrication of single-atomic catalysts for heterogeneous catalysis.

Chenxi Guo received his PhD degree from the Queen’s University of Belfast in 2018. He is currently an Assistant Research Associate at Dalian Institute of Chemical Physics, Chinese Academy of Science. His research interests focus on the first principles calculations, theoretical catalysis, and rational design of catalytic materials.

Shubo Tian received his BSc (2013), MSc (2016), and PhD (2019) degrees from Hebei Normal University, University of the Chinese Academy of Sciences, and Tsinghua University, respectively. He is currently a postdoctor in the National University of Singapore. His research interests are focused on the syntheses and applications of isolated single-atom-site and cluster catalysts.

Dingsheng Wang received his BSc degree from the Department of Chemistry and Physics, University of Science and Technology of China in 2004, and his PhD degree from the Department of Chemistry, Tsinghua University in 2009, under the supervision of Prof. Yadong Li. He did his postdoctoral research at the Department of Physics, Tsinghua University, with Prof. Shoushan Fan. He joined the faculty of the Department of Chemistry, Tsinghua University in 2012.

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Xu, Q., Guo, C., Tian, S. et al. Coordination structure dominated performance of single-atomic Pt catalyst for anti-Markovnikov hydroboration of alkenes. Sci. China Mater. 63, 972–981 (2020). https://doi.org/10.1007/s40843-020-1334-6

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