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Thermochemical heterolytic hydrogenation catalysis proceeds through polarization-driven hydride transfer

Nature Chemistry (2025)Cite this article

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Abstract

Heterolytic hydrogenations, which split H2 across a hydride acceptor and proton acceptor, comprise a key reaction class that spans the chemical value chain, including CO2 hydrogenation to formate and NADH regeneration from nicotinamide adenine dinucleotide (NAD+). The dominant mechanistic models for heterogeneous catalysis of these reactions invoke classical surface reaction steps, largely ignoring the role of interfacial charge separation. Here we quantify the electrochemical potential of the catalyst during turnover and uncover evidence supporting an interfacial electrochemical hydride transfer mechanism for this overall thermochemical reaction class. We find that the proton acceptor induces spontaneous electrochemical polarization of the metal catalyst surface, thereby controlling the thermodynamic hydricity of the surface M–H intermediates and driving rate-determining electrochemical hydride transfer to the hydride acceptor substrate. This mechanistic framework, which applies across diverse reaction media and for the hydrogenation of CO2 to formate and NAD+ to NADH, enables the determination of intrinsic reaction kinetics and exposes design principles for the future development of sustainable hydrogenation reactivity.

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Fig. 1: Heterogeneous heterolytic hydrogenation catalysis and proposed mechanistic pathways.
Fig. 2: BIM+ as a model substrate for heterolytic hydrogenation catalysis and mechanistic studies.
Fig. 3: Proposed electrochemical mechanism for heterolytic hydrogenation catalysis of BIM+.
Fig. 4: Evidence for an electrochemical mechanism in thermochemical NADH regeneration.
Fig. 5: Evidence for an electrochemical mechanism in thermochemical CO2 hydrogenation.
Fig. 6: Exchange reaction rates for heterolytic hydrogenation catalysis.

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Data availability

The data that support the findings of this study are included in the published article (and its Supplementary Information) as .zip files or available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

We thank the entire Surendranath Laboratory for their support, with particular acknowledgement to T. Wesley, W. L. Toh and B. Y. Tang for fruitful discussion and H. W. Chung, D. Harraz and K. Westendorff for examining the paper. This research was supported by the National Science Foundation, under grant award number CHE-2400167 (Y.S.). H.-X.W. gratefully acknowledges support from the Croucher Fellowship.

Author information

Author notes

  1. Hai-Xu Wang

    Present address: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, P. R. China

Authors and Affiliations

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

    Hai-Xu Wang & Yogesh Surendranath

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  1. Hai-Xu Wang
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  2. Yogesh Surendranath
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Contributions

H.-X.W. and Y.S. conceived the research and developed experiments. H.-X.W. conducted the experiments. H.-X.W. and Y.S. analysed the data and wrote the paper.

Corresponding author

Correspondence to Yogesh Surendranath.

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The authors declare no competing interests.

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Nature Chemistry thanks Ning Yan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–25, Discussion and Tables 1–4.

Supplementary Data 1

NMR data for BIM+ hydrogenation.

Supplementary Data 2

Open-circuit potential data for potential sensing experiments.

Supplementary Data 3

Open-circuit potential data and calculated hydricity values.

Supplementary Data 4

Comparison of open-circuit potential data for potential sensing experiments.

Supplementary Data 5

NMR data for BIM+ hydrogenation catalyzed by Pt/SiO2 using D2.

Supplementary Data 6

NMR data for BIM+ hydrogenation catalyzed by Pt/C using D2.

Supplementary Data 7

NMR data for BIM+ hydrogenation catalyzed by Pt/SiO2 using D2 in the absence of HOAc.

Supplementary Data 8

NMR spectral changes for BIM+ hydrogenation using MTBD.

Supplementary Data 9

Time course data and linear fits for BIM+ hydrogenation using various buffers.

Supplementary Data 10

Time course data and linear fits for BIM+ hydrogenation using various acid/base ratios.

Supplementary Data 12

Crude UV–Vis data for NAD+ hydrogenation at various pH values.

Supplementary Data 13

Crude UV–Vis data for NAD+ hydrogenation after treated with lipoamide dehydrogenase.

Supplementary Data 14

NMR data for H/D tracer experiment of NAD+.

Supplementary Data 15

UV–Vis spectral changes for NAD+ hydrogenation.

Supplementary Data 16

Time course data and linear fits for NAD+ hydrogenation.

Supplementary Data 17

Time course data, Tafel data and their linear fits for NAD+ hydrogenation.

Supplementary Data 18

NMR data for CO2 hydrogenation using various bases.

Supplementary Data 19

NMR data for H/D tracer reaction of CO2.

Supplementary Data 20

Time course data and linear fits for CO2 hydrogenation using various bases.

Supplementary Data 21

Time course data and linear fits for CO2 hydrogenation using various acid/base ratios.

Supplementary Data 22

Time course data, Tafel data and their linear fits for CO2 hydrogenation using Rh/C as catalyst.

Supplementary Data 23

Open-circuit potential data and calculated hydricity values for CO2 hydrogenation.

Supplementary Data 24

Open-circuit potential data for CO2 hydrogenation.

Source data

Source Data Fig. 2

Experimental data and linear fits used to plot Fig. 2b–e,g,h.

Source Data Fig. 4

Experimental data and linear fits used to plot Fig. 4c,d.

Source Data Fig. 5

Experimental data and linear fits used to plot Fig. 5c,d.

Source Data Fig. 6

Experimental data, linear fits and extrapolated data.

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Wang, HX., Surendranath, Y. Thermochemical heterolytic hydrogenation catalysis proceeds through polarization-driven hydride transfer. Nat. Chem. (2025). https://doi.org/10.1038/s41557-025-01939-0

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