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

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

doi:10.1002/anie.201800367

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

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

Research output: Contribution to journal › Article › peer-review

136 Scopus citations

Abstract

Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO₂ 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 CO₂ 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.

Original language	English (US)
Pages (from-to)	4981-4985
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	18
DOIs	https://doi.org/10.1002/anie.201800367
State	Published - Apr 23 2018
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry

Keywords

CO reduction
electrocatalysis
N-heterocyclic carbenes
palladium
surface chemistry

Access to Document

10.1002/anie.201800367

Cite this

Cao, Z., Derrick, J. S., Xu, J., Gao, R., Gong, M., Nichols, E. M., Smith, P. T., Liu, X., Wen, X., Copéret, C., & Chang, C. J. (2018). Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO₂ Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry. Angewandte Chemie - International Edition, 57(18), 4981-4985. https://doi.org/10.1002/anie.201800367

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abstract = "Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO2 reduction. Palladium functionalized with a chelating tris-N-heterocyclic carbene (NHC) ligand (Pd-timtmbMe) exhibits a 32-fold increase in activity for electrochemical reduction of CO2 to C1 products with high Faradaic efficiency (FEC1=86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC-ligated Pd electrode (Pd-mimtmbMe). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular-materials interfaces enabled by surface organometallic chemistry.",

keywords = "CO reduction, electrocatalysis, N-heterocyclic carbenes, palladium, surface chemistry",

author = "Zhi Cao and Derrick, {Jeffrey S.} and Jun Xu and Rui Gao and Ming Gong and Nichols, {Eva M.} and Smith, {Peter T.} and Xingwu Liu and Xiaodong Wen and Christophe Cop{\'e}ret and Chang, {Christopher J.}",

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year = "2018",

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doi = "10.1002/anie.201800367",

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Cao, Z, Derrick, JS, Xu, J, Gao, R, Gong, M, Nichols, EM, Smith, PT, Liu, X, Wen, X, Copéret, C & Chang, CJ 2018, 'Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO₂ Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry', Angewandte Chemie - International Edition, vol. 57, no. 18, pp. 4981-4985. https://doi.org/10.1002/anie.201800367

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T1 - Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO2 Reduction to Formate and Carbon Monoxide

T2 - Surface Organometallic Chemistry

AU - Cao, Zhi

AU - Derrick, Jeffrey S.

AU - Xu, Jun

AU - Gao, Rui

AU - Gong, Ming

AU - Nichols, Eva M.

AU - Smith, Peter T.

AU - Liu, Xingwu

AU - Wen, Xiaodong

AU - Copéret, Christophe

AU - Chang, Christopher J.

PY - 2018/4/23

Y1 - 2018/4/23

N2 - Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO2 reduction. Palladium functionalized with a chelating tris-N-heterocyclic carbene (NHC) ligand (Pd-timtmbMe) exhibits a 32-fold increase in activity for electrochemical reduction of CO2 to C1 products with high Faradaic efficiency (FEC1=86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC-ligated Pd electrode (Pd-mimtmbMe). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular-materials interfaces enabled by surface organometallic chemistry.

AB - Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO2 reduction. Palladium functionalized with a chelating tris-N-heterocyclic carbene (NHC) ligand (Pd-timtmbMe) exhibits a 32-fold increase in activity for electrochemical reduction of CO2 to C1 products with high Faradaic efficiency (FEC1=86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC-ligated Pd electrode (Pd-mimtmbMe). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular-materials interfaces enabled by surface organometallic chemistry.

KW - CO reduction

KW - electrocatalysis

KW - N-heterocyclic carbenes

KW - palladium

KW - surface chemistry

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