title: Synergistic Enhancement of Electrocatalytic CO2Reduction with Gold Nanoparticles Embedded in Functional Graphene Nanoribbon Composite Electrodes.
abstract: Regulating the complex environment accounting for the stability, selectivity, and activity of catalytic metal nanoparticle interfaces represents a challenge to heterogeneous catalyst design. Here we demonstrate the intrinsic performance enhancement of a composite material composed of gold nanoparticles (AuNPs) embedded in a bottom-up synthesized graphene nanoribbon (GNR) matrix for the electrocatalytic reduction of CO2. Electrochemical studies reveal that the structural and electronic properties of the GNR composite matrix increase the AuNP electrochemically active surface area (ECSA), lower the requisite CO2reduction overpotential by hundreds of millivolts (catalytic onset > -0.2 V versus reversible hydrogen electrode (RHE)), increase the Faraday efficiency (>90%), markedly improve stability (catalytic performance sustained over >24 h), and increase the total catalytic output (>100-fold improvement over traditional amorphous carbon AuNP supports). The inherent structural and electronic tunability of bottom-up synthesized GNR-AuNP composites affords an unrivaled degree of control over the catalytic environment, providing a means for such profound effects as shifting the rate-determining step in the electrocatalytic reduction of CO2to CO, and thereby altering the electrocatalytic mechanism at the nanoparticle surface.
authors.affiliation: Department of Chemistry, University of California Berkeley , Berkeley, California 94720, United States.
authors.forename: Cameron
authors.initials: C
authors.lastname: Rogers
authors.affiliation: Department of Chemistry, University of California Berkeley , Berkeley, California 94720, United States.
authors.forename: Wade S
authors.initials: WS
authors.lastname: Perkins
authors.affiliation: Department of Chemistry, University of California Berkeley , Berkeley, California 94720, United States.
authors.forename: Gregory
authors.initials: G
authors.lastname: Veber
authors.affiliation: The Molecular Foundry, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Teresa E
authors.initials: TE
authors.lastname: Williams
authors.affiliation: Department of Chemistry, University of California Berkeley , Berkeley, California 94720, United States.
authors.forename: Ryan R
authors.identifier: 0000-0001-7618-6970
authors.initials: RR
authors.lastname: Cloke
authors.affiliation: Department of Chemistry, University of California Berkeley , Berkeley, California 94720, United States.|Material Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Kavli Energy Nanosciences Institute at the University of California Berkeley and Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Felix R
authors.identifier: 0000-0003-4723-3111
authors.initials: FR
authors.lastname: Fischer
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D055664:Electrochemical Techniques; D004566:Electrodes; D006046:Gold / Q000737:chemistry*; D006108:Graphite / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D015394:Molecular Structure; D037742:Nanotubes, Carbon / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D037742:Nanotubes, Carbon; D002245:Carbon Dioxide; D006046:Gold; D006108:Graphite