TY - JOUR

T1 - Electrochemical carbonyl reduction on single-site M–N–C catalysts

AU - Ju, Wen

AU - Bagger, Alexander

AU - Saharie, Nastaran Ranjbar

AU - Möhle, Sebastian

AU - Wang, Jingyi

AU - Jaouen, Frederic

AU - Rossmeisl, Jan

AU - Strasser, Peter

N1 - Funding Information: The authors acknowledge EU project 851441 – SELECTCO2 and 101006701 – Ecofuel. P.S. and W.J. are grateful for Funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy – EXC 2008 – 390540038” – UniSysCat and FCH Joint Undertaking 2 (CRESCENDO Project, Grant Agreement n°779366). JR acknowledges the Danish National Research Foundation Center for High Entropy Alloy Catalysis (DNRF 149). A.B. acknowledges support from the Carlsberg Foundation (CF21-0144). Funding Information: The authors acknowledge EU project 851441 – SELECTCO2 and 101006701 – Ecofuel. P.S. and W.J. are grateful for Funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy – EXC 2008 – 390540038” – UniSysCat and FCH Joint Undertaking 2 (CRESCENDO Project, Grant Agreement n°779366). JR acknowledges the Danish National Research Foundation Center for High Entropy Alloy Catalysis (DNRF 149). A.B. acknowledges support from the Carlsberg Foundation (CF21-0144). Publisher Copyright: © 2023, Springer Nature Limited.

PY - 2023

Y1 - 2023

N2 - Electrochemical conversion of organic compounds holds promise for advancing sustainable synthesis and catalysis. This study explored electrochemical carbonyl hydrogenation on single-site M–N–C (Metal Nitrogen-doped Carbon) catalysts using formaldehyde, acetaldehyde, and acetone as model reactants. We strive to correlate and understand the selectivity dependence on the nature of the metal centers. Density Functional Theory calculations revealed similar binding energetics for carbonyl groups through oxygen-down or carbon-down adsorption due to oxygen and carbon scaling. Fe–N–C exhibited specific oxyphilicity and could selectively reduce aldehydes to hydrocarbons. By contrast, the carbophilic Co–N–C selectively converted acetaldehyde and acetone to ethanol and 2-propanol, respectively. We claim that the oxyphilicity of the active sites and consequent adsorption geometry (oxygen-down vs. carbon-down) are crucial in controlling product selectivity. These findings offer mechanistic insights into electrochemical carbonyl hydrogenation and can guide the development of efficient and sustainable electrocatalytic valorization of biomass-derived compounds.

AB - Electrochemical conversion of organic compounds holds promise for advancing sustainable synthesis and catalysis. This study explored electrochemical carbonyl hydrogenation on single-site M–N–C (Metal Nitrogen-doped Carbon) catalysts using formaldehyde, acetaldehyde, and acetone as model reactants. We strive to correlate and understand the selectivity dependence on the nature of the metal centers. Density Functional Theory calculations revealed similar binding energetics for carbonyl groups through oxygen-down or carbon-down adsorption due to oxygen and carbon scaling. Fe–N–C exhibited specific oxyphilicity and could selectively reduce aldehydes to hydrocarbons. By contrast, the carbophilic Co–N–C selectively converted acetaldehyde and acetone to ethanol and 2-propanol, respectively. We claim that the oxyphilicity of the active sites and consequent adsorption geometry (oxygen-down vs. carbon-down) are crucial in controlling product selectivity. These findings offer mechanistic insights into electrochemical carbonyl hydrogenation and can guide the development of efficient and sustainable electrocatalytic valorization of biomass-derived compounds.

U2 - 10.1038/s42004-023-01008-y

DO - 10.1038/s42004-023-01008-y

M3 - Journal article

C2 - 37777576

AN - SCOPUS:85173729738

VL - 6

JO - Communications Chemistry

JF - Communications Chemistry

SN - 2399-3669

IS - 1

M1 - 212

ER -