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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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Insight into the Formation and Transfer Process of the First Intermediate of CO2 Reduction over Ag-Decorated Dendritic Cu.

TL;DR: Spectroscopic evidence is provided that the first intermediate of CO 2 reduction on Ag-decorated Cu is carboxylate anion *CO 2 - bonded with the catalyst surface through C and O atom.
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2022 roadmap on low temperature electrochemical CO2 reduction

TL;DR: In this article , the authors discuss the outstanding challenges towards commercialization of electrochemical CO2 reduction technology: energy efficiencies, selectivities, low current densities, and stability, and highlight the opportunities in establishing rigorous standards for benchmarking performance, advances in in operando characterization, the discovery of new materials towards high value products, the investigation of phenomena across multiple-length scales and the application of data science towards doing so.
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Linking dynamic chemical state of catalysts with product profile of electrocatalytic CO2 reduction.

TL;DR: In this article, the dynamic chemical state of Cu sites under CO2 RR conditions extracted by in situ/operando characterizations is analyzed and a critical link between the chemical states of Cu and the product profile of CO2 is established.
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CO2 valorisation towards alcohols by Cu-based electrocatalysts: challenges and perspectives

TL;DR: In this paper, the most recent advances on the electrochemical transformation of CO2 to alcohols, mainly methanol, ethanol and n-propanol, as a promising way to produce renewable liquid fuels are discussed.
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Highly dispersed, single-site copper catalysts for the electroreduction of CO2 to methane

TL;DR: In this paper, a single-site Cu(I) center was identified as the catalytically active site for the preferential formation of methane over ethylene, with an unexpected selectivity towards methane even in alkaline media, with a methane Faradaic efficiency as high as 42%.
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.
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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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