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Research Article | Open Access

Mixed-valence Cu-based metal-organic framework for selective CO2 electroreduction to C1 liquid fuels with high energy conversion efficiency

Luyao Wang1, Fengting Li1,2,3 (), Yifan Gu1,2,3 ()
College of Environmental Science and Engineering, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092, China
Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China
Key Laboratory of Cities’ Mitigation and Adaptation to Climate Change, Shanghai, China Meteorological Administration (CMA), Tongji University, Shanghai 200092, China
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This work demonstrates the preparation of a novel mixed-valence Cu-based metal-organic framework Tongji University Environment (TJE)-ttfp (ttfp = 4-{2-[4,5-di(4-pyridinyl)-1,3-dithiol-2-ylidene]-5-(4-pyridinyl)-1,3-dithiol-4-yl}pyridine) using an electron-rich linker for electrocatalytic reduction of CO2. The designed material delivered a remarkable Faradaic efficiency of 99.2% for C1 liquid fuels at a low reduction potential of −0.1 V versus reversible hydrogen electrode.

Abstract

Efficient CO2 electroreduction requires catalysts for enhanced energy conversion efficiency and carbon product selectivity with low overpotential, in consideration of the interference of competitive H2 evolution reaction and complex intermediate species involved. We proposed that adaptive electronic structures based on dynamic mixed-valence interconversion would facilitate electron transfer and intermediate turnover during the catalysis, ensuring high activity, selectivity, and durability. Herein, a novel mixed-valence Cu-based metal-organic framework was prepared using an electron-rich linker for electrocatalytic reduction of CO2. The designed material delivered a remarkable Faradaic efficiency of 99.2% for C1 liquid fuels at a low reduction potential of −0.1 V versus reversible hydrogen electrode, considerably higher than that of the commercial copper foam and competitive to the Cu-based electrocatalysts reported. The experimental data and theoretical calculations verified the Cu(I)/Cu(II) interconversion and the much higher energy barrier of H2 evolution than carbon product generation. Such a feasible strategy, simultaneously improving energy conversion efficiency, carbon product selectivity, and structural robustness, provides great insights into rational catalyst customization for sustainable CO2 conversion.

Keywords

metal-organic frameworksCO2 electroreductionmixed-valenceenergy conversion efficiencyliquid fuelscatalysis

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Nano Research
Volume 18 Issue 4,
April 2025
Article number: 94907317
DOI: 10.26599/NR.2025.94907317
Cite this article:
Wang L, Li F, Gu Y. Mixed-valence Cu-based metal-organic framework for selective CO2 electroreduction to C1 liquid fuels with high energy conversion efficiency. Nano Research, 2025, 18(4): 94907317. https://doi.org/10.26599/NR.2025.94907317
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