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Title: Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts

Abstract

Ni, N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni-N bonding and correlating CO2 reduction (CO2R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni, N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO¬2R to CO partial current density increased with increased Ni content before plateauing at 2 wt% which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft x-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [3];  [4];  [5];  [5]; ORCiD logo [6];  [7];  [8]
  1. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering
  2. McMaster Univ., Hamilton, ON (Canada). Dept. of Chemical Engineering
  3. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
  6. Department of Chemical Engineering, McMaster University, Hamilton ON Canada
  7. SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA 94305 USA
  8. SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA 94305 USA; SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA 94025 USA
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1592531
Alternate Identifier(s):
OSTI ID: 1595507
Grant/Contract Number:  
AC02-76SF00515; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English

Citation Formats

Koshy, David M., Chen, Shucheng, Lee, Dong Un, Stevens, Michaela Burke, Abdellah, Ahmed M., Dull, Samuel M., Chen, Gan, Nordlund, Dennis, Gallo, Alessandro, Hahn, Christopher, Higgins, Drew C., Bao, Zhenan, and Jaramillo, Thomas F. Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts. United States: N. p., 2020. Web. doi:10.1002/anie.201912857.
Koshy, David M., Chen, Shucheng, Lee, Dong Un, Stevens, Michaela Burke, Abdellah, Ahmed M., Dull, Samuel M., Chen, Gan, Nordlund, Dennis, Gallo, Alessandro, Hahn, Christopher, Higgins, Drew C., Bao, Zhenan, & Jaramillo, Thomas F. Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts. United States. doi:10.1002/anie.201912857.
Koshy, David M., Chen, Shucheng, Lee, Dong Un, Stevens, Michaela Burke, Abdellah, Ahmed M., Dull, Samuel M., Chen, Gan, Nordlund, Dennis, Gallo, Alessandro, Hahn, Christopher, Higgins, Drew C., Bao, Zhenan, and Jaramillo, Thomas F. Thu . "Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts". United States. doi:10.1002/anie.201912857.
@article{osti_1592531,
title = {Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts},
author = {Koshy, David M. and Chen, Shucheng and Lee, Dong Un and Stevens, Michaela Burke and Abdellah, Ahmed M. and Dull, Samuel M. and Chen, Gan and Nordlund, Dennis and Gallo, Alessandro and Hahn, Christopher and Higgins, Drew C. and Bao, Zhenan and Jaramillo, Thomas F.},
abstractNote = {Ni, N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni-N bonding and correlating CO2 reduction (CO2R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni, N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO¬2R to CO partial current density increased with increased Ni content before plateauing at 2 wt% which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft x-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.},
doi = {10.1002/anie.201912857},
journal = {Angewandte Chemie (International Edition)},
number = ,
volume = ,
place = {United States},
year = {2020},
month = {1}
}

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Works referenced in this record:

Catalysis Research of Relevance to Carbon Management:  Progress, Challenges, and Opportunities
journal, April 2001

  • Arakawa, Hironori; Aresta, Michele; Armor, John N.
  • Chemical Reviews, Vol. 101, Issue 4
  • DOI: 10.1021/cr000018s

Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017


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

General Techno-Economic Analysis of CO 2 Electrolysis Systems
journal, February 2018

  • Jouny, Matthew; Luc, Wesley; Jiao, Feng
  • Industrial & Engineering Chemistry Research, Vol. 57, Issue 6
  • DOI: 10.1021/acs.iecr.7b03514

Understanding and Breaking Scaling Relations in Single-Site Catalysis: Methane to Methanol Conversion by Fe IV ═O
journal, January 2018


Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst
journal, August 2017


Correlations between Mass Activity and Physicochemical Properties of Fe/N/C Catalysts for the ORR in PEM Fuel Cell via 57 Fe Mössbauer Spectroscopy and Other Techniques
journal, January 2014

  • Kramm, Ulrike I.; Lefèvre, Michel; Larouche, Nicholas
  • Journal of the American Chemical Society, Vol. 136, Issue 3
  • DOI: 10.1021/ja410076f

Carbon-based electrocatalysts for advanced energy conversion and storage
journal, August 2015


Electrochemical Reduction of CO 2 on Metal-Nitrogen-Doped Carbon Catalysts
journal, June 2019


Nickel-Nitrogen-Modified Graphene: An Efficient Electrocatalyst for the Reduction of Carbon Dioxide to Carbon Monoxide
journal, September 2016


Exclusive Ni–N 4 Sites Realize Near-Unity CO Selectivity for Electrochemical CO 2 Reduction
journal, October 2017

  • Li, Xiaogang; Bi, Wentuan; Chen, Minglong
  • Journal of the American Chemical Society, Vol. 139, Issue 42
  • DOI: 10.1021/jacs.7b09074

Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction
journal, February 2018


Coordinatively unsaturated nickel–nitrogen sites towards selective and high-rate CO 2 electroreduction
journal, January 2018

  • Yan, Chengcheng; Li, Haobo; Ye, Yifan
  • Energy & Environmental Science, Vol. 11, Issue 5
  • DOI: 10.1039/C8EE00133B

Isolated Ni single atoms in graphene nanosheets for high-performance CO 2 reduction
journal, January 2018

  • Jiang, Kun; Siahrostami, Samira; Zheng, Tingting
  • Energy & Environmental Science, Vol. 11, Issue 4
  • DOI: 10.1039/C7EE03245E

Achieving highly efficient CO 2 to CO electroreduction exceeding 300 mA cm −2 with single-atom nickel electrocatalysts
journal, January 2019

  • Jeong, Hui-Yun; Balamurugan, Mani; Choutipalli, Venkata Surya Kumar
  • Journal of Materials Chemistry A, Vol. 7, Issue 17
  • DOI: 10.1039/C9TA02405K

Powerful CO 2 electroreduction performance with N–carbon doped with single Ni atoms
journal, January 2019

  • Yuan, Cheng-Zong; Liang, Kuang; Xia, Xian-Ming
  • Catalysis Science & Technology, Vol. 9, Issue 14
  • DOI: 10.1039/C9CY00363K

Highly Efficient Electroreduction of CO 2 on Nickel Single‐Atom Catalysts: Atom Trapping and Nitrogen Anchoring
journal, October 2019


Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014

  • Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R.
  • Journal of the American Chemical Society, Vol. 136, Issue 40
  • DOI: 10.1021/ja505791r

Highly Tunable and Facile Synthesis of Uniform Carbon Flower Particles
journal, July 2018

  • Chen, Shucheng; Koshy, David Mathai; Tsao, Yuchi
  • Journal of the American Chemical Society, Vol. 140, Issue 32
  • DOI: 10.1021/jacs.8b05825

O 2 Reduction in PEM Fuel Cells: Activity and Active Site Structural Information for Catalysts Obtained by the Pyrolysis at High Temperature of Fe Precursors
journal, November 2000

  • Lefèvre, M.; Dodelet, J. P.; Bertrand, P.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 47
  • DOI: 10.1021/jp002444n

Nature of WO x Sites on SiO 2 and Their Molecular Structure–Reactivity/Selectivity Relationships for Propylene Metathesis
journal, April 2016


Influence of chemical bond of carbon on Ni catalyzed graphitization
journal, June 1997

  • Yudasaka, Masako; Tasaka, Kohji; Kikuchi, Rie
  • Journal of Applied Physics, Vol. 81, Issue 11
  • DOI: 10.1063/1.365339

Growth of single-crystal graphite by pyrolysis of acetylene over metals
journal, February 1969


High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011


Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER
journal, January 2019

  • Jiang, Hao; Gu, Jinxing; Zheng, Xusheng
  • Energy & Environmental Science, Vol. 12, Issue 1
  • DOI: 10.1039/C8EE03276A

Computational and experimental evidence for a new TM–N 3 /C moiety family in non-PGM electrocatalysts
journal, January 2015

  • Kabir, Sadia; Artyushkova, Kateryna; Kiefer, Boris
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 27
  • DOI: 10.1039/C5CP02230D

Multitechnique Characterization of a Polyaniline–Iron–Carbon Oxygen Reduction Catalyst
journal, July 2012

  • Ferrandon, Magali; Kropf, A. Jeremy; Myers, Deborah J.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 30
  • DOI: 10.1021/jp302396g

X-ray photoelectron spectroscopy of graphitic carbon nanomaterials doped with heteroatoms
journal, January 2015

  • Susi, Toma; Pichler, Thomas; Ayala, Paola
  • Beilstein Journal of Nanotechnology, Vol. 6
  • DOI: 10.3762/bjnano.6.17

Investigation of the Ligand Exchange Behavior of Square-Planar Nickel(II) Complexes by X-ray Absorption Spectroscopy and X-ray Diffraction
journal, March 2003

  • Feth, Martin P.; Klein, Axel; Bertagnolli, Helmut
  • European Journal of Inorganic Chemistry, Vol. 2003, Issue 5
  • DOI: 10.1002/ejic.200390114

X-ray spectroscopic studies of nickel complexes, with application to the structure of nickel sites in hydrogenases
journal, March 1991

  • Colpas, Gerard J.; Maroney, Michael J.; Bagyinka, Csaba.
  • Inorganic Chemistry, Vol. 30, Issue 5
  • DOI: 10.1021/ic00005a010

Simultaneous reduction of carbon dioxide and nitrate ions at gas-diffusion electrodes with various metallophthalocyanine catalysts
journal, November 2003


General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities
journal, January 2018