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Wireless potentiometry of thermochemical heterogeneous catalysis

Nature Catalysis volume 8, pages 315–327 (2025)Cite this article

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Abstract

The electrochemical potential of a catalyst defines the free-energy landscape of catalysis in liquid media and is readily measured for catalysts supported on conductive materials or wired to external circuits. However, the potential is difficult to quantify for thermochemical catalysts supported on electrical insulators, thereby impeding a unifying understanding of the role of electrochemical polarization during thermochemical catalysis. Here we develop a methodology to quantify the electrochemical potential of metal catalysts supported on insulators by introducing low concentrations of redox-active molecules that establish wireless electrical connections between the catalyst and a sensing electrode. Using this approach in tandem with simultaneous rate measurements, we demonstrate distinct rate-potential scalings for oxidative dehydrogenation of formic acid on SiO2-supported and Al2O3-supported versus TiO2-supported Pt and find deactivation modes specific to SiO2-supported Pt. These developments enable the comprehensive investigation of the role of electrochemical polarization in thermochemical catalysis and complement the existing toolkit for mechanistic investigation in catalysis.

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Fig. 1: Wired and wireless electrochemical potential measurement.
Fig. 2: Wireless potentiometry model system and measurement of catalyst potential.
Fig. 3: Tracking transients in catalyst potential.
Fig. 4: Potential measurement in neutral and alkaline water.
Fig. 5: Potential measurement in acetonitrile.
Fig. 6: Aerobic formic acid oxidation on supported Pt catalysts as a function of HCOOH concentration.
Fig. 7: Aerobic HCOOH oxidation on supported Pt catalysts with varying O2 partial pressure.
Fig. 8: Non-monotonic trends in Ecat and TOF over Pt/SiO2 during formic acid oxidation after lowering O2 partial pressure.

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The data that support the findings of this study are included in the article and its Supplementary Information or from the corresponding author on reasonable request.

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Acknowledgements

We thank the entire Surendranath Lab for their support and scientific discussions. This work was supported by the Gordon and Betty Moore Foundation, under grant ID: GBMF11510 (https://doi.org/10.37807/GBMF11510). N.K.R. is grateful for the generous support from the Arnold O. Beckman Postdoctoral Fellowship. K.S.W. acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant No. 174530.

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  1. These authors contributed equally: Neil K. Razdan, Karl S. Westendorff.

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

    Neil K. Razdan, Karl S. Westendorff & Yogesh Surendranath

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  1. Neil K. Razdan
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  2. Karl S. Westendorff
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Contributions

N.K.R. and Y.S. conceived the research and developed the experiments. N.K.R. conducted the majority of the experiments. K.S.W. conducted characterization experiments, O2 reaction order experiments and contributed to data analysis. N.K.R., K.S.W. and Y.S. wrote the paper.

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Correspondence to Yogesh Surendranath.

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Nature Catalysis thanks Steven McIntosh, Kotaro Takeyasu and Bin Zhang for their contribution to the peer review of this work.

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Razdan, N.K., Westendorff, K.S. & Surendranath, Y. Wireless potentiometry of thermochemical heterogeneous catalysis. Nat Catal 8, 315–327 (2025). https://doi.org/10.1038/s41929-025-01308-7

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