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Title: Electrochemical CO2 Reduction over Metal-/Nitrogen-Doped Graphene Single-Atom Catalysts Modeled Using the Grand-Canonical Density Functional Theory

Abstract

Renewably driven, electrochemical conversion of carbon dioxide into value-added products is expected to be a critical tool in global decarbonization. However, theoretical studies based on the computational hydrogen electrode largely ignore the nonlinear effects of the applied potential on the calculated results, leading to inaccurate predictions of catalytic behavior or mechanistic pathways. Here, we use grand canonical density functional theory (GC-DFT) to model electrochemical CO2 reduction (CO2R) over metal- and nitrogen-doped graphene catalysts (MNCs) and explicitly include the effects of the applied potential. We used GC-DFT to compute the CO2 to CO reaction intermediate energies at -0.3, -0.7, and -1.2 VSHE catalyzed by MNCs each doped with 1 of the 10 3d block metals coordinated by four pyridinic nitrogen atoms. Our results predict that Sc-, Ti-, Co-, Cu-, and Zn-N4Cs effectively catalyze CO2R at moderate to large reducing potentials (-0.7 to -1.2 VSHE). ZnN4C is a particularly promising electrocatalyst for CO2R to CO both at low and moderate applied potentials based on our thermodynamic analysis. Our findings also explain the observed pH independence of CO production over FeN4C and predict that the rate-determining step of CO2R over FeN4C is not *CO2- formation but rather *CO desorption. Additionally, the GC-DFT-computed densitymore » of states analysis illustrates how the electronic states of MNCs and adsorbates change non-uniformly with applied potential, resulting in a significantly increased *CO2- stability relative to other intermediates and demonstrating that the formation of the adsorbed *CO2- anion is critical to CO2R activation. This work demonstrates how GC-DFT paves the way for physically realistic and accurate theoretical simulations of reacting electrochemical systems.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1888774
Report Number(s):
NREL/JA-5900-84054
MainId:84827;UUID:c529f1f1-5a8d-4b0c-a681-4708a57ab1a7;MainAdminID:67525
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 12; Journal Issue: 16
Country of Publication:
United States
Language:
English
Subject:
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; DFT calculations; electrochemistry; grand canonical density functional theory; single-atom catalysts; surface chemistry

Citation Formats

Brimley, Paige, Almajed, Hussain, Alsunni, Yousef, Bare, Zachary J. L., Smith, Wilson A., and Musgrave, Charles B. Electrochemical CO2 Reduction over Metal-/Nitrogen-Doped Graphene Single-Atom Catalysts Modeled Using the Grand-Canonical Density Functional Theory. United States: N. p., 2022. Web. doi:10.1021/acscatal.2c01832.
Brimley, Paige, Almajed, Hussain, Alsunni, Yousef, Bare, Zachary J. L., Smith, Wilson A., & Musgrave, Charles B. Electrochemical CO2 Reduction over Metal-/Nitrogen-Doped Graphene Single-Atom Catalysts Modeled Using the Grand-Canonical Density Functional Theory. United States. https://doi.org/10.1021/acscatal.2c01832
Brimley, Paige, Almajed, Hussain, Alsunni, Yousef, Bare, Zachary J. L., Smith, Wilson A., and Musgrave, Charles B. 2022. "Electrochemical CO2 Reduction over Metal-/Nitrogen-Doped Graphene Single-Atom Catalysts Modeled Using the Grand-Canonical Density Functional Theory". United States. https://doi.org/10.1021/acscatal.2c01832.
@article{osti_1888774,
title = {Electrochemical CO2 Reduction over Metal-/Nitrogen-Doped Graphene Single-Atom Catalysts Modeled Using the Grand-Canonical Density Functional Theory},
author = {Brimley, Paige and Almajed, Hussain and Alsunni, Yousef and Bare, Zachary J. L. and Smith, Wilson A. and Musgrave, Charles B.},
abstractNote = {Renewably driven, electrochemical conversion of carbon dioxide into value-added products is expected to be a critical tool in global decarbonization. However, theoretical studies based on the computational hydrogen electrode largely ignore the nonlinear effects of the applied potential on the calculated results, leading to inaccurate predictions of catalytic behavior or mechanistic pathways. Here, we use grand canonical density functional theory (GC-DFT) to model electrochemical CO2 reduction (CO2R) over metal- and nitrogen-doped graphene catalysts (MNCs) and explicitly include the effects of the applied potential. We used GC-DFT to compute the CO2 to CO reaction intermediate energies at -0.3, -0.7, and -1.2 VSHE catalyzed by MNCs each doped with 1 of the 10 3d block metals coordinated by four pyridinic nitrogen atoms. Our results predict that Sc-, Ti-, Co-, Cu-, and Zn-N4Cs effectively catalyze CO2R at moderate to large reducing potentials (-0.7 to -1.2 VSHE). ZnN4C is a particularly promising electrocatalyst for CO2R to CO both at low and moderate applied potentials based on our thermodynamic analysis. Our findings also explain the observed pH independence of CO production over FeN4C and predict that the rate-determining step of CO2R over FeN4C is not *CO2- formation but rather *CO desorption. Additionally, the GC-DFT-computed density of states analysis illustrates how the electronic states of MNCs and adsorbates change non-uniformly with applied potential, resulting in a significantly increased *CO2- stability relative to other intermediates and demonstrating that the formation of the adsorbed *CO2- anion is critical to CO2R activation. This work demonstrates how GC-DFT paves the way for physically realistic and accurate theoretical simulations of reacting electrochemical systems.},
doi = {10.1021/acscatal.2c01832},
url = {https://www.osti.gov/biblio/1888774}, journal = {ACS Catalysis},
number = 16,
volume = 12,
place = {United States},
year = {2022},
month = {8}
}

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