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Title: Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO2

Abstract

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.

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:
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. https://doi.org/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. https://doi.org/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. https://doi.org/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 = {2017},
month = {10}
}

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Cited by: 14 works
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Works referenced in this record:

How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010

  • Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c0ee00071j

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes
journal, January 2011

  • Schouten, K. J. P.; Kwon, Y.; van der Ham, C. J. M.
  • Chemical Science, Vol. 2, Issue 10
  • DOI: 10.1039/c1sc00277e

Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst
journal, September 2014

  • Manthiram, Karthish; Beberwyck, Brandon J.; Alivisatos, A. Paul
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja5065284

New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012

  • Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee21234j

Mechanistic Pathway in the Electrochemical Reduction of CO 2 on RuO 2
journal, June 2015

  • Karamad, Mohammadreza; Hansen, Heine A.; Rossmeisl, Jan
  • ACS Catalysis, Vol. 5, Issue 7
  • DOI: 10.1021/cs501542n

Electrochemical CO 2 reduction on Cu 2 O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons
journal, January 2014

  • Kas, Recep; Kortlever, Ruud; Milbrat, Alexander
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 24
  • DOI: 10.1039/C4CP01520G

Electrochemical Reduction of CO2 to CH3OH at Copper Oxide Surfaces
journal, January 2011

  • Le, M.; Ren, M.; Zhang, Z.
  • Journal of The Electrochemical Society, Vol. 158, Issue 5
  • DOI: 10.1149/1.3561636

Electrochemical Reduction of  CO 2 at Intentionally Oxidized Copper Electrodes
journal, November 1991

  • Frese, Karl W.
  • Journal of The Electrochemical Society, Vol. 138, Issue 11
  • DOI: 10.1149/1.2085411

Structure and dynamics of liquid water on rutile TiO 2 ( 110 )
journal, October 2010


Electrochemical Reduction of CO 2 at Copper Nanofoams
journal, August 2014

  • Sen, Sujat; Liu, Dan; Palmore, G. Tayhas R.
  • ACS Catalysis, Vol. 4, Issue 9
  • DOI: 10.1021/cs500522g

Electrochemical reduction of CO2 by Cu2O-catalyzed carbon clothes
journal, May 2009


Robust carbon dioxide reduction on molybdenum disulphide edges
journal, July 2014

  • Asadi, Mohammad; Kumar, Bijandra; Behranginia, Amirhossein
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5470

Nanostructured transition metal dichalcogenide electrocatalysts for CO 2 reduction in ionic liquid
journal, July 2016


Electrochemical CO 2 and CO Reduction on Metal-Functionalized Porphyrin-like Graphene
journal, April 2013

  • Tripkovic, Vladimir; Vanin, Marco; Karamad, Mohammedreza
  • The Journal of Physical Chemistry C, Vol. 117, Issue 18
  • DOI: 10.1021/jp306172k

Electrocatalytic reduction of carbon dioxide to carbon monoxide and methane at an immobilized cobalt protoporphyrin
journal, September 2015

  • Shen, Jing; Kortlever, Ruud; Kas, Recep
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9177

Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO 2 Electroreduction to CO and Hydrocarbons
journal, July 2015

  • Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian
  • Angewandte Chemie, Vol. 127, Issue 37
  • DOI: 10.1002/ange.201502099

Tailoring Metal-Porphyrin-Like Active Sites on Graphene to Improve the Efficiency and Selectivity of Electrochemical CO 2 Reduction
journal, September 2015

  • Cheng, Mu-Jeng; Kwon, Youngkook; Head-Gordon, Martin
  • The Journal of Physical Chemistry C, Vol. 119, Issue 37
  • DOI: 10.1021/acs.jpcc.5b05518

Covalent organic frameworks comprising cobalt porphyrins for catalytic CO 2 reduction in water
journal, August 2015


Functionalization of Graphene for Efficient Energy Conversion and Storage
journal, September 2012


Three dimensional graphene based materials: Synthesis and applications from energy storage and conversion to electrochemical sensor and environmental remediation
journal, July 2015

  • Wang, Hou; Yuan, Xingzhong; Zeng, Guangming
  • Advances in Colloid and Interface Science, Vol. 221
  • DOI: 10.1016/j.cis.2015.04.005

Graphene based new energy materials
journal, January 2011

  • Sun, Yiqing; Wu, Qiong; Shi, Gaoquan
  • Energy & Environmental Science, Vol. 4, Issue 4
  • DOI: 10.1039/c0ee00683a

An overview of graphene in energy production and storage applications
journal, June 2011


Graphene-based nanomaterials for energy storage
journal, January 2011


Electrochemistry of Carbon Dioxide on Carbon Electrodes
journal, January 2016

  • Yang, Nianjun; Waldvogel, Siegfried R.; Jiang, Xin
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 42
  • DOI: 10.1021/acsami.5b09825

Recent Advances in Heteroatom-Doped Metal-Free Electrocatalysts for Highly Efficient Oxygen Reduction Reaction
journal, January 2015


Recent progress in nitrogen-doped carbon and its composites as electrocatalysts for fuel cell applications
journal, July 2013


The role of defects and doping in 2D graphene sheets and 1D nanoribbons
journal, May 2012


Nitrogen-Doped Carbon Nanotube Arrays for High-Efficiency Electrochemical Reduction of CO 2 : On the Understanding of Defects, Defect Density, and Selectivity
journal, September 2015

  • Sharma, Pranav P.; Wu, Jingjie; Yadav, Ram Manohar
  • Angewandte Chemie International Edition, Vol. 54, Issue 46
  • DOI: 10.1002/anie.201506062

Metal‐free Nanoporous Carbon as a Catalyst for Electrochemical Reduction of CO 2 to CO and CH 4
journal, February 2016

  • Li, Wanlu; Seredych, Mykola; Rodríguez‐Castellón, Enrique
  • ChemSusChem, Vol. 9, Issue 6
  • DOI: 10.1002/cssc.201501575

Highly effective sites and selectivity of nitrogen-doped graphene/CNT catalysts for CO 2 electrochemical reduction
journal, January 2016

  • Chai, Guo-Liang; Guo, Zheng-Xiao
  • Chemical Science, Vol. 7, Issue 2
  • DOI: 10.1039/C5SC03695J

Efficient Electrochemical Reduction of Carbon Dioxide to Acetate on Nitrogen-Doped Nanodiamond
journal, September 2015

  • Liu, Yanming; Chen, Shuo; Quan, Xie
  • Journal of the American Chemical Society, Vol. 137, Issue 36
  • DOI: 10.1021/jacs.5b02975

Achieving Highly Efficient, Selective, and Stable CO 2 Reduction on Nitrogen-Doped Carbon Nanotubes
journal, April 2015


Significant Contribution of Intrinsic Carbon Defects to Oxygen Reduction Activity
journal, October 2015


High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration
journal, November 2016


Interplay between nitrogen dopants and native point defects in graphene
journal, April 2012


A Nitrogen-Doped Carbon Catalyst for Electrochemical CO 2 Conversion to CO with High Selectivity and Current Density
journal, October 2016

  • Jhong, Huei-Ru Molly; Tornow, Claire E.; Smid, Bretislav
  • ChemSusChem, Vol. 10, Issue 6
  • DOI: 10.1002/cssc.201600843

Polyethylenimine-Enhanced Electrocatalytic Reduction of CO 2 to Formate at Nitrogen-Doped Carbon Nanomaterials
journal, May 2014

  • Zhang, Sheng; Kang, Peng; Ubnoske, Stephen
  • Journal of the American Chemical Society, Vol. 136, Issue 22
  • DOI: 10.1021/ja5031529

Mechanistic Insights into the Electrochemical Reduction of CO 2 to CO on Nanostructured Ag Surfaces
journal, June 2015


Monodisperse Au Nanoparticles for Selective Electrocatalytic Reduction of CO 2 to CO
journal, October 2013

  • Zhu, Wenlei; Michalsky, Ronald; Metin, Önder
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja409445p

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
journal, January 2014

  • Shi, Chuan; Hansen, Heine A.; Lausche, Adam C.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 10
  • DOI: 10.1039/c3cp54822h

Chemical bonding on surfaces probed by X-ray emission spectroscopy and density functional theory
journal, October 2004


How Doped MoS 2 Breaks Transition-Metal Scaling Relations for CO 2 Electrochemical Reduction
journal, June 2016


Embedding Covalency into Metal Catalysts for Efficient Electrochemical Conversion of CO 2
journal, August 2014

  • Lim, Hyung-Kyu; Shin, Hyeyoung; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 136, Issue 32
  • DOI: 10.1021/ja503782w

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Ultrasoft pseudopotentials and projector augmented-wave data sets: application to diatomic molecules
journal, October 2011


Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

    Works referencing / citing this record:

    Identifying Active Sites of Nitrogen-Doped Carbon Materials for the CO 2 Reduction Reaction
    journal, April 2018

    • Liu, Song; Yang, Hongbin; Huang, Xiang
    • Advanced Functional Materials, Vol. 28, Issue 21
    • DOI: 10.1002/adfm.201800499

    Nanostructured Copper-Based Electrocatalysts for CO 2 Reduction
    journal, July 2018


    Defect engineering in earth-abundant electrocatalysts for CO 2 and N 2 reduction
    journal, January 2019

    • Wang, Qichen; Lei, Yongpeng; Wang, Dingsheng
    • Energy & Environmental Science, Vol. 12, Issue 6
    • DOI: 10.1039/c8ee03781g

    Recent Advances in Electrochemical CO 2 -to-CO Conversion on Heterogeneous Catalysts
    journal, August 2018

    • Zheng, Tingting; Jiang, Kun; Wang, Haotian
    • Advanced Materials, Vol. 30, Issue 48
    • DOI: 10.1002/adma.201802066

    Highly efficient nitrogen and carbon coordinated N–Co–C electrocatalysts on reduced graphene oxide derived from vitamin-B12 for the hydrogen evolution reaction
    journal, January 2019

    • Sabhapathy, Palani; Liao, Chen-Cheng; Chen, Wei-Fu
    • Journal of Materials Chemistry A, Vol. 7, Issue 12
    • DOI: 10.1039/c8ta10935d

    Heteroatom-doped carbon materials and their composites as electrocatalysts for CO 2 reduction
    journal, January 2018

    • Cui, Huijuan; Guo, Yibo; Guo, Limin
    • Journal of Materials Chemistry A, Vol. 6, Issue 39
    • DOI: 10.1039/c8ta07430e

    Progress in development of electrocatalyst for CO 2 conversion to selective CO production
    journal, March 2020

    • Nguyen, Dang Le Tri; Kim, Younghye; Hwang, Yun Jeong
    • Carbon Energy, Vol. 2, Issue 1
    • DOI: 10.1002/cey2.27

    How to teach an old dog new (electrochemical) tricks: aziridine-functionalized CNTs as efficient electrocatalysts for the selective CO 2 reduction to CO
    journal, January 2018

    • Tuci, Giulia; Filippi, Jonathan; Ba, Housseinou
    • Journal of Materials Chemistry A, Vol. 6, Issue 34
    • DOI: 10.1039/c8ta04267e

    Review of two‐dimensional materials for electrochemical CO 2 reduction from a theoretical perspective
    journal, April 2019

    • Zhu, Xiaorong; Li, Yafei
    • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 9, Issue 6
    • DOI: 10.1002/wcms.1416

    Current progress in electrocatalytic carbon dioxide reduction to fuels on heterogeneous catalysts
    journal, January 2020

    • Liu, Anmin; Gao, Mengfan; Ren, Xuefeng
    • Journal of Materials Chemistry A, Vol. 8, Issue 7
    • DOI: 10.1039/c9ta11966c

    A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO 2 to Value‐Added Chemicals and Fuel
    journal, November 2019

    • Daiyan, Rahman; Saputera, Wibawa Hendra; Masood, Hassan
    • Advanced Energy Materials, Vol. 10, Issue 11
    • DOI: 10.1002/aenm.201902106

    Engineering of transition metal dichalcogenide-based 2D nanomaterials through doping for environmental applications
    journal, January 2019

    • Balasubramaniam, Bhuvaneshwari; Singh, Narendra; Kar, Prasenjit
    • Molecular Systems Design & Engineering, Vol. 4, Issue 4
    • DOI: 10.1039/c8me00116b