Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors
Abstract
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.
- Authors:
-
[1];
[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
- Publication Date:
- Research Org.:
- Case Western Reserve Univ., Cleveland, OH (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 2204887
- Alternate Identifier(s):
- OSTI ID: 2263493; OSTI ID: 2311107
- Grant/Contract Number:
- SC0019409
- Resource Type:
- Published Article
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition) Journal Volume: 63 Journal Issue: 1; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; CO2 Conversion; Electrocatalysis; Double Layer; Interfacial Liquid Structure; Electrolysis
Citation Formats
Coskun, Oguz Kagan, Dongare, Saudagar, Doherty, Brian, Klemm, Aidan, Tuckerman, Mark, and Gurkan, Burcu. Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors. Germany: N. p., 2023.
Web. doi:10.1002/anie.202312163.
Coskun, Oguz Kagan, Dongare, Saudagar, Doherty, Brian, Klemm, Aidan, Tuckerman, Mark, & Gurkan, Burcu. Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors. Germany. https://doi.org/10.1002/anie.202312163
Coskun, Oguz Kagan, Dongare, Saudagar, Doherty, Brian, Klemm, Aidan, Tuckerman, Mark, and Gurkan, Burcu. Mon .
"Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors". Germany. https://doi.org/10.1002/anie.202312163.
@article{osti_2204887,
title = {Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors},
author = {Coskun, Oguz Kagan and Dongare, Saudagar and Doherty, Brian and Klemm, Aidan and Tuckerman, Mark and Gurkan, Burcu},
abstractNote = {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.},
doi = {10.1002/anie.202312163},
journal = {Angewandte Chemie (International Edition)},
number = 1,
volume = 63,
place = {Germany},
year = {Mon Nov 06 00:00:00 EST 2023},
month = {Mon Nov 06 00:00:00 EST 2023}
}
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