Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors

Coskun, Oguz Kagan; Dongare, Saudagar; Doherty, Brian; Klemm, Aidan; Tuckerman, Mark; Gurkan, Burcu

doi:10.1002/ange.202312163

Title: Tailoring Electrochemical CO ₂ Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors

Journal Article · 05 November 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202312163 · OSTI ID:2204888

Coskun, Oguz Kagan ^[1]; Dongare, Saudagar ^[1]; Doherty, Brian ^[2];

^[1]; Tuckerman, Mark ^[3];

^[1]

Department of Chemical and Biomolecular Engineering Case Western Reserve University Cleveland OH 44106 USA
Department of Chemistry New York University New York NY 10003 USA
Department of Chemistry New York University New York NY 10003 USA, Simons Center for Computational Physical Chemistry at New York University New York NY 10003 USA

Abstract Electrochemical CO ₂ reduction (CO ₂ RR) on copper (Cu) shows promise for higher‐value products beyond CO. However, challenges such as the limited CO ₂ solubility, high overpotentials, and the competing hydrogen evolution reaction (HER) in aqueous electrolytes hinder the practical realization. We propose a functionalized ionic liquid (IL) which generates ion‐CO ₂ adducts and a hydrogen bond donor (HBD) upon CO ₂ absorption to modulate CO ₂ RR on Cu in a non‐aqueous electrolyte. As revealed by transient voltammetry, electrochemical impedance spectroscopy (EIS), and in situ surface‐enhanced Raman spectroscopy (SERS) complemented with image charge augmented quantum‐mechanical/molecular mechanics (IC‐QM/MM) computations, a unique microenvironment is constructed. In this microenvironment, the catalytic activity is primarily governed by the IL and HBD concentrations; former controlling the double layer thickness and the latter modulating the local proton availability. This translates to ample CO ₂ availability, reduced overpotential, and suppressed HER where C ₄ products are obtained. This study deepens the understanding of electrolyte effects in CO ₂ RR and the role of IL ions towards electrocatalytic microenvironment design.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0023427; SC0019409

OSTI ID:: 2204888

Alternate ID(s):: OSTI ID: 2274835

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 1 Vol. 136; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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