Direct CO2 Reduction to CO with an Fe4S4-Based Coordination Polymer

Le, Linh N. V.; Darù, Andrea; Kunstelj, Špela; Wuttig, Anna; Gagliardi, Laura; Anderson, John S.

doi:10.1021/jacs.5c23180

Direct CO₂ Reduction to CO with an Fe₄S₄-Based Coordination Polymer

Journal Article · Thu Apr 02 00:00:00 EDT 2026 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5c23180· OSTI ID:3025777

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Univ. of Chicago, IL (United States)

Fe₄S₄ clusters play essential roles in nature, classically in electron transport but increasingly in newly discovered reactivity or catalysis. These roles have spurred interest in developing synthetic Fe₄S₄ systems and while several molecular and material systems built from Fe₄S₄ clusters have been developed, comparatively few examples of synthetic Fe₄S₄ cluster-based catalysts exist. Herein, we present the use of an Fe₄S₄-based coordination polymer as a catalyst for the direct and selective electroreduction of CO₂ to CO. Computational studies suggest that the reaction proceeds through CO₂ binding to a reduced Fe₄S₄ cluster, followed by a series of protonation, reduction, and H₂O loss steps to yield a CO-bound cluster that can finally exchange with CO₂ to restart the catalytic cycle. CO bound clusters are predicted to be thermodynamically stable, suggesting that carbonyl species might be off-cycle intermediates. Mechanistic CV studies as well as in situ studies by IR spectroscopy provide evidence for carbonyl-ligated clusters, supporting these compounds as unusual examples of small molecule binding to Fe₄S₄ clusters. Finally, this work establishes Fe₄S₄ cluster-based coordination polymers as direct electrocatalysts for CO₂ reduction and provides mechanistic insights into how these species mediate catalytic conversions of small molecules.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023383

OSTI ID:: 3025777

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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