On the Origin of the Elusive First Intermediate of CO Electroreduction

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2018 Sep 19

PMID 30224482

Citations 62

Authors

Irina V Chernyshova

Ponisseril Somasundaran

Sathish Ponnurangam

Affiliations

Soon will be listed here.

Abstract

We resolve the long-standing controversy about the first step of the CO electroreduction to fuels in aqueous electrolytes by providing direct spectroscopic evidence that the first intermediate of the CO conversion to formate on copper is a carboxylate anion *CO coordinated to the surface through one of its C-O bonds. We identify this intermediate and gain insight into its formation, its chemical and electronic properties, as well as its dependence on the electrode potential by taking advantage of a cutting-edge methodology that includes operando surface-enhanced Raman scattering (SERS) empowered by isotope exchange and electrochemical Stark effects, reaction kinetics (Tafel) analysis, and density functional theory (DFT) simulations. The SERS spectra are measured on an operating Cu surface. These results advance the mechanistic understanding of CO electroreduction and its selectivity to carbon monoxide and formate.

Citing Articles

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Intermediate-regulated dynamic restructuring at Ag-Cu biphasic interface enables selective CO electroreduction to C fuels.

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