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Grand Canonical Quantum Mechanics with Applications to Mechanisms and Rates for Electrocatalysis

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Abstract

We outline the recently developed Grand Canonical Potential Kinetics (GCP-K) method to implement Grand Canonical Quantum Mechanics for predicting electrochemical reactions as a function of applied potential rather than with fixed numbers of electrons as in traditional Quantum Mechanics (QM) calculations. We describe here the recent validation of GCP-K for The Co/TiO2 single atom catalyst for the Oxygen Evolution Reaction (OER) on a single crystal nanoparticle where a single surface facet was present. The basal plane of transition metal dichalcogenides (TMDs) in the 1 T’ phase of WSe2 and WTe2, which leads to high-performance for the hydrogen evolution reaction (HER). We find that GCP-K predicts accurate TOF and currents as a function of applied potential and accurate Tafel slopes for both the Co/TiO2 OER and the chalcogenide HER systems for which we can be confident of the surface structure. Thus we expect that these methods will be useful in the more common situation for which there is much less certainty about the surface structure under experimental conditions.

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Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The OER study on Co/TiO2 is based on work performed by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. The HER study on chalcogenides was supported by the NSF (CBET-2005250, program manager Robert McCabe)

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  1. Materials and Process Simulation Center and Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA, 91125, USA

    William A. Goddard III & Jie Song

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Goddard, W.A., Song, J. Grand Canonical Quantum Mechanics with Applications to Mechanisms and Rates for Electrocatalysis. Top Catal 66, 1171–1177 (2023). https://doi.org/10.1007/s11244-023-01794-8

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