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Electrocatalytic metal hydride generation using CPET mediators

Author

Listed:
  • Subal Dey

    (ETH Zürich
    Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Sorbonne Université)

  • Fabio Masero

    (ETH Zürich)

  • Enzo Brack

    (ETH Zürich)

  • Marc Fontecave

    (Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Sorbonne Université)

  • Victor Mougel

    (ETH Zürich)

Abstract

Transition metal hydrides (M-H) are ubiquitous intermediates in a wide range of enzymatic processes and catalytic reactions, playing a central role in H+/H2 interconversion1, the reduction of CO2 to formic acid (HCOOH)2 and in hydrogenation reactions. The facile formation of M-H is a critical challenge to address to further improve the energy efficiency of these reactions. Specifically, the easy electrochemical generation of M-H using mild proton sources is key to enable high selectivity versus competitive CO and H2 formation in the CO2 electroreduction to HCOOH, the highest value-added CO2 reduction product3. Here we introduce a strategy for electrocatalytic M-H generation using concerted proton–electron transfer (CPET) mediators. As a proof of principle, the combination of a series of CPET mediators with the CO2 electroreduction catalyst [MnI(bpy)(CO)3Br] (bpy = 2,2′-bipyridine) was investigated, probing the reversal of the product selectivity from CO to HCOOH to evaluate the efficiency of the manganese hydride (Mn-H) generation step. We demonstrate the formation of the Mn-H species by in situ spectroscopic techniques and determine the thermodynamic boundary conditions for this mechanism to occur. A synthetic iron–sulfur cluster is identified as the best CPET mediator for the system, enabling the preparation of a benchmark catalytic system for HCOOH generation.

Suggested Citation

  • Subal Dey & Fabio Masero & Enzo Brack & Marc Fontecave & Victor Mougel, 2022. "Electrocatalytic metal hydride generation using CPET mediators," Nature, Nature, vol. 607(7919), pages 499-506, July.
  • Handle: RePEc:nat:nature:v:607:y:2022:i:7919:d:10.1038_s41586-022-04874-z
    DOI: 10.1038/s41586-022-04874-z
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    Cited by:

    1. Xin Yu Zhang & Zhen Xin Lou & Jiacheng Chen & Yuanwei Liu & Xuefeng Wu & Jia Yue Zhao & Hai Yang Yuan & Minghui Zhu & Sheng Dai & Hai Feng Wang & Chenghua Sun & Peng Fei Liu & Hua Gui Yang, 2023. "Direct OC-CHO coupling towards highly C2+ products selective electroreduction over stable Cu0/Cu2+ interface," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    2. Haifeng Shen & Huanyu Jin & Haobo Li & Herui Wang & Jingjing Duan & Yan Jiao & Shi-Zhang Qiao, 2023. "Acidic CO2-to-HCOOH electrolysis with industrial-level current on phase engineered tin sulfide," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    3. Jiexin Zhu & Jiantao Li & Ruihu Lu & Ruohan Yu & Shiyong Zhao & Chengbo Li & Lei Lv & Lixue Xia & Xingbao Chen & Wenwei Cai & Jiashen Meng & Wei Zhang & Xuelei Pan & Xufeng Hong & Yuhang Dai & Yu Mao , 2023. "Surface passivation for highly active, selective, stable, and scalable CO2 electroreduction," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    4. Xuejiao Wu & Xueting Fan & Shunji Xie & Ivan Scodeller & Xiaojian Wen & Dario Vangestel & Jun Cheng & Bert Sels, 2024. "Zinc-indium-sulfide favors efficient C − H bond activation by concerted proton-coupled electron transfer," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    5. Laihao Luo & Xinyan Liu & Xinyu Zhao & Xinyan Zhang & Hong-Jie Peng & Ke Ye & Kun Jiang & Qiu Jiang & Jie Zeng & Tingting Zheng & Chuan Xia, 2024. "Pressure-induced generation of heterogeneous electrocatalytic metal hydride surfaces for sustainable hydrogen transfer," Nature Communications, Nature, vol. 15(1), pages 1-15, December.

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