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Title: Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO 2

Abstract

Here, despite numerous experimental efforts that have been dedicated to studying carbon-based materials for electrochemical reduction of CO 2, a rationalization of the associated trends in the intrinsic activity of different active motifs has so far been elusive. In the present work, we employ density functional theory calculations to examine a variety of different active sites in N-doped graphene to give a comprehensive outline of the trends in activity. We find that adsorption energies of COOH* and CO* do not follow the linear scaling relationships observed for the pure transition metals, and this unique scaling is rationalized through differences in electronic structure between transition metals and defected graphene. This finding rationalizes most of the experimental observations on the carbon-based materials which present promising catalysts for the two-electron reduction of CO 2 to CO. With this simple thermodynamic analysis, we identify several active sites that are expected to exhibit a comparable or even better activity to the state-of-the-art gold catalyst, and several configurations are suggested to be selective for CO 2RR over HER.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [2];  [3]
  1. Stanford Univ., Stanford, CA (United States)
  2. Harvard Univ., Cambridge, MA (United States)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1457110
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 5; Journal Issue: 11; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Calculated limiting potential; Density functional theory (DFT); Free energy diagram; Hydrogen evolution reaction (HER); Scaling relation

Citation Formats

Siahrostami, Samira, Jiang, Kun, Karamad, Mohammadreza, Chan, Karen, Wang, Haotian, and Norskov, Jens. Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO2. United States: N. p., 2017. Web. doi:10.1021/acssuschemeng.7b03031.
Siahrostami, Samira, Jiang, Kun, Karamad, Mohammadreza, Chan, Karen, Wang, Haotian, & Norskov, Jens. Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO2. United States. doi:10.1021/acssuschemeng.7b03031.
Siahrostami, Samira, Jiang, Kun, Karamad, Mohammadreza, Chan, Karen, Wang, Haotian, and Norskov, Jens. Tue . "Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO2". United States. doi:10.1021/acssuschemeng.7b03031. https://www.osti.gov/servlets/purl/1457110.
@article{osti_1457110,
title = {Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO2},
author = {Siahrostami, Samira and Jiang, Kun and Karamad, Mohammadreza and Chan, Karen and Wang, Haotian and Norskov, Jens},
abstractNote = {Here, despite numerous experimental efforts that have been dedicated to studying carbon-based materials for electrochemical reduction of CO2, a rationalization of the associated trends in the intrinsic activity of different active motifs has so far been elusive. In the present work, we employ density functional theory calculations to examine a variety of different active sites in N-doped graphene to give a comprehensive outline of the trends in activity. We find that adsorption energies of COOH* and CO* do not follow the linear scaling relationships observed for the pure transition metals, and this unique scaling is rationalized through differences in electronic structure between transition metals and defected graphene. This finding rationalizes most of the experimental observations on the carbon-based materials which present promising catalysts for the two-electron reduction of CO2 to CO. With this simple thermodynamic analysis, we identify several active sites that are expected to exhibit a comparable or even better activity to the state-of-the-art gold catalyst, and several configurations are suggested to be selective for CO2RR over HER.},
doi = {10.1021/acssuschemeng.7b03031},
journal = {ACS Sustainable Chemistry & Engineering},
number = 11,
volume = 5,
place = {United States},
year = {Tue Oct 10 00:00:00 EDT 2017},
month = {Tue Oct 10 00:00:00 EDT 2017}
}

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Cited by: 5 works
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