Quantification of Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction

Angewandte Chemie
Jaeyune RyuYogesh Surendranath

Abstract

We quantified changes in interfacial pH local to the electrochemical double layer during electrocatalysis by using a concurrent non-faradaic probe reaction. In the absence of electrocatalysis, nanostructured Pt/C surfaces mediate the reaction of H2 with cis-2-butene-1,4-diol to form a mixture of 1,4-butanediol and n-butanol with selectivity that is linearly dependent on the bulk solution pH value. We show that kinetic branching occurs from a common surface-bound intermediate, ensuring that this probe reaction is uniquely sensitive to the interfacial pH value within molecular length scales of the surface. We used the pH-dependent selectivity of this reaction to track changes in interfacial pH during concurrent hydrogen oxidation electrocatalysis and found that the local pH value can vary dramatically (>3 units) relative to the bulk value even at modest current densities in well-buffered electrolytes. This study highlights the key role of interfacial pH variation in modulating inner-sphere electrocatalysis.

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Citations

Oct 17, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Shelby L BehnkeHannah S Shafaat
Apr 18, 2019·Angewandte Chemie·Harshitha Barike AiyappaWolfgang Schuhmann
Sep 29, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Camille R SchneiderHannah S Shafaat
Aug 12, 2020·Chemical Society Reviews·Young Jin SaYun Jeong Hwang
Oct 7, 2020·Chemical Communications : Chem Comm·Kendrick K L NgAlexander T Murray
Jun 6, 2021·Science Advances·Junyang HuangJeremy J Baumberg
Sep 17, 2019·Journal of the American Chemical Society·Kailun YangWilson A Smith
Dec 26, 2019·Analytical Chemistry·Mariana C O MonteiroMarc T M Koper
Aug 23, 2019·Journal of the American Chemical Society·Jaeyune Ryu, Yogesh Surendranath
Jul 7, 2020·Journal of the American Chemical Society·Jaeyune Ryu, Yogesh Surendranath
Nov 17, 2020·Inorganic Chemistry·Felix M BrunnerClifford P Kubiak
Nov 18, 2021·Langmuir : the ACS Journal of Surfaces and Colloids·Milomir Suvira, Bo Zhang

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