Tailoring Electrochemical CO2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors

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

doi:10.1002/anie.202312163

Tailoring Electrochemical CO₂ Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors

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

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

Abstract

Electrochemical CO₂ reduction (CO₂RR) on copper (Cu) shows promise for higher-value products beyond CO. However, challenges such as the limited CO₂ 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-CO₂ adducts and a hydrogen bond donor (HBD) upon CO₂ absorption to modulate CO₂RR 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 CO₂ availability, reduced overpotential, and suppressed HER where C₄ products are obtained. This study deepens the understanding of electrolyte effects in CO₂RR and the role of IL ions towards electrocatalytic microenvironment design.

Original language	English
Article number	e202312163
Journal	Angewandte Chemie - International Edition
Volume	63
Issue number	1
DOIs	https://doi.org/10.1002/anie.202312163
State	Published - Jan 2 2024
Externally published	Yes

Funding

This study was funded by an NSF CAREER award (no. 2045111) from the Division of Chemical, Bioengineering, Environmental and Transport Systems (CBET), Interfacial Engineering, and Electrochemical Systems. The authors would like to thank the NMR Instrumentation Facility at the Department of Chemistry and the Raman Spectroscopy Facility at the Department of Chemical Engineering at Case Western Reserve University for access to instrumentation. Partial support for computational analysis of the electrolyte structure at the interface was from Breakthrough Electrolytes for Energy Storage (BEES)—an Energy Frontier Research Center (EFRC) of the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0019409. S.D. was supported by the Center for Closing the Carbon Cycle (4C) EFRC, under Award # DE-SC0023427, for synthesis and chromatography analysis during electrolysis. This study was funded by an NSF CAREER award (no. 2045111) from the Division of Chemical, Bioengineering, Environmental and Transport Systems (CBET), Interfacial Engineering, and Electrochemical Systems. The authors would like to thank the NMR Instrumentation Facility at the Department of Chemistry and the Raman Spectroscopy Facility at the Department of Chemical Engineering at Case Western Reserve University for access to instrumentation. Partial support for computational analysis of the electrolyte structure at the interface was from Breakthrough Electrolytes for Energy Storage (BEES)—an Energy Frontier Research Center (EFRC) of the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE‐SC0019409. S.D. was supported by the Center for Closing the Carbon Cycle (4C) EFRC, under Award # DE‐SC0023427, for synthesis and chromatography analysis during electrolysis.

Funders	Funder number
Interfacial Engineering, and Electrochemical Systems
National Science Foundation	2045111
U.S. Department of Energy
Division of Chemical, Bioengineering, Environmental, and Transport Systems
Office of Science
Basic Energy Sciences	DE‐SC0023427, DE‐SC0019409
Energy Frontier Research Centers
Department of Chemistry, University of York

Keywords

CO Conversion
Double Layer
Electrocatalysis
Electrolysis
Interfacial Liquid Structure

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/anie.202312163

Cite this

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abstract = "Electrochemical CO2 reduction (CO2RR) on copper (Cu) shows promise for higher-value products beyond CO. However, challenges such as the limited CO2 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-CO2 adducts and a hydrogen bond donor (HBD) upon CO2 absorption to modulate CO2RR 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 CO2 availability, reduced overpotential, and suppressed HER where C4 products are obtained. This study deepens the understanding of electrolyte effects in CO2RR and the role of IL ions towards electrocatalytic microenvironment design.",

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AB - Electrochemical CO2 reduction (CO2RR) on copper (Cu) shows promise for higher-value products beyond CO. However, challenges such as the limited CO2 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-CO2 adducts and a hydrogen bond donor (HBD) upon CO2 absorption to modulate CO2RR 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 CO2 availability, reduced overpotential, and suppressed HER where C4 products are obtained. This study deepens the understanding of electrolyte effects in CO2RR and the role of IL ions towards electrocatalytic microenvironment design.

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