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Adsorbed Hydroxide Does Not Participate in the Volmer Step of Alkaline Hydrogen Electrocatalysis
Journal article   Peer reviewed

Adsorbed Hydroxide Does Not Participate in the Volmer Step of Alkaline Hydrogen Electrocatalysis

Saad Intikhab, Joshua D. Snyder and Maureen H. Tang
ACS catalysis, v 7(12), pp 8314-8319
01 Dec 2017

Abstract

Chemistry Chemistry, Physical Physical Sciences Science & Technology
The sluggish kinetics of the alkaline hydrogen electrode have been attributed to the need to adsorb both H and OH optimally. In this work, single-crystal voltammetry and microkinetic modeling show that an OH-mediated mechanism is not viable on Pt(110). Only a direct Volmer step can explain observed kinetic trends with OH adsorption strength in KOH and LiOH electrolytes. Instead, OH behaves as a rapidly equilibrated spectator species that decreases available surface sites and slows hydrogen kinetics. These results identify kinetic barriers from interfacial water structure, not adsorption energies, as key to explaining changes in hydrogen kinetics with pH.

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Chemistry, Physical
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