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Journal ArticleDOI

CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface

TLDR
A copper electrocatalyst at an abrupt reaction interface in an alkaline electrolyte reduces CO2 to ethylene with 70% faradaic efficiency at a potential of −0.55 volts versus a reversible hydrogen electrode (RHE).
Abstract
Carbon dioxide (CO 2 ) electroreduction could provide a useful source of ethylene, but low conversion efficiency, low production rates, and low catalyst stability limit current systems. Here we report that a copper electrocatalyst at an abrupt reaction interface in an alkaline electrolyte reduces CO 2 to ethylene with 70% faradaic efficiency at a potential of −0.55 volts versus a reversible hydrogen electrode (RHE). Hydroxide ions on or near the copper surface lower the CO 2 reduction and carbon monoxide (CO)–CO coupling activation energy barriers; as a result, onset of ethylene evolution at −0.165 volts versus an RHE in 10 molar potassium hydroxide occurs almost simultaneously with CO production. Operational stability was enhanced via the introduction of a polymer-based gas diffusion layer that sandwiches the reaction interface between separate hydrophobic and conductive supports, providing constant ethylene selectivity for an initial 150 operating hours.

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Citations
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Journal ArticleDOI

Hydroxide Is Not a Promoter of C2+ Product Formation in the Electrochemical Reduction of CO on Copper

TL;DR: It is demonstrated that higher concentrations of cations (Na + ), rather than OH - , exert the main promotional effect on the production of C 2+ products by systematically varying the concentration of Na + and OH - at identical absolute electrode potential.
Journal ArticleDOI

Direct and continuous generation of pure acetic acid solutions via electrocatalytic carbon monoxide reduction.

TL;DR: In this paper, the authors demonstrate a direct and continuous generation of pure acetic acid solutions via electrochemical CO reduction by coupling rational designs in a Cu catalyst and porous solid electrolyte (PSE) reactor.
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Oxygen induced promotion of electrochemical reduction of CO 2 via co-electrolysis.

TL;DR: It is found that co-electrolysis of CO2 with O2 can enhance copper’s catalytic activities and is a promising strategy to introduce catalytically active species in electrocatalysis.
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Electronic Effects Determine the Selectivity of Planar Au–Cu Bimetallic Thin Films for Electrochemical CO2 Reduction

TL;DR: The formation of CO and HCOO– as main CO2 reduction products on planar Au–Cu alloys followed the shift of the d-band center, which indicates that the electronic effect is the major governing factor for the electrocatalytic activity ofCO2 reduction on Au– Cu bimetallic thin films.
Journal ArticleDOI

A Planar, Conjugated N 4 -Macrocyclic Cobalt Complex for Heterogeneous Electrocatalytic CO 2 Reduction with High Activity

TL;DR: A novel planar and conjugated N4-macrocyclic cobalt complex (Co(II)CPY) derived from phenanthroline subunits is prepared, which delivers high activity for heterogeneous CO 2 electrocatalysis to CO in an aqueous medium and outperforms most of the metal complexes reported so far.
References
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Journal ArticleDOI

Generalized Gradient Approximation Made Simple

TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.
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Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.

TL;DR: An efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set is presented and the application of Pulay's DIIS method to the iterative diagonalization of large matrices will be discussed.
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From ultrasoft pseudopotentials to the projector augmented-wave method

TL;DR: In this paper, the formal relationship between US Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived and the Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional.
Journal ArticleDOI

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points

TL;DR: An improved way of estimating the local tangent in the nudged elastic band method for finding minimum energy paths is presented, and examples given where a complementary method, the dimer method, is used to efficiently converge to the saddle point.
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A grid-based Bader analysis algorithm without lattice bias

TL;DR: This paper describes how accurate off-lattice ascent paths can be represented with respect to the grid points, and maintains the efficient linear scaling of an earlier version of the algorithm, and eliminates a tendency for the Bader surfaces to be aligned along the grid directions.
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