Issue 12, 2023

The electrostatic effect and its role in promoting electrocatalytic reactions by specifically adsorbed anions

Abstract

The adsorption of anions and its impact on electrocatalytic reactions are fundamental topics in electrocatalysis. Previous studies revealed that adsorbed anions display an overall poisoning effect in most cases. However, for a few reactions such as the hydrogen evolution reaction (HER), oxidation of small organic molecules (SOMs), and reduction of CO2 and O2, some specifically adsorbed anions can promote their reaction kinetics under certain conditions. The promotion effect is frequently attributed to the adsorbate induced modification of the nature of the active sites, the change of the adsorption configuration and free energy of the key reactive intermediate which consequently change the activation energy, the pre-exponential factor of the rate determining step etc. In this paper, we will give a mini review of the indispensable role of the classical double layer effect in enhancing the kinetics of electrocatalytic reactions by anion adsorption. The ubiquitous electrostatic interactions change both the potential distribution and the concentration distribution of ionic species across the electric double layer (EDL), which alters the electrochemical driving force and effective concentration of the reactants. The contribution to the overall kinetics is highlighted by taking HER, oxidation of SOMs, reduction of CO2 and O2, as examples.

Graphical abstract: The electrostatic effect and its role in promoting electrocatalytic reactions by specifically adsorbed anions

Article information

Article type
Perspective
Submitted
29 Sep 2022
Accepted
03 Feb 2023
First published
06 Feb 2023

Phys. Chem. Chem. Phys., 2023,25, 8317-8330

The electrostatic effect and its role in promoting electrocatalytic reactions by specifically adsorbed anions

W. Chen, L. Zhang, Z. Wei, M. Zhang, J. Cai and Y. Chen, Phys. Chem. Chem. Phys., 2023, 25, 8317 DOI: 10.1039/D2CP04547H

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