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

被引：120

作者：

Cao, Zhi ^{[1
]}

Derrick, Jeffrey S. ^{[1
,3
]}

Xu, Jun ^{[4
]}

Gao, Rui ^{[5
,6
]}

Gong, Ming ^{[1
,3
]}

Nichols, Eva M. ^{[1
,3
]}

Smith, Peter T. ^{[1
,3
]}

Liu, Xingwu ^{[5
,6
]}

Wen, Xiaodong ^{[5
,6
]}

Coperet, Christophe ^{[4
]}

Chang, Christopher J. ^{[1
,2
,3
]}

机构：

[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[2] Univ Calif Berkeley, Howard Hughes Med Inst, Dept Mol & Cell Biol, Berkeley, CA 94720 USA

[3] Lawrence Berkeley Natl Lab, Chem Sci Div, Berkeley, CA 94720 USA

[4] ETH, Dept Chem & Appl Biosci, Vladimir Prelog Weg 1-5, CH-8093 Zurich, Switzerland

[5] Chinese Acad Sci, Inst Coal Chem, Taiyuan 030001, Shanxi, Peoples R China

[6] Synfuels China, Beijing 100195, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 18期

基金：

美国国家科学基金会; 中国国家自然科学基金;

关键词：

CO2; reduction; electrocatalysis; N-heterocyclic carbenes; palladium; surface chemistry; SELF-ASSEMBLED MONOLAYERS; RUTHENIUM NANOPARTICLES; GOLD NANOPARTICLES; PINCER COMPLEXES; PALLADIUM NANOPARTICLES; FORMIC-ACID; CATALYSTS; WATER; STABILIZATION; SELECTIVITY;

D O I：

10.1002/anie.201800367

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 (FEC1=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.

引用

页码：4981 / 4985

页数：5

共 50 条

[41] Ligand-Structure Effects on N-Heterocyclic Carbene Rhenium Photo- and Electrocatalysts of CO2 Reduction
Kearney, Lauren
Brandon, Michael P.
Coleman, Andrew
Chippindale, Ann M.
Hartl, Frantisek
Lalrempuia, Ralte
Pizl, Martin
Pryce, Mary T.
MOLECULES, 2023, 28 (10):
[42] Carbon monoxide as a reagent: A report on the role of N-heterocyclic carbene (NHC) ligands in metal-catalyzed carbonylation reactions
Veige, Adam S.
POLYHEDRON, 2008, 27 (15) : 3177 - 3189
[43] Bifunctional N-heterocyclic carbene ligands for Cu-catalyzed direct C-H carboxylation with CO2
Park, Da-Ae
Ryu, Ji Yeon
Lee, Junseong
Hong, Sukwon
RSC ADVANCES, 2017, 7 (83): : 52496 - 52502
[44] Bifunctional N-heterocyclic carbene ligands for Cu-catalyzed direct C-H carboxylation with CO2
Park, Da-Ae
Ryu, Ji Yeon
Lee, Junseong
Hong, Sukwon
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2018, 256
[45] Comparing the Activity of N-Heterocyclic Carbene Iron Complexes and Free Carbene Precursors in the Hydrosilylation of CO2
Nylund, Pamela V. S.
Rigoni, Giacomo
Albrecht, Martin
ORGANOMETALLICS, 2023, 42 (14) : 1740 - 1745
[46] Metalloradical intermediates in electrocatalytic reduction of CO2 to CO: Mn versus Re bis-N-heterocyclic carbene pincers
Myren, Tessa H. T.
Atherz, Abdutaziz
Stinson, Taylor A.
Huntzinger, Chloe G.
Lama, Bimala
Musgrave, Charles B.
Luca, Oana R.
DALTON TRANSACTIONS, 2020, 49 (07) : 2053 - 2057
[47] CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane
Khadka, Nimesh
Dean, Dennis R.
Smith, Dayle
Hoffman, Brian M.
Raugei, Simone
Seefeldt, Lance C.
INORGANIC CHEMISTRY, 2016, 55 (17) : 8321 - 8330
[48] N-Heterocyclic Carbene Functionalized Polymer for Reversible Fixation-Release of CO2
Zhou, Hui
Zhang, Wen-Zhen
Wang, Yi-Ming
Qu, Jing-Ping
Lu, Xiao-Bing
MACROMOLECULES, 2009, 42 (15) : 5419 - 5421
[49] Nickel N-heterocyclic carbene-pyridine complexes that exhibit selectivity for electrocatalytic reduction of carbon dioxide over water
Thoi, V. Sara
Chang, Christopher J.
CHEMICAL COMMUNICATIONS, 2011, 47 (23) : 6578 - 6580
[50] Percent buried volume for phosphine and N-heterocyclic carbene ligands: steric properties in organometallic chemistry (vol 46, pg 841, 2010)
Clavier, Herve
Nolan, Steven P.
CHEMICAL COMMUNICATIONS, 2010, 46 (48) : 9260 - 9261

← 1 2 3 4 5 →