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

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

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.\}",

note = "Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2018",

month = apr,

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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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