共 76 条
Mechanism of CO2 Reduction at Copper Surfaces: Pathways to C2 Products
被引:758
作者:
Garza, Alejandro J.
[1
]
Bell, Alexis T.
[2
]
Head-Gordon, Martin
[3
]
机构:
[1] Lawrence Berkeley Natl Lab, Joint Ctr Artificial Photosynth, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Dept Chem & Biomol Engn, Berkeley, CA 94720 USA
[3] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
关键词:
artificial photosynthesis;
DFT;
electrocatalysis;
mechanisms;
ethanol;
ethylene;
SINGLE-CRYSTAL ELECTRODES;
FREE-ENERGY CALCULATIONS;
FINDING SADDLE-POINTS;
ELECTROCHEMICAL REDUCTION;
CU(100) SURFACE;
CARBON-MONOXIDE;
THEORETICAL INSIGHTS;
ELECTROREDUCTION;
ADSORPTION;
KINETICS;
D O I:
10.1021/acscatal.7b03477
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:
On the basis of constraints from reported experimental observations and density functional theory simulations, we propose a mechanism for the reduction of CO2 to C-2 products on copper electrodes. To model the effects of an applied potential bias on the reactions, calculations are carried out with a variable, fractional number of electrons on the unit cell, which is optimized so that the Fermi level matches the actual chemical potential of electrons (i.e., the applied bias); an implicit electrolyte model allows for compensation of the surface charge so that neutrality is maintained in the overall simulation cell. Our mechanism explains the presence of the seven C-2 species that have been detected in the reaction, as well as other notable experimental observations. Furthermore, our results shed light on the difference in activities toward C-2 products between the (100) and (111) facets of copper. We compare our methodologies and findings with those in other recent mechanistic studies of the copper-catalyzed CO2 reduction reaction.
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页码:1490 / 1499
页数:10
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