Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO2 Conversion with Carbon-Based Materials

David M. Koshy; Sindhu S. Nathan; Arun S. Asundi; Ahmed M. Abdellah; Samuel M. Dull; David A. Cullen; Drew Higgins; Zhenan Bao; Stacey F. Bent; Thomas F. Jaramillo

doi:10.1002/anie.202101326

Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO₂ Conversion with Carbon-Based Materials

David M. Koshy, Sindhu S. Nathan, Arun S. Asundi, Ahmed M. Abdellah, Samuel M. Dull, David A. Cullen, Drew Higgins, Zhenan Bao, Stacey F. Bent, Thomas F. Jaramillo

Materials MicroAnalysis

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

34 Scopus citations

Abstract

Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO₂ to CO (CO₂R), can also selectively catalyze thermal CO₂ to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO₂R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO₂R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.

Original language	English
Pages (from-to)	17472-17480
Number of pages	9
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	32
DOIs	https://doi.org/10.1002/anie.202101326
State	Published - Aug 2 2021

Funding

This research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. The electrochemical CO reduction experiments were supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE‐SC0004993. ADF‐STEM was conducted at the Center for Nanophase Materials Sciences at Oak Ridge National Lab, which is a DOE Office of Science User Facility. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS‐1542152. Use of Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory is supported by the US Department of Energy, Office of Science, Office of Basic Energy Science, under Contract DE‐AC02‐76SF00515. STEM‐HAADF imaging and EDS mapping was carried out at the Canadian Centre for Electron Microscopy, a facility supported by the Canada Foundation for Innovation under the Major Science Initiative program, NSERC, and McMaster University. The authors thank A. S. Hoffman, J. Hong, and S. R. Bare for valuable discussions on the EXAFS modelling and analysis. 2

Funders	Funder number
Catalysis Science Program
DOE Energy Innovation Hub	DE‐SC0004993
Joint Center for Artificial Photosynthesis
National Science Foundation	ECCS‐1542152
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE‐AC02‐76SF00515
McMaster University
Chemical Sciences, Geosciences, and Biosciences Division
Natural Sciences and Engineering Research Council of Canada
Canada Foundation for Innovation

Keywords

carbon dioxide
catalysis
electrochemistry
nitrogen-doped carbon
reverse water-gas shift

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/anie.202101326

Cite this

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title = "Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO2 Conversion with Carbon-Based Materials",

abstract = "Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO2 to CO (CO2R), can also selectively catalyze thermal CO2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO2R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO2R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.",

keywords = "carbon dioxide, catalysis, electrochemistry, nitrogen-doped carbon, reverse water-gas shift",

author = "Koshy, {David M.} and Nathan, {Sindhu S.} and Asundi, {Arun S.} and Abdellah, {Ahmed M.} and Dull, {Samuel M.} and Cullen, {David A.} and Drew Higgins and Zhenan Bao and Bent, {Stacey F.} and Jaramillo, {Thomas F.}",

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AU - Koshy, David M.

AU - Nathan, Sindhu S.

AU - Asundi, Arun S.

AU - Abdellah, Ahmed M.

AU - Dull, Samuel M.

AU - Cullen, David A.

AU - Higgins, Drew

AU - Bao, Zhenan

AU - Bent, Stacey F.

AU - Jaramillo, Thomas F.

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AB - Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO2 to CO (CO2R), can also selectively catalyze thermal CO2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO2R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO2R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.

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