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Title: Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface

Abstract

To date, effective control over the electrochemical reduction of CO2 to multicarbon products (C ≥ 2) has been very challenging. Here, we report a design principle for the creation of a selective yet robust catalytic interface for heterogeneous electrocatalysts in the reduction of CO2 to C2 oxygenates, demonstrated by rational tuning of an assembly of nitrogen-doped nanodiamonds and copper nanoparticles. The catalyst exhibits a Faradaic efficiency of ~63% towards C2 oxygenates at applied potentials of only -0.5 V versus reversible hydrogen electrode. Moreover, this catalyst shows an unprecedented persistent catalytic performance up to 120 h, with steady current and only 19% activity decay. Density functional theory calculations show that CO binding is strengthened at the copper/nanodiamond interface, suppressing CO desorption and promoting C2 production by lowering the apparent barrier for CO dimerization. The inherent compositional and electronic tunability of the catalyst assembly offers an unrivalled degree of control over the catalytic interface, and thereby the reaction energetics and kinetics.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4];  [4];  [4]; ORCiD logo [4];  [4];  [4];  [4];  [2]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [3];  [7];  [8] more »; ORCiD logo [9] « less
  1. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; Beijing Univ. of Chemical Technology (China)
  2. Stanford Univ., CA (United States). Dept. of Physics
  3. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
  4. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
  5. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
  7. Beijing Univ. of Chemical Technology (China). Beijing Advanced Innovation Center for Soft Matter Science and Engineering; Beijing Univ. of Chemical Technology (China). National Energy R&D Center for Biorefinery
  8. Stanford Univ., CA (United States). Dept. of Physics and Dept. of Molecular and Cellular Physiology
  9. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1605382
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 15; Journal Issue: 2; Journal ID: ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wang, Hongxia, Tzeng, Yan-Kai, Ji, Yongfei, Li, Yanbin, Li, Jun, Zheng, Xueli, Yang, Ankun, Liu, Yayuan, Gong, Yongji, Cai, Lili, Li, Yuzhang, Zhang, Xiaokun, Chen, Wei, Liu, Bofei, Lu, Haiyu, Melosh, Nicholas A., Shen, Zhi-Xun, Chan, Karen, Tan, Tianwei, Chu, Steven, and Cui, Yi. Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface. United States: N. p., 2020. Web. doi:10.1038/s41565-019-0603-y.
Wang, Hongxia, Tzeng, Yan-Kai, Ji, Yongfei, Li, Yanbin, Li, Jun, Zheng, Xueli, Yang, Ankun, Liu, Yayuan, Gong, Yongji, Cai, Lili, Li, Yuzhang, Zhang, Xiaokun, Chen, Wei, Liu, Bofei, Lu, Haiyu, Melosh, Nicholas A., Shen, Zhi-Xun, Chan, Karen, Tan, Tianwei, Chu, Steven, & Cui, Yi. Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface. United States. doi:https://doi.org/10.1038/s41565-019-0603-y
Wang, Hongxia, Tzeng, Yan-Kai, Ji, Yongfei, Li, Yanbin, Li, Jun, Zheng, Xueli, Yang, Ankun, Liu, Yayuan, Gong, Yongji, Cai, Lili, Li, Yuzhang, Zhang, Xiaokun, Chen, Wei, Liu, Bofei, Lu, Haiyu, Melosh, Nicholas A., Shen, Zhi-Xun, Chan, Karen, Tan, Tianwei, Chu, Steven, and Cui, Yi. Mon . "Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface". United States. doi:https://doi.org/10.1038/s41565-019-0603-y. https://www.osti.gov/servlets/purl/1605382.
@article{osti_1605382,
title = {Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface},
author = {Wang, Hongxia and Tzeng, Yan-Kai and Ji, Yongfei and Li, Yanbin and Li, Jun and Zheng, Xueli and Yang, Ankun and Liu, Yayuan and Gong, Yongji and Cai, Lili and Li, Yuzhang and Zhang, Xiaokun and Chen, Wei and Liu, Bofei and Lu, Haiyu and Melosh, Nicholas A. and Shen, Zhi-Xun and Chan, Karen and Tan, Tianwei and Chu, Steven and Cui, Yi},
abstractNote = {To date, effective control over the electrochemical reduction of CO2 to multicarbon products (C ≥ 2) has been very challenging. Here, we report a design principle for the creation of a selective yet robust catalytic interface for heterogeneous electrocatalysts in the reduction of CO2 to C2 oxygenates, demonstrated by rational tuning of an assembly of nitrogen-doped nanodiamonds and copper nanoparticles. The catalyst exhibits a Faradaic efficiency of ~63% towards C2 oxygenates at applied potentials of only -0.5 V versus reversible hydrogen electrode. Moreover, this catalyst shows an unprecedented persistent catalytic performance up to 120 h, with steady current and only 19% activity decay. Density functional theory calculations show that CO binding is strengthened at the copper/nanodiamond interface, suppressing CO desorption and promoting C2 production by lowering the apparent barrier for CO dimerization. The inherent compositional and electronic tunability of the catalyst assembly offers an unrivalled degree of control over the catalytic interface, and thereby the reaction energetics and kinetics.},
doi = {10.1038/s41565-019-0603-y},
journal = {Nature Nanotechnology},
number = 2,
volume = 15,
place = {United States},
year = {2020},
month = {1}
}

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Works referenced in this record:

Metal–Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide
journal, October 2015

  • Kornienko, Nikolay; Zhao, Yingbo; Kley, Christopher S.
  • Journal of the American Chemical Society, Vol. 137, Issue 44
  • DOI: 10.1021/jacs.5b08212

Doping Metal–Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction, and Organic Photocatalysis
journal, August 2011

  • Wang, Cheng; Xie, Zhigang; deKrafft, Kathryn E.
  • Journal of the American Chemical Society, Vol. 133, Issue 34, p. 13445-13454
  • DOI: 10.1021/ja203564w

Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006

  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014

  • Li, Christina W.; Ciston, Jim; Kanan, Matthew W.
  • Nature, Vol. 508, Issue 7497
  • DOI: 10.1038/nature13249

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

Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements
journal, October 1994


A grid-based Bader analysis algorithm without lattice bias
journal, January 2009


Nitrogen-doped graphenes as efficient electrocatalysts for the selective reduction of carbon dioxide to formate in aqueous solution
journal, January 2016

  • Wang, Hongxia; Chen, Yabin; Hou, Xiaoli
  • Green Chemistry, Vol. 18, Issue 11
  • DOI: 10.1039/C6GC00410E

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?
journal, January 2018

  • Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 3
  • DOI: 10.1021/acs.jpclett.7b03180

Enhancing CO 2 Electroreduction with the Metal–Oxide Interface
journal, April 2017

  • Gao, Dunfeng; Zhang, Yi; Zhou, Zhiwen
  • Journal of the American Chemical Society, Vol. 139, Issue 16
  • DOI: 10.1021/jacs.7b00102

A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


Self-Selective Catalyst Synthesis for CO2 Reduction
journal, August 2019


A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO 2
journal, June 2016

  • Verma, Sumit; Kim, Byoungsu; Jhong, Huei-Ru “Molly”
  • ChemSusChem, Vol. 9, Issue 15
  • DOI: 10.1002/cssc.201600394

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


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel
journal, January 2016


Copper nanoparticle ensembles for selective electroreduction of CO 2 to C 2 –C 3 products
journal, September 2017

  • Kim, Dohyung; Kley, Christopher S.; Li, Yifan
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 40
  • DOI: 10.1073/pnas.1711493114

The properties and applications of nanodiamonds
journal, December 2011

  • Mochalin, Vadym N.; Shenderova, Olga; Ho, Dean
  • Nature Nanotechnology, Vol. 7, Issue 1
  • DOI: 10.1038/nnano.2011.209

Dipole correction for surface supercell calculations
journal, May 1999


Visible-light-driven methane formation from CO2 with a molecular iron catalyst
journal, July 2017

  • Rao, Heng; Schmidt, Luciana C.; Bonin, Julien
  • Nature, Vol. 548, Issue 7665
  • DOI: 10.1038/nature23016

Size-Dependent Electrocatalytic Reduction of CO 2 over Pd Nanoparticles
journal, March 2015

  • Gao, Dunfeng; Zhou, Hu; Wang, Jing
  • Journal of the American Chemical Society, Vol. 137, Issue 13
  • DOI: 10.1021/jacs.5b00046

Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction
journal, January 2018


An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002

  • Bahn, S. R.; Jacobsen, K. W.
  • Computing in Science & Engineering, Vol. 4, Issue 3
  • DOI: 10.1109/5992.998641

The Importance of Cannizzaro-Type Reactions during Electrocatalytic Reduction of Carbon Dioxide
journal, January 2017

  • Birdja, Yuvraj Y.; Koper, Marc T. M.
  • Journal of the American Chemical Society, Vol. 139, Issue 5
  • DOI: 10.1021/jacs.6b12008

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


Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction
journal, January 2018

  • Diercks, Christian S.; Lin, Song; Kornienko, Nikolay
  • Journal of the American Chemical Society, Vol. 140, Issue 3
  • DOI: 10.1021/jacs.7b11940

Nanostructured Tin Catalysts for Selective Electrochemical Reduction of Carbon Dioxide to Formate
journal, January 2014

  • Zhang, Sheng; Kang, Peng; Meyer, Thomas J.
  • Journal of the American Chemical Society, Vol. 136, Issue 5
  • DOI: 10.1021/ja4113885

Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO 2 Reduction
journal, October 2017

  • Cavalca, Filippo; Ferragut, Rafael; Aghion, Stefano
  • The Journal of Physical Chemistry C, Vol. 121, Issue 45
  • DOI: 10.1021/acs.jpcc.7b08278

Electrocatalytic CO2 Conversion to Oxalate by a Copper Complex
journal, January 2010


Selective increase in CO 2 electroreduction activity at grain-boundary surface terminations
journal, November 2017


Synthesis and characterization of highly-conducting nitrogen-doped ultrananocrystalline diamond films
journal, September 2001

  • Bhattacharyya, S.; Auciello, O.; Birrell, J.
  • Applied Physics Letters, Vol. 79, Issue 10, p. 1441-1443
  • DOI: 10.1063/1.1400761

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Structural characterization of nitrogen doped diamond-like carbon films deposited by arc ion plating
journal, March 2005


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

Nanoporous Metals as Electrocatalysts: State-of-the-Art, Opportunities, and Challenges
journal, August 2017


Low-dimensional catalysts for hydrogen evolution and CO2 reduction
journal, January 2018

  • Voiry, Damien; Shin, Hyeon Suk; Loh, Kian Ping
  • Nature Reviews Chemistry, Vol. 2, Issue 1
  • DOI: 10.1038/s41570-017-0105

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction
journal, January 2018


High-Selectivity Electrochemical Conversion of CO 2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode
journal, September 2016


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

A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst
journal, October 2012


CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface
journal, May 2018


Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO 2 Reduction
journal, October 2017

  • Liu, Chang; Lourenço, Maicon P.; Hedström, Svante
  • The Journal of Physical Chemistry C, Vol. 121, Issue 45
  • DOI: 10.1021/acs.jpcc.7b08269

The path towards sustainable energy
journal, December 2016

  • Chu, Steven; Cui, Yi; Liu, Nian
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4834

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

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

Promoting Ethylene Selectivity from CO 2 Electroreduction on CuO Supported onto CO 2 Capture Materials
journal, February 2018


Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction
journal, June 2016

  • Cao, Zhi; Kim, Dohyung; Hong, Dachao
  • Journal of the American Chemical Society, Vol. 138, Issue 26
  • DOI: 10.1021/jacs.6b02878

Efficient electrocatalytic CO2 reduction on a three-phase interface
journal, July 2018


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

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22
  • DOI: 10.1063/1.1323224

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

Water splitting–biosynthetic system with CO 2 reduction efficiencies exceeding photosynthesis
journal, June 2016


Time-Resolved Luminescence Nanothermometry with Nitrogen-Vacancy Centers in Nanodiamonds
journal, May 2015


Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts
journal, January 2016


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 International Edition, Vol. 54, Issue 37
  • DOI: 10.1002/anie.201502099

Surface interaction of benzoic acid with a copper electrode
journal, August 1995


pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019


Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene
journal, June 2016

  • Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12123

Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures
journal, March 2017

  • Zhang, Xing; Wu, Zishan; Zhang, Xiao
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14675

Understanding trends in electrochemical carbon dioxide reduction rates
journal, May 2017

  • Liu, Xinyan; Xiao, Jianping; Peng, Hongjie
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15438