Issue

Vol. 18 (2026)

Hetero-Solvent Microenvironment for Selective CO2 to Ethanol Electrolysis via Interfacial Water Control

https://doi.org/10.1007/s40820-026-02282-w
Dohun Kim
Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu 42988, Republic of Korea
Suyun Lee
Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu 42988, Republic of Korea
Seeun Jung
Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea
Jaemin Kim
Department of Chemical and Biomolecular Engineering, Sogang University, Seoul 04107, Republic of Korea
Junsic Cho
Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea
Dong Ki Lee
Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea
Seoin Back
Department of Integrative Energy Engineering, Korea University, Seoul 02841, Republic of Korea
Chang Hyuck Choi
Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea
Chanyeon Kim
Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu 42988, Republic of Korea

Corresponding Author: Chanyeon Kim

chanyeon@dgist.ac.kr

Nano-Micro Letters, Vol. 18 (2026), Article Number: 423

Abstract

Electrochemical reduction of carbon dioxide (CO2RR) offers a route for sustainable chemical production using water as a clean proton source. However, water also promotes the competing hydrogen evolution reaction, limiting CO2RR performance. Here we establish interfacial water as a decisive but overlooked design parameter for selective CO2-to-ethanol electrolysis. A hetero-solvent microenvironment confining diglyme (DiG) near the Cu catalyst substantially suppresses HER under both neutral and alkaline conditions, where protons are supplied via water dissociation. In situ infrared absorption spectroscopy and theoretical calculation results reveal that DiG strengthens the hydrogen-bonding network of interfacial water, reducing free-water population prone to dissociation. Concurrently, the modulated water network effectively hinders solvent-mediated hydrogenation that favors ethylene formation, thereby promoting ethanol formation. Because this strategy modulates the microenvironment rather than the catalyst, it readily extends to Cu–Ag bimetallic catalyst. Moreover, confining hetero-solvent within microenvironment rather than in the bulk electrolyte enables high-current operation at low cell voltages, achieving an ethanol partial current density of 184.2 mA cm−2 at 3.6 V under neutral condition.


Highlights:
1 A hetero-solvent-confined microenvironment regulates interfacial water during CO2 electrolysis on Cu, substantially suppressing hydrogen evolution by inhibiting water dissociation.
2 Inhibited water dissociation suppresses ethylene formation, which requires solvent-mediated hydrogenation, thereby steering selectivity toward ethanol.
3 This strategy is readily extended to Cu–Ag catalyst, enabling record-high ethanol production under neutral conditions while minimizing cell voltage by confining hetero-solvent within microenvironment rather than bulk electrolyte.

Keywords

Electrochemical CO2 reduction Microenvironment Diglyme Hetero-solvent Ethanol production
Kim, Dohun, Suyun Lee, Seeun Jung, Jaemin Kim, Junsic Cho, Dong Ki Lee, Seoin Back, Chang Hyuck Choi, and Chanyeon Kim. 2026. “Hetero-Solvent Microenvironment for Selective CO2 to Ethanol Electrolysis via Interfacial Water Control”. Nano-Micro Letters 18 (July):423. https://doi.org/10.1007/s40820-026-02282-w.
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