Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry

Abstract

Abstract Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO 2 reduction. Palladium functionalized with a chelating tris‐N‐heterocyclic carbene (NHC) ligand (Pd‐timtmb Me ) exhibits a 32‐fold increase in activity for electrochemical reduction of CO 2 to C1 products with high Faradaic efficiency (FE C1 =86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC‐ligated Pd electrode (Pd‐mimtmb Me ). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular‐materials interfaces enabled by surface organometallic chemistry.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [2];  [2];  [2];  [4];  [4];  [3]; ORCiD logo [2]
+ Show Author Affiliations
  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. ETH Zurich, Zurich (Switzerland)
  4. Chinese Academy of Sciences (CAS), Shanxi (China); Synfuels China, Beijing (China)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1480786
Alternate Identifier(s):
OSTI ID: 1429150
Grant/Contract Number:  
AC02-05CH11231; 101528-002
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 18; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO 2 reduction; electrocatalysis; N-heterocyclic carbenes; palladium; surface chemistry

Citation Formats

Cao, Zhi, Derrick, Jeffrey S., Xu, Jun, Gao, Rui, Gong, Ming, Nichols, Eva M., Smith, Peter T., Liu, Xingwu, Wen, Xiaodong, Copéret, Christophe, and Chang, Christopher J. Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry. United States: N. p., 2018. Web. doi:10.1002/anie.201800367.
Copy to clipboard
Cao, Zhi, Derrick, Jeffrey S., Xu, Jun, Gao, Rui, Gong, Ming, Nichols, Eva M., Smith, Peter T., Liu, Xingwu, Wen, Xiaodong, Copéret, Christophe, & Chang, Christopher J. Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry. United States. https://doi.org/10.1002/anie.201800367
Copy to clipboard
Cao, Zhi, Derrick, Jeffrey S., Xu, Jun, Gao, Rui, Gong, Ming, Nichols, Eva M., Smith, Peter T., Liu, Xingwu, Wen, Xiaodong, Copéret, Christophe, and Chang, Christopher J. Thu . "Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry". United States. https://doi.org/10.1002/anie.201800367. https://www.osti.gov/servlets/purl/1480786.
Copy to clipboard
@article{osti_1480786,
title = {Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry},
author = {Cao, Zhi and Derrick, Jeffrey S. and Xu, Jun and Gao, Rui and Gong, Ming and Nichols, Eva M. and Smith, Peter T. and Liu, Xingwu and Wen, Xiaodong and Copéret, Christophe and Chang, Christopher J.},
abstractNote = {Abstract Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO 2 reduction. Palladium functionalized with a chelating tris‐N‐heterocyclic carbene (NHC) ligand (Pd‐timtmb Me ) exhibits a 32‐fold increase in activity for electrochemical reduction of CO 2 to C1 products with high Faradaic efficiency (FE C1 =86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC‐ligated Pd electrode (Pd‐mimtmb Me ). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular‐materials interfaces enabled by surface organometallic chemistry.},
doi = {10.1002/anie.201800367},
journal = {Angewandte Chemie (International Edition)},
number = 18,
volume = 57,
place = {United States},
year = {Thu Mar 01 00:00:00 EST 2018},
month = {Thu Mar 01 00:00:00 EST 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/anie.201800367
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 99 works
Citation information provided by
Web of Science

Figures / Tables:

Scheme 1 Scheme 1: Synthetic scheme for the preparation of tripodal N-heterocyclic carbenes and functionalization of Pd surfaces: (i) = NaI, Me2CO, RT, 5 min; (ii) = imidazole (1-methylimidazole, 1- isopropylimidazole, or 1-tert-butylimidazole), Me2CO, RT, 5 h; (iii) CO2, H2O2, RT, 1 h; (iv) MeOH, Pd foil.
All figures and tables (4 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Asymmetric Nanocatalysis: N-Heterocyclic Carbenes as Chiral Modifiers of Fe3O4/Pd nanoparticles
journal, September 2010

  • Ranganath, Kalluri V. S.; Kloesges, Johannes; Schäfer, Andreas H.
  • Angewandte Chemie International Edition, Vol. 49, Issue 42
  • DOI: 10.1002/anie.201002782

Electrocatalytic Reduction of CO 2 with Palladium Bis-N-heterocyclic Carbene Pincer Complexes
journal, October 2014

  • Therrien, Jeffrey A.; Wolf, Michael O.; Patrick, Brian O.
  • Inorganic Chemistry, Vol. 53, Issue 24
  • DOI: 10.1021/ic502056w

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

Water-Soluble N-Heterocyclic Carbene-Protected Gold Nanoparticles: Size-Controlled Synthesis, Stability, and Optical Properties
journal, April 2017

  • Salorinne, Kirsi; Man, Renee W. Y.; Li, Chien-Hung
  • Angewandte Chemie, Vol. 129, Issue 22
  • DOI: 10.1002/ange.201701605

Ultrastable Gold Nanoparticles Modified by Bidentate N -Heterocyclic Carbene Ligands
journal, January 2018

  • Man, Renee W. Y.; Li, Chien-Hung; MacLean, Michael W. A.
  • Journal of the American Chemical Society, Vol. 140, Issue 5
  • DOI: 10.1021/jacs.7b08516

Ruthenium Nanoparticles Stabilized by N-Heterocyclic Carbenes: Ligand Location and Influence on Reactivity
journal, October 2011

  • Lara, Patricia; Rivada-Wheelaghan, Orestes; Conejero, Salvador
  • Angewandte Chemie International Edition, Vol. 50, Issue 50
  • DOI: 10.1002/anie.201106348

N-Heterocyclic carbene coated metal nanoparticles
journal, January 2009

  • Hurst, Eleanor C.; Wilson, Karen; Fairlamb, Ian J. S.
  • New Journal of Chemistry, Vol. 33, Issue 9
  • DOI: 10.1039/b905559b

N -Heterocyclic carbenes on close-packed coinage metal surfaces: bis-carbene metal adatom bonding scheme of monolayer films on Au, Ag and Cu
journal, January 2017

  • Jiang, Li; Zhang, Bodong; Médard, Guillaume
  • Chemical Science, Vol. 8, Issue 12
  • DOI: 10.1039/C7SC03777E

NHC-stabilized ruthenium nanoparticles as new catalysts for the hydrogenation of aromatics
journal, January 2013

  • Gonzalez-Galvez, David; Lara, Patricia; Rivada-Wheelaghan, Orestes
  • Catal. Sci. Technol., Vol. 3, Issue 1
  • DOI: 10.1039/C2CY20561K

Silica-Supported Cu Nanoparticle Catalysts for Alkyne Semihydrogenation: Effect of Ligands on Rates and Selectivity
journal, December 2016

  • Fedorov, Alexey; Liu, Hsueh-Ju; Lo, Hung-Kun
  • Journal of the American Chemical Society, Vol. 138, Issue 50
  • DOI: 10.1021/jacs.6b10817

Tunable Heterogeneous Catalysis: N-Heterocyclic Carbenes as Ligands for Supported Heterogeneous Ru/K-Al 2 O 3 Catalysts To Tune Reactivity and Selectivity
journal, August 2016

  • Ernst, Johannes B.; Muratsugu, Satoshi; Wang, Fei
  • Journal of the American Chemical Society, Vol. 138, Issue 34
  • DOI: 10.1021/jacs.6b03821

New Route to Stabilize Ruthenium Nanoparticles with Non-Isolable Chiral N-Heterocyclic Carbenes
journal, October 2015

  • Martínez-Prieto, Luis Miguel; Ferry, Angélique; Lara, Patricia
  • Chemistry - A European Journal, Vol. 21, Issue 48
  • DOI: 10.1002/chem.201502601

Soluble Platinum Nanoparticles Ligated by Long-Chain N-Heterocyclic Carbenes as Catalysts
journal, July 2017

  • Martínez-Prieto, Luis M.; Rakers, Lena; López-Vinasco, Angela M.
  • Chemistry - A European Journal, Vol. 23, Issue 52
  • DOI: 10.1002/chem.201702288

Molecular Adsorbates Switch on Heterogeneous Catalysis: Induction of Reactivity by N-Heterocyclic Carbenes
journal, June 2017

  • Ernst, Johannes B.; Schwermann, Christian; Yokota, Gen-ichi
  • Journal of the American Chemical Society, Vol. 139, Issue 27
  • DOI: 10.1021/jacs.7b05112

N -Heterocyclic Carbene Self-assembled Monolayers on Copper and Gold: Dramatic Effect of Wingtip Groups on Binding, Orientation and Assembly
journal, November 2017

  • Larrea, Christian R.; Baddeley, Christopher J.; Narouz, Mina R.
  • ChemPhysChem, Vol. 18, Issue 24
  • DOI: 10.1002/cphc.201701045

Ruthenium Nanoparticles Stabilized by N-Heterocyclic Carbenes: Ligand Location and Influence on Reactivity
journal, October 2011

  • Lara, Patricia; Rivada-Wheelaghan, Orestes; Conejero, Salvador
  • Angewandte Chemie, Vol. 123, Issue 50
  • DOI: 10.1002/ange.201106348

Highly Stable Water-Soluble Platinum Nanoparticles Stabilized by Hydrophilic N-Heterocyclic Carbenes
journal, September 2014

  • Baquero, Edwin A.; Tricard, Simon; Flores, Juan Carlos
  • Angewandte Chemie, Vol. 126, Issue 48
  • DOI: 10.1002/ange.201407758

Highly Stable Water-Soluble Platinum Nanoparticles Stabilized by Hydrophilic N-Heterocyclic Carbenes
journal, September 2014

  • Baquero, Edwin A.; Tricard, Simon; Flores, Juan Carlos
  • Angewandte Chemie International Edition, Vol. 53, Issue 48
  • DOI: 10.1002/anie.201407758

Water-Soluble N-Heterocyclic Carbene-Protected Gold Nanoparticles: Size-Controlled Synthesis, Stability, and Optical Properties
journal, April 2017

  • Salorinne, Kirsi; Man, Renee W. Y.; Li, Chien-Hung
  • Angewandte Chemie International Edition, Vol. 56, Issue 22
  • DOI: 10.1002/anie.201701605

Negatively Charged N-Heterocyclic Carbene-Stabilized Pd and Au Nanoparticles and Efficient Catalysis in Water
journal, August 2015

Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes
journal, June 2017

Modular Bidentate Hybrid NHC-Thioether Ligands for the Stabilization of Palladium Nanoparticles in Various Solvents
journal, April 2016

  • Rühling, Andreas; Schaepe, Kira; Rakers, Lena
  • Angewandte Chemie International Edition, Vol. 55, Issue 19
  • DOI: 10.1002/anie.201508933

The Influence of para Substituents in Bis(N-Heterocyclic Carbene) Palladium Pincer Complexes for Electrocatalytic CO 2 Reduction
journal, January 2017

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

Influence of the Number and Geometry of Binding Sites on Host–Guest Affinity: Imidazolium-Substituted Receptor Molecules for Small Inorganic Anions
journal, April 2006

  • Fahlbusch, Tilmann; Frank, Markus; Schatz, Jürgen
  • European Journal of Organic Chemistry, Vol. 2006, Issue 8
  • DOI: 10.1002/ejoc.200500825

Carbene Ligands in Surface Chemistry: From Stabilization of Discrete Elemental Allotropes to Modification of Nanoscale and Bulk Substrates
journal, September 2015

  • Zhukhovitskiy, Aleksandr V.; MacLeod, Michelle J.; Johnson, Jeremiah A.
  • Chemical Reviews, Vol. 115, Issue 20
  • DOI: 10.1021/acs.chemrev.5b00220

Rational Design of Efficient Palladium Catalysts for Electroreduction of Carbon Dioxide to Formate
journal, November 2016

Polyannulated Bis(N-heterocyclic carbene)palladium Pincer Complexes for Electrocatalytic CO 2 Reduction
journal, December 2015

NHC-stabilized Ru nanoparticles: Synthesis and surface studies
journal, April 2016

A new entry to N-heterocyclic carbene chemistry: synthesis and characterisation of a triscarbene complex of thallium( i )
journal, January 2003

  • Nakai, Hidetaka; Tang, Yongjun; Gantzel, Peter
  • Chem. Commun., Issue 1
  • DOI: 10.1039/B209071F

Ballbot-type motion of N-heterocyclic carbenes on gold surfaces
journal, October 2016

  • Wang, Gaoqiang; Rühling, Andreas; Amirjalayer, Saeed
  • Nature Chemistry, Vol. 9, Issue 2
  • DOI: 10.1038/nchem.2622

Palladium Nanoparticles in Suzuki Cross-Couplings: Tapping into the Potential of Tris-Imidazolium Salts for Nanoparticle Stabilization
journal, February 2012

  • Planellas, Marc; Pleixats, Roser; Shafir, Alexandr
  • Advanced Synthesis & Catalysis, Vol. 354, Issue 4
  • DOI: 10.1002/adsc.201100574

Simple direct formation of self-assembled N-heterocyclic carbene monolayers on gold and their application in biosensing
journal, September 2016

  • Crudden, Cathleen M.; Horton, J. Hugh; Narouz, Mina R.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12654

Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold
journal, March 2014

  • Crudden, Cathleen M.; Horton, J. Hugh; Ebralidze, Iraklii I.
  • Nature Chemistry, Vol. 6, Issue 5
  • DOI: 10.1038/nchem.1891

N-Heterocyclic carbene-stabilized gold nanoparticles and their assembly into 3D superlattices
journal, January 2009

  • Vignolle, Joan; Tilley, T. Don
  • Chemical Communications, Issue 46
  • DOI: 10.1039/b913884f

Asymmetrische Nanokatalyse: N-heterocyclische Carbene als chirale Modifikatoren von Fe3O4/Pd-Nanopartikeln
journal, September 2010

  • Ranganath, Kalluri V. S.; Kloesges, Johannes; Schäfer, Andreas H.
  • Angewandte Chemie, Vol. 122, Issue 42
  • DOI: 10.1002/ange.201002782

Addressable Carbene Anchors for Gold Surfaces
journal, May 2013

  • Zhukhovitskiy, Aleksandr V.; Mavros, Michael G.; Van Voorhis, Troy
  • Journal of the American Chemical Society, Vol. 135, Issue 20
  • DOI: 10.1021/ja401965d

PEGylated N -Heterocyclic Carbene Anchors Designed To Stabilize Gold Nanoparticles in Biologically Relevant Media
journal, June 2015

  • MacLeod, Michelle J.; Johnson, Jeremiah A.
  • Journal of the American Chemical Society, Vol. 137, Issue 25
  • DOI: 10.1021/jacs.5b02452

Modulare zweizähnige NHC-Thioether-Hybridliganden zur Stabilisierung von Palladium-Nanopartikeln in diversen Lösungsmitteln
journal, April 2016

  • Rühling, Andreas; Schaepe, Kira; Rakers, Lena
  • Angewandte Chemie, Vol. 128, Issue 19
  • DOI: 10.1002/ange.201508933

Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities
journal, January 2016

Platinum N-Heterocyclic Carbene Nanoparticles as New and Effective Catalysts for the Selective Hydrogenation of Nitroaromatics
journal, November 2013

  • Lara, Patricia; Suárez, Andrés; Collière, Vincent
  • ChemCatChem, Vol. 6, Issue 1
  • DOI: 10.1002/cctc.201300821

Long-chain NHC-stabilized RuNPs as versatile catalysts for one-pot oxidation/hydrogenation reactions
journal, January 2016

  • Martínez-Prieto, L. M.; Ferry, A.; Rakers, L.
  • Chemical Communications, Vol. 52, Issue 26
  • DOI: 10.1039/C6CC01130F

Tailor-made N-heterocyclic carbenes for nanoparticle stabilization
journal, January 2014

  • Richter, Christian; Schaepe, Kira; Glorius, Frank
  • Chemical Communications, Vol. 50, Issue 24
  • DOI: 10.1039/c4cc00654b

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

Spontaneously Bi decorated carbon supported Pt nanoparticles for formic acid electro-oxidation
journal, March 2013

Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction
journal, September 2017

A stable tridentate carbene ligand
journal, February 1994

Tin Oxide Dependence of the CO 2 Reduction Efficiency on Tin Electrodes and Enhanced Activity for Tin/Tin Oxide Thin-Film Catalysts
journal, January 2012

  • Chen, Yihong; Kanan, Matthew W.
  • Journal of the American Chemical Society, Vol. 134, Issue 4
  • DOI: 10.1021/ja2108799

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

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Cyclic two-step electrolysis for stable electrochemical conversion of carbon dioxide to formate
    journal, September 2019

      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Scheme 1 (p. 2)figure
      Figure 2 (p. 3)figure
      Figure 3 (p. 3)figure
      Figure 4 (p. 4)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: