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Implications and Applications of Local pH in Electrocatalysis

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Implications and Applications of Local pH in Electrocatalysis
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45
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CC Attribution 4.0 International:
You are free to use, adapt and copy, distribute and transmit the work or content in adapted or unchanged form for any legal purpose as long as the work is attributed to the author in the manner specified by the author or licensor.
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Production Year2026
Production PlaceFrankfurt am Main

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Abstract
Electrochemistry can transform abundant resources like water and carbon dioxide into useful chemical and sustainable fuels. These reactions often involve protons, which are either consumed or produced at the surface of electrodes. The concentration of protons at the electrode (i.e., local pH) fundamentally governs the efficiency and selectivity of myriad electrochemical transformations (e.g., the oxygen evolution reaction [OER]). As more and more protons are consumed or produced during operation, however, this local pH can change dramatically. Taking bulk pH, buffer composition, and mass-transport into account, we develop an accessible and robust model for describing this local pH. Our model explores how pH gradients form and dissipate during operation, which we correspondingly validate using rotating (ring) disc electrodes. We may employ this model to predict the local pH over a wide range of current densities, including under industrially relevant conditions, and propose that dramatic changes in local pH may be inevitable regardless of bulk conditions. The complicating effects of morphology on local pH are further described to highlight how understanding and controlling this environment is crucial to improving the efficiency of electrochemical transformations.
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