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Title: A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction

Abstract

Conversion of the greenhouse gas carbon dioxide (CO2) to value-added products is an important challenge for sustainable energy research, and nanomaterials offer a broad class of heterogeneous catalysts for such transformations. Here we report a molecular surface functionalization approach to tuning gold nanoparticle (Au NP) electrocatalysts for reduction of CO2 to CO. The N-heterocyclic (NHC) carbene-functionalized Au NP catalyst exhibits improved faradaic efficiency (FE = 83%) for reduction of CO2 to CO in water at neutral pH at an overpotential of 0.46 V with a 7.6-fold increase in current density compared to that of the parent Au NP (FE = 53%). Tafel plots of the NHC carbene-functionalized Au NP (72 mV/decade) vs parent Au NP (138 mV/decade) systems further show that the molecular ligand influences mechanistic pathways for CO2 reduction. The results establish molecular surface functionalization as a complementary approach to size, shape, composition, and defect control for nanoparticle catalyst design.

Authors:
 [1];  [1];  [1];  [2];  [1];  [2];  [3];  [2];  [1];  [1];  [4];  [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Chinese Academy of Sciences, Shanxi (China); Synfuels China, Beijing (China)
  4. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy Nanosciences Institute, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466697
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 26; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cao, Zhi, Kim, Dohyung, Hong, Dachao, Yu, Yi, Xu, Jun, Lin, Song, Wen, Xiaodong, Nichols, Eva M., Jeong, Keunhong, Reimer, Jeffrey A., Yang, Peidong, and Chang, Christopher J. A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction. United States: N. p., 2016. Web. doi:10.1021/jacs.6b02878.
Cao, Zhi, Kim, Dohyung, Hong, Dachao, Yu, Yi, Xu, Jun, Lin, Song, Wen, Xiaodong, Nichols, Eva M., Jeong, Keunhong, Reimer, Jeffrey A., Yang, Peidong, & Chang, Christopher J. A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction. United States. doi:10.1021/jacs.6b02878.
Cao, Zhi, Kim, Dohyung, Hong, Dachao, Yu, Yi, Xu, Jun, Lin, Song, Wen, Xiaodong, Nichols, Eva M., Jeong, Keunhong, Reimer, Jeffrey A., Yang, Peidong, and Chang, Christopher J. Mon . "A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction". United States. doi:10.1021/jacs.6b02878. https://www.osti.gov/servlets/purl/1466697.
@article{osti_1466697,
title = {A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction},
author = {Cao, Zhi and Kim, Dohyung and Hong, Dachao and Yu, Yi and Xu, Jun and Lin, Song and Wen, Xiaodong and Nichols, Eva M. and Jeong, Keunhong and Reimer, Jeffrey A. and Yang, Peidong and Chang, Christopher J.},
abstractNote = {Conversion of the greenhouse gas carbon dioxide (CO2) to value-added products is an important challenge for sustainable energy research, and nanomaterials offer a broad class of heterogeneous catalysts for such transformations. Here we report a molecular surface functionalization approach to tuning gold nanoparticle (Au NP) electrocatalysts for reduction of CO2 to CO. The N-heterocyclic (NHC) carbene-functionalized Au NP catalyst exhibits improved faradaic efficiency (FE = 83%) for reduction of CO2 to CO in water at neutral pH at an overpotential of 0.46 V with a 7.6-fold increase in current density compared to that of the parent Au NP (FE = 53%). Tafel plots of the NHC carbene-functionalized Au NP (72 mV/decade) vs parent Au NP (138 mV/decade) systems further show that the molecular ligand influences mechanistic pathways for CO2 reduction. The results establish molecular surface functionalization as a complementary approach to size, shape, composition, and defect control for nanoparticle catalyst design.},
doi = {10.1021/jacs.6b02878},
journal = {Journal of the American Chemical Society},
number = 26,
volume = 138,
place = {United States},
year = {2016},
month = {6}
}

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Works referencing / citing this record:

N-heterocyclic carbene-functionalized magic-number gold nanoclusters
journal, April 2019

  • Narouz, Mina R.; Osten, Kimberly M.; Unsworth, Phillip J.
  • Nature Chemistry, Vol. 11, Issue 5
  • DOI: 10.1038/s41557-019-0246-5

N-Heterocyclic carbene-stabilized gold nanoparticles with tunable sizes
journal, January 2018

  • Bridonneau, N.; Hippolyte, L.; Mercier, D.
  • Dalton Transactions, Vol. 47, Issue 19
  • DOI: 10.1039/c8dt00416a

The role of reticular chemistry in the design of CO2 reduction catalysts
journal, February 2018


Current achievements and the future direction of electrochemical CO 2 reduction: A short review
journal, June 2019


Review on optofluidic microreactors for artificial photosynthesis
journal, January 2018

  • Huang, Xiaowen; Wang, Jianchun; Li, Tenghao
  • Beilstein Journal of Nanotechnology, Vol. 9
  • DOI: 10.3762/bjnano.9.5

N-heterocyclic carbene-functionalized magic-number gold nanoclusters
journal, April 2019

  • Narouz, Mina R.; Osten, Kimberly M.; Unsworth, Phillip J.
  • Nature Chemistry, Vol. 11, Issue 5
  • DOI: 10.1038/s41557-019-0246-5

The role of reticular chemistry in the design of CO2 reduction catalysts
journal, February 2018


N-Heterocyclic carbene-stabilized gold nanoparticles with tunable sizes
journal, January 2018

  • Bridonneau, N.; Hippolyte, L.; Mercier, D.
  • Dalton Transactions, Vol. 47, Issue 19
  • DOI: 10.1039/c8dt00416a

Current achievements and the future direction of electrochemical CO 2 reduction: A short review
journal, June 2019


Review on optofluidic microreactors for artificial photosynthesis
journal, January 2018

  • Huang, Xiaowen; Wang, Jianchun; Li, Tenghao
  • Beilstein Journal of Nanotechnology, Vol. 9
  • DOI: 10.3762/bjnano.9.5