pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles

Lamoureux, Philomena Schlexer; Singh, Aayush R.; Chan, Karen

doi:10.1021/acscatal.9b00268

Title: pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles

Journal Article · 05 June 2019 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.9b00268 · OSTI ID:1546960

^[1];

^[2]

Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Technical Univ. of Denmark, Lyngby (Denmark)

A long-standing question in electrocatalysis is how the electrolyte pH affects the catalytic activity of proton–electron transfer reactions. A prime example for this is the hydrogen evolution/oxidation reaction (HER/HOR) over metal catalysts. While it has long been established that alkaline conditions result in a more sluggish reaction kinetics than in acidic conditions, the underlying reason for this trend remains contentious. Here, we apply density functional calculations to evaluate prevailing hypotheses for the origin of this effect: shifts in hydrogen binding, proton donor, and water reorganization energy. We present a microkinetic model, based on ab initio reaction energetics of all possible elementary steps. Our model shows a good agreement with experimental trends. We find that with increasing pH, the proton donor changes from hydronium to water. In conclusion, our model suggests that the intrinsically larger barriers for the splitting of water with respect to hydronium are the cause of HER kinetics being slower in alkaline than in acidic media.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1546960

Journal Information:: ACS Catalysis, Vol. 9, Issue 7; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 111 works

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Title: pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles

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