Dopant- and Surfactant-Tuned Electrode-Electrolyte Interface Enabling Efficient Alkynol Semi-Hydrogenation

Yuan Zhao; Jipeng Xu; Kai Huang; Wangxin Ge; Zhen Liu; Cheng Lian; Honglai Liu; Hongliang Jiang; Chunzhong Li

doi:10.1021/jacs.3c00565

Dopant- and Surfactant-Tuned Electrode-Electrolyte Interface Enabling Efficient Alkynol Semi-Hydrogenation

J Am Chem Soc. 2023 Mar 22;145(11):6516-6525. doi: 10.1021/jacs.3c00565. Epub 2023 Mar 13.

Authors

Yuan Zhao^{1

2}, Jipeng Xu³, Kai Huang³, Wangxin Ge², Zhen Liu¹, Cheng Lian³, Honglai Liu³, Hongliang Jiang¹, Chunzhong Li^{1

2}

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, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.

PMID: 36913524
DOI: 10.1021/jacs.3c00565

Abstract

Electrochemical alkynol semi-hydrogenation has emerged as a sustainable and environmentally benign route for the production of high-value alkenols, featuring water as the hydrogen source instead of H₂. It is highly challenging to design the electrode-electrolyte interface with efficient electrocatalysts and their matched electrolytes to break the selectivity-activity stereotype. Here, boron-doped Pd catalysts (PdB) and surfactant-modified interface are proposed to enable the simultaneous increase in alkenol selectivity and alkynol conversion. Typically, compared to pure Pd and commercial Pd/C catalysts, the PdB catalyst achieves both higher turnover frequency (139.8 h^-1) and specific selectivity (above 90%) for the semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY). Quaternary ammonium cationic surfactants that are employed as electrolyte additives are assembled at the electrified interface in response to applied bias potential, establishing an interfacial microenvironment that can facilitate alkynol transfer and hinder water transfer suitably. Eventually the hydrogen evolution reaction is inhibited and alkynol semi-hydrogenation is promoted, without inducing the decrease of alkenol selectivity. This work offers a distinct perspective on creating a suitable electrode-electrolyte interface for electrosynthesis.