2023
(Invited) Water Oxidation Catalysis with Atomically Defined Active Sites on Nanostructured Materials for Solar Energy Applications
Brudvig G. (Invited) Water Oxidation Catalysis with Atomically Defined Active Sites on Nanostructured Materials for Solar Energy Applications. ECS Meeting Abstracts 2023, MA2023-01: 2149-2149. DOI: 10.1149/ma2023-01372149mtgabs.Peer-Reviewed Original ResearchWater oxidation catalystsMolecular catalystsSolar fuel productionWater oxidationMolecular water oxidation catalystsPhoto-electrochemical water oxidationWater oxidation catalysisNatural photosynthetic systemsPhotoelectrochemical water oxidationMetal oxide surfacesMetal oxide photoanodesFuel productionOxidation catalysisCatalytic performanceOxide photoanodesOxide surfaceNanostructured materialsBioinspired materialsCatalystLimited stabilityActive siteOxide materialsHigh activityPhotosynthetic systemsSolar energy applicationsObservation of Support-Dependent Water Oxidation Kinetics on Molecularly-Derived Heterogeneous Ir-Oxide Catalysts
Zhang H, Liu T, Dulock N, William B, Wang Y, Chen B, Wikar H, Wang D, Brudvig G, Wang D, Waegele M. Observation of Support-Dependent Water Oxidation Kinetics on Molecularly-Derived Heterogeneous Ir-Oxide Catalysts. ECS Meeting Abstracts 2023, MA2023-01: 2154-2154. DOI: 10.1149/ma2023-01372154mtgabs.Peer-Reviewed Original ResearchWater oxidation activityIndium tin oxideActive siteHeterogeneous catalystsOxidation activityHeterogeneous water oxidation catalysisHigh water oxidation activityMost heterogeneous catalystsWater oxidation catalysisWater oxidation catalystsWater oxidation kineticsRate-determining stepOxidation catalysisCeO2 supportSurface chemistryOxidative chargeCatalyst influenceOxidation catalystMolecular structurePhotocatalytic activityCatalystElectronic structureDifferent oxidesTin oxideOxidation kineticsMultielectrode electrochemical cell for in situ structural characterization of amorphous thin‐film catalysts using high‐energy X‐ray scattering
Kwon G, Kisslinger K, Hwang S, Wright G, Layne B, Zhong H, Pattammattel A, Lynch J, Kim J, Hu G, Brudvig G, Lee W, Nam C. Multielectrode electrochemical cell for in situ structural characterization of amorphous thin‐film catalysts using high‐energy X‐ray scattering. Journal Of Applied Crystallography 2023, 56: 1392-1402. DOI: 10.1107/s1600576723006933.Peer-Reviewed Original ResearchThin film catalystElectrochemical cellGlassy carbonHigh-energy X-ray scatteringStructural characterizationX-ray scatteringWater oxidation catalystsPorous electrode architectureThree-electrode configurationHigh-energy x-ray scattering techniquesSitu structural characterizationPDF analysisIridium oxide filmsMetal oxide layerPair distribution function techniqueElectrode architectureOxidation catalystX-ray Scattering MeasurementsX-ray scattering techniquesReaction conditionsCatalystElectrochemical potentialAtomic pair distribution function (PDF) techniqueElectrodeDeposition technique
2020
Surface-Attached Molecular Catalysts on Visible-Light-Absorbing Semiconductors: Opportunities and Challenges for a Stable Hybrid Water-Splitting Photoanode
Liu H, Cody C, Jayworth J, Crabtree R, Brudvig G. Surface-Attached Molecular Catalysts on Visible-Light-Absorbing Semiconductors: Opportunities and Challenges for a Stable Hybrid Water-Splitting Photoanode. ACS Energy Letters 2020, 5: 3195-3202. DOI: 10.1021/acsenergylett.0c01719.Peer-Reviewed Original ResearchMolecular water oxidation catalystsWater splitting photoanodesSolar fuel generationWater oxidation catalystsHybrid photoanodeLong-term stabilityMolecular catalystsFuel generationCharacterization techniquesPhotoanodeStudy of degradationGreat promiseCell consistsCatalystPractical applicationsSemiconductorsDesign strategyStabilityCrucial subjectFuture directionsApplicationsPromiseDegradation
2018
Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst
Rudshteyn B, Fisher K, Lant H, Yang K, Mercado B, Brudvig G, Crabtree R, Batista V. Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst. ACS Catalysis 2018, 8: 7952-7960. DOI: 10.1021/acscatal.8b02466.Peer-Reviewed Original ResearchKinetic isotope effectsWater nucleophilic attack mechanismWater oxidation catalystsWater nucleophilic attackD Kinetic Isotope EffectO bond formationUV-visible spectraDensity functional theoryElectrochemical stepWater oxidationElectrochemical analysisTurnover frequencyDerivative complexesBond formationRadical speciesRational designCis formFunctional theoryIsotope effectRate-limiting stepCatalystComplexesAttack mechanismMechanistic findingsDeprotonation
2017
Photodriven Oxidation of Surface-Bound Iridium-Based Molecular Water-Oxidation Catalysts on Perylene-3,4-dicarboximide-Sensitized TiO2 Electrodes Protected by an Al2O3 Layer
Kamire R, Materna K, Hoffeditz W, Phelan B, Thomsen J, Farha O, Hupp J, Brudvig G, Wasielewski M. Photodriven Oxidation of Surface-Bound Iridium-Based Molecular Water-Oxidation Catalysts on Perylene-3,4-dicarboximide-Sensitized TiO2 Electrodes Protected by an Al2O3 Layer. The Journal Of Physical Chemistry C 2017, 121: 3752-3764. DOI: 10.1021/acs.jpcc.6b11672.Peer-Reviewed Original ResearchMolecular water oxidation catalystsDye-sensitized photoelectrochemical cellsWater oxidation catalystsCharge transfer dynamicsSolar fuel productionCharge recombinationAtomic layer depositionHigher photocurrentTransfer dynamicsDye-sensitized TiO2 photoanodesFemtosecond transient absorption spectroscopyCharge transfer rateTransient absorption spectroscopyALD layersFuel productionDicarboximide chromophorePhotodriven oxidationMononuclear catalystsDinuclear catalystsCatalyst oxidationDye moleculesInitial charge injectionMolecular structurePhotoelectrochemical experimentsAbsorption spectroscopy
2016
Rutile TiO2 as an Anode Material for Water-Splitting Dye-Sensitized Photoelectrochemical Cells
Swierk J, Regan K, Jiang J, Brudvig G, Schmuttenmaer C. Rutile TiO2 as an Anode Material for Water-Splitting Dye-Sensitized Photoelectrochemical Cells. ACS Energy Letters 2016, 1: 603-606. DOI: 10.1021/acsenergylett.6b00279.Peer-Reviewed Original ResearchWater-splitting dye-sensitized photoelectrochemical cellsPhotoelectrochemical cellsDye-sensitized photoelectrochemical cellsR-TiO2Sensitized Photoelectrochemical CellsWater-Splitting DyeWater oxidation catalystsLight-absorbing dyeWide bandgap metal oxide semiconductorsWater oxidationWS-DSPECsRedox mediatorAnode materialsInjection yieldLight harvesterPhotocurrent generationMetal oxide semiconductorDye stabilityAnatase TiO2Rutile polymorphTiO2Injected electronsRutile TiO2Oxide semiconductorsDyeHeterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor
Materna K, Rudshteyn B, Brennan B, Kane M, Bloomfield A, Huang D, Shopov D, Batista V, Crabtree R, Brudvig G. Heterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor. ACS Catalysis 2016, 6: 5371-5377. DOI: 10.1021/acscatal.6b01101.Peer-Reviewed Original ResearchIridium Water Oxidation CatalystsMetal oxide semiconductor surfacesWater oxidation catalystsExperimental IR spectraOxide semiconductor surfaceWater oxidationHeterogenized catalystTurnover frequencyIR spectraSilatrane precursorCovalent attachmentFunctional groupsTurnover numberM KNO3CatalystSemiconductor surfacesPrecatalystOverpotentialCatalysisComputational modelingOxidationPrecursorsKNO3SpectraSurfaceComparison of heterogenized molecular and heterogeneous oxide catalysts for photoelectrochemical water oxidation
Li W, He D, Sheehan S, He Y, Thorne J, Yao X, Brudvig G, Wang D. Comparison of heterogenized molecular and heterogeneous oxide catalysts for photoelectrochemical water oxidation. Energy & Environmental Science 2016, 9: 1794-1802. DOI: 10.1039/c5ee03871e.Peer-Reviewed Original ResearchWater oxidation catalystsHeterogeneous oxide catalystsSurface recombination rateOxide catalystsPerformance of hematiteBulk metal oxide catalystsHeterogeneous water oxidation catalystsPerformance of photoelectrodesO interfacePhotoelectrochemical water oxidationChemical energy conversionRecombination rateMetal oxide catalystsImproved charge transferAdditional charge-transfer pathwaysCharge transfer pathwayCombination of catalystsPEC performancePEC systemHematite photoanodesWater splittingWater oxidationIr catalystOxidation catalystPhotoelectrochemical reactions
2015
Hematite‐Based Solar Water Splitting in Acidic Solutions: Functionalization by Mono‐ and Multilayers of Iridium Oxygen‐Evolution Catalysts
Li W, Sheehan S, He D, He Y, Yao X, Grimm R, Brudvig G, Wang D. Hematite‐Based Solar Water Splitting in Acidic Solutions: Functionalization by Mono‐ and Multilayers of Iridium Oxygen‐Evolution Catalysts. Angewandte Chemie 2015, 127: 11590-11594. DOI: 10.1002/ange.201504427.Peer-Reviewed Original ResearchWater oxidation catalystsSolar water splittingWater splittingAcidic solutionMolecular water oxidation catalystsStable water oxidation catalystsNear-unity Faradaic efficiencyOxygen evolution catalystsStable solar water splittingFaradaic efficiencyPhotoelectrochemical cellsImportant technological implicationsCatalystLow pHMonolayers
2011
Photosynthesis: Energy Conversion
Ulas G, Brudvig G. Photosynthesis: Energy Conversion. 2011 DOI: 10.1002/9781119951438.eibc0455.Peer-Reviewed Original ResearchSolar fuel productionSustainable solar fuel productionWater oxidation catalysisWater oxidation catalystsLight-driven oxidationNatural photosynthetic systemsHigh-energy chemicalsEnergy conversionCarbon dioxide reductionSolar energy conversionFuel productionArtificial photosynthesisWater oxidationRedox levelingHalf reactionOxygenic photosynthesisElectron transferCatalytic turnoverCatalytic mechanismChemical energyDirect light absorptionElectron transport machineryLight absorptionPhotosynthetic systemsLight energy captureAn Iridium(IV) Species, [Cp*Ir(NHC)Cl]+, Related to a Water-Oxidation Catalyst
Brewster T, Blakemore J, Schley N, Incarvito C, Hazari N, Brudvig G, Crabtree R. An Iridium(IV) Species, [Cp*Ir(NHC)Cl]+, Related to a Water-Oxidation Catalyst. Organometallics 2011, 30: 965-973. DOI: 10.1021/om101016s.Peer-Reviewed Original ResearchWater oxidation catalystsOne-electron stepsX-ray crystallographyWingtip groupsElectrochemical characterizationLigand environmentElectrochemical behaviorOxidation stateEPR spectroscopyNew compoundsCatalystRhombic symmetryCompoundsΚ2 CC donorsPrecatalystNHCChelatesCrystallographySpectroscopyLigandsCatalyticPrecursorsCharacterizationWaterA visible light water-splitting cell with a photoanode formed by codeposition of a high-potential porphyrin and an iridium water-oxidation catalyst
Moore G, Blakemore J, Milot R, Hull J, Song H, Cai L, Schmuttenmaer C, Crabtree R, Brudvig G. A visible light water-splitting cell with a photoanode formed by codeposition of a high-potential porphyrin and an iridium water-oxidation catalyst. Energy & Environmental Science 2011, 4: 2389-2392. DOI: 10.1039/c1ee01037a.Peer-Reviewed Original ResearchAnodic deposition of a robust iridium-based water-oxidation catalyst from organometallic precursors
Blakemore J, Schley N, Olack G, Incarvito C, Brudvig G, Crabtree R. Anodic deposition of a robust iridium-based water-oxidation catalyst from organometallic precursors. Chemical Science 2011, 2: 94-98. DOI: 10.1039/c0sc00418a.Peer-Reviewed Original ResearchWater oxidation catalystsOrganometallic precursorsAnodic depositionRobust water oxidation catalystsLight-driven oxidationInorganic heterogeneous catalystsArtificial photosynthesisWater oxidationCatalyst materialsHeterogeneous catalystsFour-electronAqueous solutionCatalystPhotosystem IIOxidationPrecursorsSustainable sourceElectrodepositionIridiumDepositionMaterialsComplexesReactionOxygenAqua
2009
Deposition of an oxomanganese water oxidation catalyst on TiO 2 nanoparticles : computational modeling, assembly and characterization
Li G, Sproviero E, Snoeberger R, Iguchi N, Blakemore J, Crabtree R, Brudvig G, Batista V. Deposition of an oxomanganese water oxidation catalyst on TiO 2 nanoparticles : computational modeling, assembly and characterization. Energy & Environmental Science 2009, 2: 230-238. DOI: 10.1039/b818708h.Peer-Reviewed Original ResearchWater oxidation catalystsOxidation catalystTiO2 nanoparticlesUV-visible spectroscopyTiO 2 nanoparticlesMixed valence stateAmorphous TiO2 nanoparticlesWater ligandsElectrochemical studiesElectrochemical measurementsEPR spectroscopySurface complexesMimic photosynthesisDirect adsorptionSitu synthesisTiO2 surfaceSuccessful attachmentEPR dataNanoparticlesCatalystSolar cellsSpectroscopyComputational modelingAdsorptionEPR
2005
Photosynthesis: Energy Conversion
Ulas G, Brudvig G. Photosynthesis: Energy Conversion. 2005 DOI: 10.1002/0470862106.ia805.Peer-Reviewed Original ResearchSolar fuel productionSustainable solar fuel productionWater oxidation catalysisWater oxidation catalystsLight-driven oxidationNatural photosynthetic systemsHigh-energy chemicalsEnergy conversionCarbon dioxide reductionSolar energy conversionFuel productionArtificial photosynthesisWater oxidationRedox levelingHalf reactionOxygenic photosynthesisElectron transferCatalytic turnoverCatalytic mechanismChemical energyDirect light absorptionElectron transport machineryLight absorptionPhotosynthetic systemsLight energy captureCatalytic Oxygen Evolution by a Bioinorganic Model of the Photosystem II Oxygen-Evolving Complex
Howard D, Tinoco A, Brudvig G, Vrettos J, Allen B. Catalytic Oxygen Evolution by a Bioinorganic Model of the Photosystem II Oxygen-Evolving Complex. Journal Of Chemical Education 2005, 82: 791. DOI: 10.1021/ed082p791.Peer-Reviewed Original ResearchBioinorganic modelsWater oxidationMn4 clusterArtificial water oxidation catalystsBioinorganic model complexesCatalytic oxygen evolutionWater oxidation catalystsPhotosystem IIPhotosynthetic water oxidationUV-visible spectroscopyOxygen-Evolving ComplexDeuterium kinetic isotope effectsPhotosystem II Oxygen Evolving ComplexKinetic isotope effectsBioinorganic chemistryTerpy complexesInorganic synthesisPlace of H2OManganese complexesModel complexesPrimary oxidantManganese clusterOne-electronOxygen evolutionActive site