Tertiary Amine-Assisted Electroreduction of Carbon Dioxide to Formate Catalyzed by Iron Tetraphenylporphyrin

被引：64

作者：

Margarit, Charles G. ^{[1
]}

Asimow, Naomi G. ^{[1
]}

Costentin, Cyrille ^{[1
,2
,3
]}

Nocera, Daniel G. ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

[2] Univ Paris Diderot, Sorbonne Paris Cite, F-75205 Paris 13, France

[3] Univ Grenoble Alpes, CNRS, UMR 5250, Dept Chim Mol, F-3800 Grenoble, France

来源：

ACS ENERGY LETTERS | 2020年 / 5卷 / 01期

关键词：

ELECTROCHEMICAL REDUCTION; MOLECULAR CATALYSIS; ELECTROCATALYTIC REDUCTION; CO2; BOND; PORPHYRINS; CONVERSION; EVOLUTION; INSERTION;

D O I：

10.1021/acsenergylett.9b02093

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The reduction of CO, by electrogenerated Fe(0)TPP can be directed toward formate with a good selectivity (ca. 70%) upon addition of a tertiary amine in the presence of a weak proton donor. Whereas most systems generating formate from CO2 involve the initial formation of a hydride, we demonstrate herein that the hydride pathway is avoided by preferential binding of CO2 that may then be protonated by weak acids. The net result is that hydrogen production via the hydride is disfavored, thus leading to high yields of formate. These results demonstrate an alternative route for the activation of CO2 to formate.

引用

页码：72 / +

页数：13

共 36 条

[1] Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO2-to-CO Electrochemical Conversion [J].

Azcarate, Iban ;

Costentin, Cyrille ;

Robert, Marc ;

Saveant, Jean-Michel .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (51) :16639-16644

[2] Catalysis of the electrochemical reduction of carbon dioxide by iron(0) porphyrins. Synergistic effect of Lewis acid cations [J].

Bhugun, I ;

Lexa, D ;

Saveant, JM .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (51) :19981-19985

[3] Catalysis of the electrochemical reduction of carbon dioxide by iron(O) porphyrins: Synergystic effect of weak Bronsted acids [J].

Bhugun, I ;

Lexa, D ;

Saveant, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (07) :1769-1776

[4] Homogeneous catalysis of electrochemical hydrogen evolution by iron(0) porphyrins [J].

Bhugun, I ;

Lexa, D ;

Saveant, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (16) :3982-3983

[5] Directing the reactivity of metal hydrides for selective CO2 reduction [J].

Ceballos, Bianca M. ;

Yang, Jenny Y. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2018, 115 (50) :12686-12691

[6] Electrocatalytic Reduction of CO2 into Formate with Glassy Carbon Modified by [Fe4N(CO)11(PPh2Ph-linker)]- [J].

Cluff, David B. ;

Arnold, Amela ;

Fettinger, James C. ;

Berben, Louise A. .

ORGANOMETALLICS, 2019, 38 (06) :1230-1235

[7] Towards an intelligent design of molecular electrocatalysts [J].

Costentin, Cyrille ;

Saveant, Jean-Michel .

NATURE REVIEWS CHEMISTRY, 2017, 1 (11)

[8] Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime [J].

Costentin, Cyrille ;

Nocera, Daniel G. ;

Brodsky, Casey N. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2017, 114 (43) :11303-11308

[9] Ultraefficient homogeneous catalyst for the CO2-to-CO electrochemical conversion [J].

Costentin, Cyrille ;

Passard, Guillaume ;

Robert, Marc ;

Saveant, Jean-Michel .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2014, 111 (42) :14990-14994

[10] Molecular Catalysis of H2 Evolution: Diagnosing Heterolytic versus Homolytic Pathways [J].

Costentin, Cyrille ;

Dridi, Hachem ;

Saveant, Jean-Michel .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (39) :13727-13734

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