Molecular Electrochemical Catalysis of CO-to-Formaldehyde Conversion with a Cobalt Complex

Ajeet Singh; Afridi Zamader; Reza Khakpour; Kari Laasonen; Michael Busch; Marc Robert

doi:10.1021/jacs.4c06878

Molecular Electrochemical Catalysis of CO-to-Formaldehyde Conversion with a Cobalt Complex

Ajeet Singh
, Afridi Zamader
, Reza Khakpour
, Kari Laasonen
, Michael Busch
, Marc Robert^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

26 Citations (Scopus)

Abstract

Formox, a highly energy-intensive process, currently serves as the primary source of formaldehyde (HCHO), for which there is a crucial and steadily growing chemical demand. The alternative electrochemical production of HCHO from C1 carbon sources such as CO₂ and CO is still in its early stages, with even the few identified cases lacking mechanistic rationalization. In this study, we demonstrate that cobalt phthalocyanine (CoPc) immobilized on multiwalled carbon nanotubes (MW-CNTs) constitutes an excellent electrocatalytic system for producing HCHO with productivity through the direct reduction of CO, the two-electron reduction product of CO₂. By carefully adjusting both the pH and the applied potential, we identified conditions that enable the production of HCHO with a partial current density of 0.64 mA cm^-2 (17.5% Faradaic efficiency, FE) and a total FE of 61.2% for the liquid products (formaldehyde and methanol). A reduction mechanism is proposed.

Original language	English
Pages (from-to)	22129–22133
Journal	Journal of the American Chemical Society
Volume	146
Issue number	32
Early online date	31 Jul 2024
DOIs	https://doi.org/10.1021/jacs.4c06878
Publication status	Published - 14 Aug 2024
MoE publication type	A1 Journal article-refereed

Funding

This work has benefited from French State aid managed by the Agence Nationale de la Recherche under France 2030 plan (ANR-22-PESP-0010 Projet cible\u0301 \u201CPOWERCO2\u201D) within the PEPR project SPLEEN. K.L. and R.K. gratefully acknowledge the support received from the Jane and Aatos Erkko Foundation and Finland CSC-IT Center for generous grants of computer time. M.B. acknowledges financial support by the Wallenberg Initiative Materials Science for Sustainability (WISE) funded by the Knut and Alice Wallenberg Foundation. Partial financial support to M.R. from the Institut Universitaire de France (IUF) is warmly acknowledged.

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title = "Molecular Electrochemical Catalysis of CO-to-Formaldehyde Conversion with a Cobalt Complex",

abstract = "Formox, a highly energy-intensive process, currently serves as the primary source of formaldehyde (HCHO), for which there is a crucial and steadily growing chemical demand. The alternative electrochemical production of HCHO from C1 carbon sources such as CO2 and CO is still in its early stages, with even the few identified cases lacking mechanistic rationalization. In this study, we demonstrate that cobalt phthalocyanine (CoPc) immobilized on multiwalled carbon nanotubes (MW-CNTs) constitutes an excellent electrocatalytic system for producing HCHO with productivity through the direct reduction of CO, the two-electron reduction product of CO2. By carefully adjusting both the pH and the applied potential, we identified conditions that enable the production of HCHO with a partial current density of 0.64 mA cm-2 (17.5\% Faradaic efficiency, FE) and a total FE of 61.2\% for the liquid products (formaldehyde and methanol). A reduction mechanism is proposed.",

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AU - Singh, Ajeet

AU - Zamader, Afridi

AU - Khakpour, Reza

AU - Laasonen, Kari

AU - Busch, Michael

AU - Robert, Marc

PY - 2024/8/14

Y1 - 2024/8/14

N2 - Formox, a highly energy-intensive process, currently serves as the primary source of formaldehyde (HCHO), for which there is a crucial and steadily growing chemical demand. The alternative electrochemical production of HCHO from C1 carbon sources such as CO2 and CO is still in its early stages, with even the few identified cases lacking mechanistic rationalization. In this study, we demonstrate that cobalt phthalocyanine (CoPc) immobilized on multiwalled carbon nanotubes (MW-CNTs) constitutes an excellent electrocatalytic system for producing HCHO with productivity through the direct reduction of CO, the two-electron reduction product of CO2. By carefully adjusting both the pH and the applied potential, we identified conditions that enable the production of HCHO with a partial current density of 0.64 mA cm-2 (17.5% Faradaic efficiency, FE) and a total FE of 61.2% for the liquid products (formaldehyde and methanol). A reduction mechanism is proposed.

AB - Formox, a highly energy-intensive process, currently serves as the primary source of formaldehyde (HCHO), for which there is a crucial and steadily growing chemical demand. The alternative electrochemical production of HCHO from C1 carbon sources such as CO2 and CO is still in its early stages, with even the few identified cases lacking mechanistic rationalization. In this study, we demonstrate that cobalt phthalocyanine (CoPc) immobilized on multiwalled carbon nanotubes (MW-CNTs) constitutes an excellent electrocatalytic system for producing HCHO with productivity through the direct reduction of CO, the two-electron reduction product of CO2. By carefully adjusting both the pH and the applied potential, we identified conditions that enable the production of HCHO with a partial current density of 0.64 mA cm-2 (17.5% Faradaic efficiency, FE) and a total FE of 61.2% for the liquid products (formaldehyde and methanol). A reduction mechanism is proposed.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 32

ER -

Molecular Electrochemical Catalysis of CO-to-Formaldehyde Conversion with a Cobalt Complex

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