Water Clustering Modulates Activity and Enables Hydrogenated Product Formation during Carbon Monoxide Electroreduction in Aprotic Media

Hannah Fejzić; Ritesh Kumar; Reginaldo J. Gomes; Lilin He; Theodore J. Houser; Jaemin Kim; Matin Mohebi; Nora Molten; Chibueze V. Amanchukwu

doi:10.1021/jacs.4c07865

Water Clustering Modulates Activity and Enables Hydrogenated Product Formation during Carbon Monoxide Electroreduction in Aprotic Media

Hannah Fejzić
, Ritesh Kumar
, Reginaldo J. Gomes
, Lilin He
, Theodore J. Houser
, Jaemin Kim
, Matin Mohebi
, Nora Molten
, Chibueze V. Amanchukwu

SANS & Spin Echo

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

4 Scopus citations

Abstract

Water solvation plays a critical role in a wide range of electrochemical transformations, but its role is often convoluted since water is typically used as both a solvent and a proton source. Here, we experimentally control water speciation and activity using aprotic solvent media during the carbon monoxide reduction reaction (CORR). Remarkably, we show that aprotic solvents that support microheterogeneous water-water clusters lead to significant amounts of CORR products (methane and ethylene) with a maximum ethylene Faradaic efficiency of 22% in acetonitrile (χ_H₂O = 0.2). In contrast, microhomogeneous systems-where water integrates into the solvents’ intermolecular binding network and has lower activity-primarily support the undesired hydrogen evolution reaction (HER). Insights gained expand our understanding of water activity and nonaqueous electrolyte design for other important transformation reactions beyond CO reduction, such as CO2RR and HER.

Original language	English
Pages (from-to)	18445-18459
Number of pages	15
Journal	Journal of the American Chemical Society
Volume	147
Issue number	22
DOIs	https://doi.org/10.1021/jacs.4c07865
State	Published - Jun 4 2025

Funding

This work was primarily supported by the U.S. Department of Energy Office of Science Basic Energy Sciences, Early Career Research Program (DE-SC0024103). C.V.A. acknowledges the CIFAR Azrieli Global Scholar Award and partial support from the Catalyst Design for Decarbonization Center (CD4DC), an Energy Frontier Research Center, which is funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) DE-SC0023383. H.F. was supported by the National Science Foundation Graduate Research Fellowship Program. R.K. was supported by the Eric and Wendy Schmidt AI in Science Postdoctoral Fellowship, a Schmidt Futures Program. R.J.G. was partially supported by the Roberto Rocca Scholars Program. This work made use of the shared facilities (Raman) at the University of Chicago Materials Research Science and Engineering Center, supported by the National Science Foundation under award number DMR-2011854. FTIR was performed at the Soft Matter Characterization Facility of the University of Chicago. MD calculations were performed with the computational resources provided by the University of Chicago’s Research Computing Center. The authors thank Caroline Koustis and Cole Gardner from Shimadzu Scientific Instruments for UHPLC. The authors also appreciate Alexander Filatov and Ke-Hsin Wang for performing the XPS measurements. This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This work benefited from the use of the SasView application, originally developed under NSF award DMR-0520547. SasView contains code developed with funding from the European Union’s Horizon 2020 research and innovation program under the SINE2020 project, grant agreement No 654000.

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title = "Water Clustering Modulates Activity and Enables Hydrogenated Product Formation during Carbon Monoxide Electroreduction in Aprotic Media",

abstract = "Water solvation plays a critical role in a wide range of electrochemical transformations, but its role is often convoluted since water is typically used as both a solvent and a proton source. Here, we experimentally control water speciation and activity using aprotic solvent media during the carbon monoxide reduction reaction (CORR). Remarkably, we show that aprotic solvents that support microheterogeneous water-water clusters lead to significant amounts of CORR products (methane and ethylene) with a maximum ethylene Faradaic efficiency of 22\% in acetonitrile (χH2O = 0.2). In contrast, microhomogeneous systems-where water integrates into the solvents{\textquoteright} intermolecular binding network and has lower activity-primarily support the undesired hydrogen evolution reaction (HER). Insights gained expand our understanding of water activity and nonaqueous electrolyte design for other important transformation reactions beyond CO reduction, such as CO2RR and HER.",

author = "Hannah Fejzi{\'c} and Ritesh Kumar and Gomes, \{Reginaldo J.\} and Lilin He and Houser, \{Theodore J.\} and Jaemin Kim and Matin Mohebi and Nora Molten and Amanchukwu, \{Chibueze V.\}",

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AU - Fejzić, Hannah

AU - Kumar, Ritesh

AU - Gomes, Reginaldo J.

AU - He, Lilin

AU - Houser, Theodore J.

AU - Kim, Jaemin

AU - Mohebi, Matin

AU - Molten, Nora

AU - Amanchukwu, Chibueze V.

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AB - Water solvation plays a critical role in a wide range of electrochemical transformations, but its role is often convoluted since water is typically used as both a solvent and a proton source. Here, we experimentally control water speciation and activity using aprotic solvent media during the carbon monoxide reduction reaction (CORR). Remarkably, we show that aprotic solvents that support microheterogeneous water-water clusters lead to significant amounts of CORR products (methane and ethylene) with a maximum ethylene Faradaic efficiency of 22% in acetonitrile (χH2O = 0.2). In contrast, microhomogeneous systems-where water integrates into the solvents’ intermolecular binding network and has lower activity-primarily support the undesired hydrogen evolution reaction (HER). Insights gained expand our understanding of water activity and nonaqueous electrolyte design for other important transformation reactions beyond CO reduction, such as CO2RR and HER.

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Water Clustering Modulates Activity and Enables Hydrogenated Product Formation during Carbon Monoxide Electroreduction in Aprotic Media

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