Distinguishing the mechanism of electrochemical carboxylation in CO2 eXpanded Electrolytes

Matthew A. Stalcup; Christian K. Nilles; Bala Subramaniam; James D. Blakemore; Kevin C. Leonard

doi:10.1039/D2CC06560F

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Distinguishing the mechanism of electrochemical carboxylation in CO₂ eXpanded Electrolytes†

Matthew A. Stalcup,^ab Christian K. Nilles,^bc Bala Subramaniam,

*^ab James D. Blakemore

*^bc and Kevin C. Leonard

*^ab

Author affiliations

* Corresponding authors

^a Department of Chemical & Petroleum Engineering, University of Kansas, 4132 Learned Hall 1530 W 15th St, Lawrence, KS, USA
E-mail: bsubramaniam@ku.edu, kcleonard@ku.edu

^b Center for Environmentally Beneficial Catalysis, University of Kansas, 1501 Wakarusa Drive LSRL Building A, Suite 110, Lawrence, KS, USA
E-mail: blakemore@ku.edu

^c Department of Chemistry, University of Kansas, 1140 Gray-Little Hall, 1567 Irving Hill Road, Lawrence, KS, USA

Abstract

We shed light on the mechanism and rate-determining steps of the electrochemical carboxylation of acetophenone as a function of CO₂ concentration by using a robust finite element analysis model that incorporates each reaction step. Specifically, we show that the first electrochemical reduction of acetophenone is followed by the homogeneous chemical addition of CO₂. The electrochemical reduction of the acetophenone-CO₂ adduct is more facile than that of acetophenone, resulting in an Electrochemical–Chemical–Electrochemical (ECE) reaction pathway that appears as a single voltammetric wave. These modeling results provide new fundamental insights into the complex microenvironment in CO₂-rich media that produces an optimum electrochemical carboxylation rate as a function of CO₂ pressure.

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Article information

DOI: https://doi.org/10.1039/D2CC06560F
Article type: Communication
Submitted: 01 Dec 2022
Accepted: 11 Apr 2023
First published: 11 Apr 2023

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Chem. Commun., 2023,59, 5713-5716

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Distinguishing the mechanism of electrochemical carboxylation in CO₂ eXpanded Electrolytes

M. A. Stalcup, C. K. Nilles, B. Subramaniam, J. D. Blakemore and K. C. Leonard, Chem. Commun., 2023, 59, 5713 DOI: 10.1039/D2CC06560F

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