Potential- and Buffer-Dependent Selectivity for the Conversion of CO2 to CO by a Cobalt Porphyrin-Peptide Electrocatalyst in Water

被引：11

作者：

Alvarez-Hernandez, Jose L. ^{[1
,2
]}

Salamatian, Alison A. ^{[1
]}

Han, Ji Won ^{[1
]}

Bren, Kara L. ^{[1
]}

机构：

[1] Univ Rochester, Dept Chem, Rochester, NY 14627 USA

[2] Yale Univ, Dept Chem, New Haven, CT 06520 USA

来源：

ACS CATALYSIS | 2022年 / 12卷 / 23期

基金：

美国国家科学基金会;

关键词：

biocatalyst; carbon dioxide reduction; cobalt porphyrin; electrocatalysis; overpotential; COUPLED ELECTRON-TRANSFER; ACID-BASE CATALYSIS; CARBON-DIOXIDE; ELECTROCHEMICAL REDUCTION; HOMOGENEOUS CATALYSIS; MOLECULAR CATALYSIS; HYDROGEN EVOLUTION; CYCLIC VOLTAMMETRY; NICKEL(II) CYCLAM; BRONSTED ACID;

D O I：

10.1021/acscatal.2c03297

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：

A semisynthetic electrocatalyst for carbon dioxide reduction to carbon monoxide in water is reported. Cobalt microperoxidase-11 (CoMP11-Ac) is shown to reduce CO2 to CO with a turnover number of up to 32,000 and a selectivity of up to 88:5 CO:H2. Higher selectivity for CO production is favored by a less cathodic applied potential and use of a higher pKa buffer. A mechanistic hypothesis is presented in which avoiding the formation and protonation of a formal Co(I) species favors CO production. These results demonstrate how tuning reaction conditions impact reactivity toward CO2 reduction for a biocatalyst previously developed for H2 production.

引用

页码：14689 / 14697

页数：9

共 82 条

[1] Linear Free Energy Relationships in Hydrogen Evolution Catalysis by a Cobalt Tripeptide in Water [J].

Alvarez-Hernandez, Jose L. ;

Han, Ji Won ;

Sopchak, Andrew E. ;

Guo, Yixing ;

Bren, Kara L. .

ACS ENERGY LETTERS, 2021, 6 (06) :2256-2261

[2] Buffer pKa Impacts the Mechanism of Hydrogen Evolution Catalyzed by a Cobalt Porphyrin-Peptide [J].

Alvarez-Hernandez, Jose L. ;

Sopchak, Andrew E. ;

Bren, Kara L. .

INORGANIC CHEMISTRY, 2020, 59 (12) :8061-8069

[3] Activating the Fe(I) State of Iron Porphyrinoid with Second-Sphere Proton Transfer Residues for Selective Reduction of CO2 to HCOOH via Fe(III/II)-COOH Intermediate(s) [J].

Amanullah, Sk ;

Saha, Paramita ;

Dey, Abhishek .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2021, 143 (34) :13579-13592

[4] Determining the Overpotential for a Molecular Electrocatalyst [J].

Appel, Aaron M. ;

Helm, Monte L. .

ACS CATALYSIS, 2014, 4 (02) :630-633

[5] Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2 Fixation [J].

Appel, Aaron M. ;

Bercaw, John E. ;

Bocarsly, Andrew B. ;

Dobbek, Holger ;

DuBois, Daniel L. ;

Dupuis, Michel ;

Ferry, James G. ;

Fujita, Etsuko ;

Hille, Russ ;

Kenis, Paul J. A. ;

Kerfeld, Cheal A. ;

Morris, Robert H. ;

Peden, Charles H. F. ;

Portis, Archie R. ;

Ragsdale, Stephen W. ;

Rauchfuss, Thomas B. ;

Reek, Joost N. H. ;

Seefeldt, Lance C. ;

Thauer, Rudolf K. ;

Waldrop, Grover L. .

CHEMICAL REVIEWS, 2013, 113 (08) :6621-6658

[6] Solar fuels generation and molecular systems: is it homogeneous or heterogeneous catalysis? [J].

Artero, Vincent ;

Fontecave, Marc .

CHEMICAL SOCIETY REVIEWS, 2013, 42 (06) :2338-2356

[7] THE ADSORPTION OF NI(CYCLAM)+ AT MERCURY-ELECTRODES AND ITS RELATION TO THE ELECTROCATALYTIC REDUCTION OF CO2 [J].

BALAZS, GB ;

ANSON, FC .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1992, 322 (1-2) :325-345

[8] Inhibiting the Hydrogen Evolution Reaction (HER) with Proximal Cations: A Strategy for Promoting Selective Electrocatalytic Reduction [J].

Barlow, Jeffrey M. ;

Ziller, Joseph W. ;

Yang, Jenny Y. .

ACS CATALYSIS, 2021, 11 (13) :8155-8164

[9] NICKEL(II) CYCLAM - AN EXTREMELY SELECTIVE ELECTROCATALYST FOR REDUCTION OF CO2 IN WATER [J].

BELEY, M ;

COLLIN, JP ;

RUPPERT, R ;

SAUVAGE, JP .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (19) :1315-1316

[10] ELECTROCATALYTIC REDUCTION OF CO2 BY NI CYCLAM2+ IN WATER - STUDY OF THE FACTORS AFFECTING THE EFFICIENCY AND THE SELECTIVITY OF THE PROCESS [J].

BELEY, M ;

COLLIN, JP ;

RUPPERT, R ;

SAUVAGE, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (24) :7461-7467

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