Supramolecular Porphyrin Cages Assembled at Molecular-Materials Interfaces for Electrocatalytic CO Reduction

被引：65

作者：

Gong, Ming ^{[1
,4
]}

Cao, Zhi ^{[1
]}

Liu, Wei ^{[1
,3
]}

Nichols, Eva M. ^{[1
,4
]}

Smith, Peter T. ^{[1
]}

Derrick, Jeffrey S. ^{[1
,4
]}

Liu, Yi-Sheng ^{[5
]}

Liu, Jinjia ^{[6
]}

Wen, Xiaodong ^{[6
,7
]}

Chang, Christopher J. ^{[1
,2
,3
,4
]}

机构：

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

[2] Univ Calif Berkeley, Dept Mol & Cell Biol, 229 Stanley Hall, Berkeley, CA 94720 USA

[3] Univ Calif Berkeley, Howard Hughes Med Inst, Berkeley, CA 94720 USA

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

[5] Lawrence Berkeley Natl Lab, Adv Light Source, Berkeley, CA 94720 USA

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

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

来源：

ACS CENTRAL SCIENCE | 2017年 / 3卷 / 09期

关键词：

CO2-TO-CO ELECTROCHEMICAL CONVERSION; HYDROGEN-EVOLUTION REACTION; METAL-ORGANIC FRAMEWORKS; CARBON-DIOXIDE REDUCTION; VISIBLE-LIGHT; UNDERPOTENTIAL DEPOSITION; SELECTIVE CONVERSION; MANGANESE-PORPHYRIN; COPPER NANOCRYSTALS; C-2; PRODUCTS;

D O I：

10.1021/acscentsci.7b00316

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon-carbon coupled products via self-assembly of supramolecular cages at molecular-materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiolterminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C-2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm(2)) at a potential of -0.40 V vs RHE. The cagefunctionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation.

引用

页码：1032 / 1040

页数：9

共 78 条

[1] SYNTHESIS OF A CYCLIC PORPHYRIN TRIMER WITH A SEMI-RIGID CAVITY [J].

ANDERSON, HL ;

SANDERS, JKM .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (22) :1714-1715

[2] AMINE-TEMPLATE-DIRECTED SYNTHESIS OF CYCLIC PORPHYRIN OLIGOMERS [J].

ANDERSON, HL ;

SANDERS, JKM .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1990, 29 (12) :1400-1403

[3] 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

[4] 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

[5] Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins [J].

Bediako, D. Kwabena ;

Solis, Brian H. ;

Dogutan, Dilek K. ;

Roubelakis, Manolis M. ;

Maher, Andrew G. ;

Lee, Chang Hoon ;

Chambers, Matthew B. ;

Hammes-Schiffer, Sharon ;

Nocera, Daniel G. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2014, 111 (42) :15001-15006

[6] 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

[7] Iodide-Selective Synthetic Ion Channels Based on Shape-Persistent Organic Cages [J].

Benke, Bahiru Punja ;

Aich, Pulakesh ;

Kim, Younghoon ;

Kim, Kyung Lock ;

Rohman, Md Rumum ;

Hong, Soonsang ;

Hwang, In-Chul ;

Lee, Eun Hui ;

Roh, Joon Ho ;

Kim, Kimoon .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (22) :7432-7435

[8] Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper [J].

Bertheussen, Erlend ;

Verdaguer-Casadevall, Arnau ;

Ravasio, Davide ;

Montoya, Joseph H. ;

Trimarco, Daniel B. ;

Roy, Claudie ;

Meier, Sebastian ;

Wendland, Juergen ;

Norskov, Jens K. ;

Stephens, Ifan E. L. ;

Chorkendorff, Ib .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (04) :1450-1454

[9] UNDERPOTENTIAL DEPOSITION OF LEAD ON COPPER(111) - A STUDY USING A SINGLE-CRYSTAL ROTATING-RING ELECTRODE AND EX-SITU LOW-ENERGY-ELECTRON DIFFRACTION AND AUGER-ELECTRON SPECTROSCOPY [J].

BRISARD, GM ;

ZENATI, E ;

GASTEIGER, HA ;

MARKOVIC, NM ;

ROSS, PN .

LANGMUIR, 1995, 11 (06) :2221-2230

[10] A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction [J].

Cao, Zhi ;

Kim, Dohyung ;

Hong, Dachao ;

Yu, Yi ;

Xu, Jun ;

Lin, Song ;

Wen, Xiaodong ;

Nichols, Eva M. ;

Jeong, Keunhong ;

Reimer, Jeffrey A. ;

Yang, Peidong ;

Chang, Christopher J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (26) :8120-8125

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