Bioinspired Electrocatalyst for CO2 Electroreduction to Ethanol via Secondary-Sphere Synergy in Fe Porphyrinic-Based Metal-Organic Frameworks

Abstract

Carbon dioxide electroreduction reaction (CO2RR) to ethanol (C2H5OH) represents a sustainable route toward carbon neutrality. Herein, we present the design of enzyme-inspired zirconium-Fe porphyrinic-based metal-organic framework (MOF) nanosheets functionalized with 5-benzimidazolecarboxylic acid (FeTCPP-NSs-BAA) for CO2RR. Electrochemical performances in H-cell reveal that FeTCPP-NSs-BAA achieves C2H5OH Faradaic efficiencies (FEs) of 79.8% under neutral and 89.2% under acidic conditions, with C2H5OH FEs exceeding 60% over wide potential windows of –0.3 to –0.6 V and –0.3 to –0.8 V, respectively. In flow cell tests under acidic conditions, FeTCPP-NSs-BAA delivers a highest C2H5OH partial current density of 8.1 mA cm–2 with pure CO2, and a C2H5OH partial current density of 5.6 mA cm–2 when using 30% low-concentration CO2. Operando spectroscopic characterizations and theoretical calculations reveal that the superior C2H5OH performance of FeTCPP-NSs-BAA arises from the enzyme-like non-covalent synergistic effects between FeTCPP and the secondary-sphere functionalities of BAA and Zr6 clusters. Specifically, BAA enhances CO2 enrichment and facilitates the formation of tilted *CO adsorption at Fe centers on FeTCPP, which significantly reduces energy barriers for *CO-CO coupling compared to linearly adsorbed *CO. Meanwhile, the subsequent hydrogenation of *CO-CO to C2H5OH can be further accelerated by proton shuttling mediated through hydrogen-bonding networks introduced by Zr6 clusters.

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Article information

Article type
Paper
Submitted
10 Mar 2025
Accepted
20 May 2025
First published
28 May 2025

Energy Environ. Sci., 2025, Accepted Manuscript

Bioinspired Electrocatalyst for CO2 Electroreduction to Ethanol via Secondary-Sphere Synergy in Fe Porphyrinic-Based Metal-Organic Frameworks

K. Sun, S. Xie, P. Guan, Z. Zhuang, X. Tan, W. Yan, J. Zhang and C. Chen, Energy Environ. Sci., 2025, Accepted Manuscript , DOI: 10.1039/D5EE01388G

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