Mechanistic Insights into Surfactant-Modulated Electrode-Electrolyte Interface for Steering H2O2 Electrosynthesis

Yu Fan; Yuxin Chen; Wangxin Ge; Lei Dong; Yanbin Qi; Cheng Lian; Xiaodong Zhou; Honglai Liu; Zhen Liu; Hongliang Jiang; Chunzhong Li

doi:10.1021/jacs.3c13660

Mechanistic Insights into Surfactant-Modulated Electrode-Electrolyte Interface for Steering H₂O₂ Electrosynthesis

J Am Chem Soc. 2024 Mar 20;146(11):7575-7583. doi: 10.1021/jacs.3c13660. Epub 2024 Mar 11.

Authors

Yu Fan^{1

2}, Yuxin Chen³, Wangxin Ge², Lei Dong^{1

2}, Yanbin Qi², Cheng Lian³, Xiaodong Zhou¹, Honglai Liu³, Zhen Liu¹, Hongliang Jiang^{1

4}, Chunzhong Li^{1

2

4}

Affiliations

¹ Key Laboratory for Ultrafine Materials of Ministry of Education, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China.
² Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
³ State Key Laboratory of Chemical Engineering, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China.
⁴ Department of Chemical Engineering, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.

PMID: 38466222
DOI: 10.1021/jacs.3c13660

Abstract

Electrocatalytic reactions taking place at the electrified electrode-electrolyte interface involve processes of proton-coupled electron transfer. Interfacial protons are delivered to the electrode surface via a H₂O-dominated hydrogen-bond network. Less efforts are made to regulate the interfacial proton transfer from the perspective of interfacial hydrogen-bond network. Here, we present quaternary ammonium salt cationic surfactants as electrolyte additives for enhancing the H₂O₂ selectivity of the oxygen reduction reaction (ORR). Through in situ vibrational spectroscopy and molecular dynamics calculation, it is revealed that the surfactants are irreversibly adsorbed on the electrode surface in response to a given bias potential range, leading to the weakening of the interfacial hydrogen-bond network. This decreases interfacial proton transfer kinetics, particularly at high bias potentials, thus suppressing the 4-electron ORR pathway and achieving a highly selective 2-electron pathway toward H₂O₂. These results highlight the opportunity for steering H₂O-involved electrochemical reactions via modulating the interfacial hydrogen-bond network.