Chelating N‐Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO 2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry

Cao, Zhi; Derrick, Jeffrey S.; Xu, Jun; Gao, Rui; Gong, Ming; Nichols, Eva M.; Smith, Peter T.; Liu, Xingwu; Wen, Xiaodong; Copéret, Christophe; Chang, Christopher J.

doi:10.1002/ange.201800367

Chelating N‐Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO ₂ Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry

Journal Article · Fri Mar 23 00:00:00 EDT 2018 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201800367· OSTI ID:1429155

^[1]; Derrick, Jeffrey S. ^[2]; Xu, Jun ^[3]; Gao, Rui ^[4]; Gong, Ming ^[2]; Nichols, Eva M. ^[2]; Smith, Peter T. ^[2]; Liu, Xingwu ^[4]; Wen, Xiaodong ^[4]; Copéret, Christophe ^[3]; ^[5]

Department of Chemistry University of California Berkeley CA 94720 USA
Department of Chemistry University of California Berkeley CA 94720 USA, Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
Department of Chemistry and Applied Biosciences ETH Zürich Vladimir Prelog Weg 1–5 8093 Zürich Switzerland
Institute of Coal Chemistry Chinese Academy of Sciences Taiyuan Shanxi 030001 China, Synfuels China Beijing 100195 China
Department of Chemistry University of California Berkeley CA 94720 USA, Department of Molecular and Cell Biology Howard Hughes Medical Institute University of California Berkeley CA 94720 USA, Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Abstract

Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO ₂ reduction. Palladium functionalized with a chelating tris‐N‐heterocyclic carbene (NHC) ligand (Pd‐timtmb ^Me ) exhibits a 32‐fold increase in activity for electrochemical reduction of CO ₂ to C1 products with high Faradaic efficiency (FE _C1 =86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC‐ligated Pd electrode (Pd‐mimtmb ^Me ). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular‐materials interfaces enabled by surface organometallic chemistry.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1429155

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 18 Vol. 130; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO₂ Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry

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Chelating N‐Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO 2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry

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Chelating N‐Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO ₂ Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry