In-situ reconstructed Cu-In2O3 electron-rich interfaces facilitate high selective CO2-to-CO conversion at low potentials

doi:10.1016/S1872-2067(26)65017-6

Abstract

Abstract:

The electroreduction of CO₂ to CO is fundamentally hindered by sluggish COOH intermediate formation and the competing hydrogen evolution reaction. Herein, we show that this challenge can be addressed through the dynamic in-situ reconstruction of a CuO/In₂O₃ precursor under electrochemical CO₂ reduction conditions. By employing in-situ electrochemical spectroscopy techniques in combination with theoretical calculations, we demonstrate that the presence of In₂O₃ facilitates the complete reduction of CuO to metallic Cu. This in-situ reconstruction produces electron-rich Cu-In₂O₃ interfaces, characterized by a reduced work function and an upshifted Cu 3d-band center, which promote CO₂ activation and the formation of COOH/CO intermediates. Those interfacial properties lead to a pronounced electronic coupling that endows the electrocatalyst with high CO₂-to-CO selectivity at low potentials. Specifically, the optimised Cu/In₂O₃ achieves CO Faradaic efficiency above 90% across −0.5 to −0.9 V vs. the reversible hydrogen electrode, reaching 97.6% at −0.6 V in a H-type cell, and sustains a high CO selectivity of 96.0% even at an ultralow potential of −0.2 V in a flow-cell configuration. These findings underscore the crucial role of electron-rich interfaces in directing CO₂ reduction with exceptional selectivity and activity toward CO formation.

Key words: CO₂ reduction reaction, In-situ reconstruction, Cu/In₂O₃ composite, Electron-rich interface, CO₂-to-CO conversion

Bin Yang, Ouardia Akdim, Chengcheng Yuan, Ruina Li, Luo Yu, Hermenegildo García, Jiaguo Yu, Graham J. Hutchings, Panyong Kuang. In-situ reconstructed Cu-In₂O₃ electron-rich interfaces facilitate high selective CO₂-to-CO conversion at low potentials[J]. Chinese Journal of Catalysis, 2026, 85: 117-129.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65017-6

https://www.cjcatal.com/EN/Y2026/V85/I6/117

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Fig. 1. (a) Schematic illustration of the synthesis process. SEM images (b,c), TEM image (d), EDX images (e), HRTEM images (f-h), and XRD pattern (i) of CuO/In2O3.

Fig. 2. FE values for CO, H2, and other products on CuO/In2O3 (a), CuO (b), and In2O3 (c) in an H-cell configuration. (d) FECO and jCO of CuO/In2O3, CuO, and In2O3 at −0.6 V. (e) TOF of CuO/In2O3, CuO, and In2O3 at various applied potentials. (f) Long-term stability test of CuO/In2O3. (g) Schematic illustration of the flow-cell setup used for high current density CO2RR testing. (h) LSV curve of CuO/In2O3 in the flow-cell. (i) Corresponding FECO and jCO values of CuO/In2O3 in the flow-cell.

Fig. 3. (a) In-situ XRD patterns of CuO/In2O3 after electroreduction at −0.6, −0.9, and −1.2 V. SEM (b), TEM (c), EDX (d,e), and HRTEM (f-j) images of CuO/In2O3 after electroreduction at −0.9 V. (k) In-situ XRD patterns of CuO after electroreduction at −0.6, −0.9, and −1.2 V. SEM (l), TEM (m), EDX (n, o), and HRTEM (p-t) images of CuO after electroreduction at −0.9 V.

Fig. 4. In-situ Cu K-edge XANES and FT-EXAFS spectra of CuO/In2O3 (a,b) and CuO (c,d) after electroreduction at −0.6, −0.9, and −1.2 V. (e) Experimentally measured ϕ of Cu/In2O3, Cu, and In2O3. (f) Hall coefficient of Cu/In2O3 and Cu/Cu2O. (g) Schematic illustration of the in-situ reconstruction of CuO/In2O3 and CuO, highlighting the formation of Cu-In2O3 electron-rich interface and Cu-Cu2O interface, respectively.

Fig. 5. In-situ ATR-SEIRAS spectra of Cu/In2O3 (a), Cu/Cu2O (b), and In2O3 (c). The order of magnitude of the intensity is 10−4. (d) Integrated peak areas of *COOH and *CO vibrational bands. (e) Calculated reaction free energy diagrams for CO2-to-CO conversion on Cu/In2O3, Cu/Cu2O, and In2O3. (f) Δρ at the Cu-In2O3 electron-rich interface. (g) Theoretically calculated ϕ of Cu/In2O3, Cu/Cu2O, and In2O3. (h) DOS and εd of Cu/In2O3 and Cu/Cu2O. (i) Schematic illustration of orbital occupation engineering at the Cu/In2O3 interface to modulate bonding and antibonding states. (j) Conceptual diagram of enhanced CO2-to-CO conversion facilitated by the Cu-In2O3 electron-rich interface.

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In-situ reconstructed Cu-In₂O₃ electron-rich interfaces facilitate high selective CO₂-to-CO conversion at low potentials

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