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Metal surfaces catalyse polarization-dependent hydride transfer from H2

Nature Catalysis volume 6, pages 351–362 (2023)Cite this article

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Abstract

Hydride transfer is a critical elementary reaction step that spans biological catalysis, organic synthesis and energy conversion. Conventionally, hydride transfer reactions are performed using (bio)molecular hydride reagents under homogeneous conditions. Here we report a conceptually distinct heterogeneous hydride transfer reaction via the net electrocatalytic hydrogen reduction reaction (HRR), which reduces H2 to hydrides. The reaction proceeds by H2 dissociative adsorption on a metal electrode to form surface M−H species, which are then negatively polarized to drive hydride transfer to molecular hydride acceptors with up to 91% Faradaic efficiency. The hydride transfer reactivity of surface M−H species is highly tunable, and, depending on the electrode potential, the thermodynamic hydricity of Pt−H on the same Pt electrode can continuously span a range of >40 kcal mol−1. This work highlights the critical role of electrical polarization on heterogeneous hydride transfer reactivity and establishes a sustainable strategy for accessing reactive hydrides directly from H2.

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Fig. 1: Design of heterogeneous hydride transfer and the HRR.
Fig. 2: Heterogeneous hydride transfer via electrocatalytic HRR.
Fig. 3: Thermodynamic studies reveal Nernstian behaviour of reversible HRR.
Fig. 4: Schematic of the polarization dependence of interfacial hydride transfer.
Fig. 5: Thermochemical cycle correlating surface hydricity to the applied potential.
Fig. 6: Kinetics studies of interfacial hydride transfer.
Fig. 7: Effect of electrode material on HRR kinetics.

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Data availability

The data that support the findings of this study are included in Supplementary Information of the published Article or are available from the corresponding author on reasonable request.

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Acknowledgements

We gratefully acknowledge A. Radosevich for fruitful discussions. We thank the entire Surendranath laboratory for their support and scientific discussions, with particular acknowledgements to D. Harraz, M. Hülsey and J. Ryu for reviewing the paper and H. W. Chung for proofreading and reproducing the data in Fig. 3. This work was supported primarily by the Air Force Office of Scientific Research (AFOSR) under award no. FA9550-18-1-0420. H.-X.W. acknowledges generous support from the Croucher Fellowship.

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  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Hai-Xu Wang, Wei Lun Toh, Bryan Y. Tang & Yogesh Surendranath

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Contributions

H.-X.W. and Y.S. conceived the research and developed experiments. H.-X.W. conducted the majority of the experiments. W.L.T. and B.Y.T. contributed to experimental design and data analysis. H.-X.W. and Y.S. wrote the paper, with input from all authors.

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Correspondence to Yogesh Surendranath.

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Wang, HX., Toh, W.L., Tang, B.Y. et al. Metal surfaces catalyse polarization-dependent hydride transfer from H2. Nat Catal 6, 351–362 (2023). https://doi.org/10.1038/s41929-023-00944-1

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