Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)
Publication date: 28th August 2024
Water activation, oxidatively to produce surface-bound hydroxide (OH*) or reductively to form surface-bound hydrogen (H*) atoms, is ubiquitous in electrocatalysis. We report the impact of cations on the kinetics of the OH* and H* formation from water on single-crystal Pt(111) in alkaline using fast-scan-rate cyclic voltammetry (CV). Isolating the dependence of the electro-adsorption kinetics on pH and ionic strength led to the observation that ion concentrations affected the OH* formation kinetics more strongly than pH. The H* formation exhibited similar behavior, even though the OH* formation rate was observed to be faster by >10´. We attributed the observed ion concentration effect to cations, given that switching cations (from Na+ to Li+) had a bigger impact on the H* and OH* formation rates than switching pH (effectively changing OH– to F–). We hypothesize the cations softened the interfacial water layer, allowing the water molecules to reorganize more easily. This result suggests that interfacial water disruption should benefit both H* and OH* electro-adsorption kinetics in alkaline electrolytes.
This material is based upon work supported by the National Science Foundation under Grant No. CHE-2155157 (electrochemistry). We acknowledge Dr. Xinyao Lu and the Center for Alkaline-Based Energy Solutions, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under Award DE-SC0019445 for conducting early works on the cations and supporting the efforts to grow platinum single crystals for this work.
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