Second-Sphere Biomimetic Multipoint Hydrogen-Bonding Patterns to Boost CO2 Reduction of Iron Porphyrins

被引：133

作者：

Gotico, Philipp ^{[1
]}

Boitrel, Bernard ^{[2
]}

Guillot, Regis ^{[3
]}

Sircoglou, Marie ^{[3
]}

Quaranta, Annamaria ^{[1
]}

Halime, Zakaria ^{[3
]}

Leibl, Winfried ^{[1
]}

Aukauloo, Ally ^{[1
,3
]}

机构：

[1] CEA Saclay, Inst Biol Integrat Cellule I2BC, Inst Sci Vivant Frederic Joliot, F-91191 Gif Sur Yvette, France

[2] Univ Rennes, CNRS, ISCR, UMR 6226, F-35000 Rennes, France

[3] Univ Paris Sud, ICMMO, CNRS, UMR 8182, F-91405 Orsay, France

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 14期

关键词：

carbon dioxide reduction; hydrogen bonding; iron; porphyrins; urea; CO2-TO-CO ELECTROCHEMICAL CONVERSION; PICKET-FENCE PORPHYRINS; CARBON-DIOXIDE; MOLECULAR CATALYSIS; COMPLEXES; BINDING; EFFICIENT; MODELS; FE;

D O I：

10.1002/anie.201814339

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Inspired by nature's orchestra of chemical subtleties to activate and reduce CO2, we have developed a family of iron porphyrin derivatives in to which we have introduced urea groups functioning as multipoint hydrogen-bonding pillars on the periphery of the porphyrinic ring. This structure closely resembles the hydrogen-bond stabilization scheme of the carbon dioxide (CO2) adduct in the carbon monoxide dehydrogenase (CODH). We found that such changes to the second coordination sphere significantly lowered the overpotential for CO2 reduction in this family of molecular catalysts and importantly increased the CO2 binding rate while maintaining high turnover frequency (TOF) and selectivity. Entrapped water molecules within the molecular clefts were found to be the source of protons for the CO2 reduction.

引用

页码：4504 / 4509

页数：6

共 36 条

[1] 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

[2] 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

[3] Structure, Function, and Mechanism of the Nickel Metalloenzymes, CO Dehydrogenase, and Acetyl-CoA Synthase [J].

Can, Mehmet ;

Armstrong, Fraser A. ;

Ragsdale, Stephen W. .

CHEMICAL REVIEWS, 2014, 114 (08) :4149-4174

[4] Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction [J].

Chapovetsky, Alon ;

Welborn, Matthew ;

Luna, John M. ;

Haiges, Ralf ;

Miller, Thomas F., III ;

Marinescu, Smaranda C. .

ACS CENTRAL SCIENCE, 2018, 4 (03) :397-404

[5] REVERSIBLE OXYGEN ADDUCT FORMATION IN FERROUS COMPLEXES DERIVED FROM A PICKET FENCE PORPHYRIN - MODEL FOR OXYMYOGLOBIN [J].

COLLMAN, JP ;

GAGNE, RR ;

HALBERT, TR ;

MARCHON, JC ;

REED, CA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (23) :7868-7870

[6] PICKET-FENCE PORPHYRINS - SYNTHETIC MODELS FOR OXYGEN BINDING HEMOPROTEINS [J].

COLLMAN, JP ;

GAGNE, RR ;

REED, CA ;

HALBERT, TR ;

LANG, G ;

ROBINSON, WT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (06) :1427-1439

[7] Highly Selective Molecular Catalysts for the CO2-to-CO Electrochemical Conversion at Very Low Overpotential. Contrasting Fe vs Co Quaterpyridine Complexes upon Mechanistic Studies [J].

Cometto, Claudio ;

Chen, Lingjing ;

Lo, Po-Kam ;

Guo, Zhenguo ;

Lau, Kai-Chung ;

Anxolabehere-Mallart, Elodie ;

Fave, Claire ;

Lau, Tai-Chu ;

Robert, Marc .

ACS CATALYSIS, 2018, 8 (04) :3411-3417

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

Costentin, Cyrille ;

Saveant, Jean-Michel .

NATURE REVIEWS CHEMISTRY, 2017, 1 (11)

[9] Efficient and selective molecular catalyst for the CO2-to-CO electrochemical conversion in water [J].

Costentin, Cyrille ;

Robert, Marc ;

Saveant, Jean-Michel ;

Tatin, Arnaud .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2015, 112 (22) :6882-6886

[10] 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

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