Selectivity of CO2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps

被引：835

作者：

Nie, Xiaowa ^{[1
]}

Esopi, Monica R. ^{[2
]}

Janik, Michael J. ^{[2
]}

Asthagiri, Aravind ^{[1
]}

机构：

[1] Ohio State Univ, William G Lowrie Dept Chem & Biomol Engn, Koffolt Labs 221A, Columbus, OH 43210 USA

[2] Penn State Univ, Dept Chem Engn, Fenske Lab 104, University Pk, PA 16802 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2013年 / 52卷 / 09期

关键词：

carbon dioxide; density functional calculations; heterogeneous catalysis; kinetics; renewable energy; ELECTROCHEMICAL REDUCTION; CARBON-DIOXIDE; METHANOL; HYDROCARBONS; ETHYLENE; GAS;

D O I：

10.1002/anie.201208320

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

On the right path: Based on DFT calculations (incorporating the role of water solvation) of the activation barriers of elementary steps, a new path that leads to methane and ethylene for CO2 electroreduction on Cu(111) was identified. Methane formation proceeds through reduction of CO to COH (path II, see picture), which leads to CHx species that can produce both methane and ethylene, as observed experimentally. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：2459 / 2462

页数：4

共 20 条

[1]

Behrens M, 2012, SCIENCE, V336, P893, DOI [10.1126/science.1219831, 10.1126/science.12198331]

[2] ELECTROCHEMICAL AND SURFACE STUDIES OF CARBON-DIOXIDE REDUCTION TO METHANE AND ETHYLENE AT COPPER ELECTRODES IN AQUEOUS-SOLUTIONS [J].

DEWULF, DW ;

JIN, T ;

BARD, AJ .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1989, 136 (06) :1686-1691

[3] Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces [J].

Durand, William J. ;

Peterson, Andrew A. ;

Studt, Felix ;

Abild-Pedersen, Frank ;

Norskov, Jens K. .

SURFACE SCIENCE, 2011, 605 (15-16) :1354-1359

[4] A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper [J].

Gattrell, M. ;

Gupta, N. ;

Co, A. .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 2006, 594 (01) :1-19

[5] Activation of an Alkyl C-H Bond Geminal to an Agostic Interaction: An Unusual Mode of Base-Induced C-H Activation [J].

Haller, L. Jonas L. ;

Page, Michael J. ;

Macgregor, Stuart A. ;

Mahon, Mary F. ;

Whittlesey, Michael K. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (13) :4604-+

[6] ELECTROREDUCTION OF CO TO CH4 AND C2H4 AT A COPPER ELECTRODE IN AQUEOUS-SOLUTIONS AT AMBIENT-TEMPERATURE AND PRESSURE [J].

HORI, Y ;

MURATA, A ;

TAKAHASHI, R ;

SUZUKI, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (16) :5022-5023

[7] FORMATION OF HYDROCARBONS IN THE ELECTROCHEMICAL REDUCTION OF CARBON-DIOXIDE AT A COPPER ELECTRODE IN AQUEOUS-SOLUTION [J].

HORI, Y ;

MURATA, A ;

TAKAHASHI, R .

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS I, 1989, 85 :2309-2326

[8]

Hori Y, 2008, MOD ASP ELECTROCHEM, P89

[9] Electrochemical reduction of CO at a copper electrode [J].

Hori, Y ;

Takahashi, R ;

Yoshinami, Y ;

Murata, A .

JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (36) :7075-7081

[10] New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces [J].

Kuhl, Kendra P. ;

Cave, Etosha R. ;

Abram, David N. ;

Jaramillo, Thomas F. .

ENERGY & ENVIRONMENTAL SCIENCE, 2012, 5 (05) :7050-7059

← 1 2 →