• Article •

### Understanding surface charge effects in electrocatalysis. Part 2: Hydrogen peroxide reactions at platinum

Jun Huanga,*, Victor Climentb, Axel Großa,c, Juan Feliub,#

1. aInstitute of Theoretical Chemistry, Ulm University, 89069 Ulm, Germany;
bInstituto de Electroquímica, Universidad de Alicante, Apdo. 99, Alicante, Spain;
cHelmholtz Institute Ulm (HIU) Electrochemical Energy Storage, 89069 Ulm, Germany
• Received:2022-03-13 Accepted:2022-05-31
• Contact: * E-mail: ju.huang@fz-julich.de; # E-mail: juan.feliu@ua.es
• Supported by:
Europe Research Stay at Alicante University from the Alexander von Humboldt Foundation, National Natural Science Foundation of China (21802170), the German Research Foundation (DFG) (INST 40/575-1 FUGG (JUSTUS 2 cluster)), the research performed at CELEST (Center for Electrochemical Energy Storage Ulm-Karlsruhe), the Ministerio de Ciencia e Innovación (Project PID2019-105653GB-100) and Generalitat Valenciana (Project PROMETEO/2020/063).

Abstract: Electrocatalytic activity is influenced by the surface charge on the solid catalyst. Conventionally, our attention has been focused on how the surface charge shapes the electric potential and concentration of ionic reactant(s) in the local reaction zone. Taking H2O2 redox reactions at Pt(111) as a model system, we reveal a peculiar surface charge effect using ab initio molecular dynamics simulations of electrified Pt(111)-water interfaces. In this scenario, the negative surface charge on Pt(111) repels the O-O bond of the reactant (H2O2) farther away from the electrode surface. This leads to a higher activation barrier for breaking the O-O bond. Incorporating this microscopic mechanism into a microkinetic-double-layer model, we are able to semi-quantitatively interpret the pH-dependent activity of H2O2 redox reactions at Pt(111), especially the anomalously suppressed activity of H2O2 reduction with decreasing electrode potential. The relevance of the present surface charge effect is also examined in wider scenarios with different electrolyte cations, solution pHs, crystal facets of the catalyst, and model parameters. In contrast with previous mechanisms focusing on how surface charge influences the local reaction condition at a fixed reaction plane, the present work gives an example in which the location of the reaction plane is adjusted by the surface charge.