Mercaptoimidazole‐Engineered Microenvironment Enables Durable CO <sub>2</sub> Electroreduction in a Zero‐Gap PEM Electrolyzer
Abstract
ABSTRACT CO 2 conversion in proton exchange membrane (PEM) electrolysis systems offers a sustainable pathway for chemical production by eliminating carbonate formation; however, it faces a trade‐off between suppressing the hydrogen evolution reaction and preventing salt precipitation. Here, we resolve this paradox through a molecular‐level engineering strategy by anchoring a mercaptoimidazole ligand on lead‐based catalyst. Operando spectroscopic analyses and theoretical studies reveal that this ligand shell creates a local alkaline microenvironment and establishes a proton‐shielding effect at the catalyst surface. When integrated into a zero‐gap PEM electrolyzer, the catalyst achieves a peak formate Faradaic efficiency of 95.8% and sustains over 90% selectivity at a current density of 600 mA cm −2 . This performance persists under strongly acidic (pH 1.0) and cation‐starved (0.001 M ) conditions. The PEM system delivers extended stability, with over 300 h of continuous operation at industrially relevant current densities. Our work establishes a design strategy that decouples the catalytic microenvironment from the bulk electrolyte and provides a route for durable and selective acidic CO 2 electrolyzers.
Article Details
Authors (10)
Jia Chen Wu
Key Laboratory for Ultrafine Materials of Ministry of Education School of Materials Science and Engineering East China University of Science and Technology 130 Meilong Road Shanghai 200237 China
Tingting Yu
Key Laboratory of Molecular Epigenetics of the Ministry of Education, Northeast Normal University
Jianming Gu
School of Materials Science and Engineering Key Laboratory for Ultrafine Materials of Ministry of Education East China University of Science and Technology Shanghai China
Huai Qin Fu
School of Environment and Science, Gold Coast Campus
Ziwei Ye
Hai Yang Yuan
Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
Cheng Lian
State Key Laboratory of Chemical Engineering, School of Chemistry and Molecular Engineering
Huiliang Cao
School of Materials Science and Engineering Key Laboratory for Ultrafine Materials of Ministry of Education East China University of Science and Technology Shanghai China
Hua Gui Yang
Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
Peng Fei Liu
Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China