2024
Structure of a biohybrid photosystem I-platinum nanoparticle solar fuel catalyst
Gisriel C, Malavath T, Qiu T, Menzel J, Batista V, Brudvig G, Utschig L. Structure of a biohybrid photosystem I-platinum nanoparticle solar fuel catalyst. Nature Communications 2024, 15: 9519. PMID: 39496605, PMCID: PMC11535483, DOI: 10.1038/s41467-024-53476-y.Peer-Reviewed Original ResearchLight-driven H2 productionFuel catalystUnity quantum efficiencyPhotosynthetic biohybrid systemsPigment-protein complexesLight-driven enzymePlatinum nanoparticlesH2 productionQuantum efficiencyPhotosystem I complexCatalystChemical energyCryo-EM structureResolution cryo-EM structureBiohybrid systemsFuel productionStored solar energyPhotosystem IBiology platformReducing equivalentsMolecular basisI complexSolar energyBinding sitesStructureWater Ligands Regulate the Redox Leveling Mechanism of the Oxygen-Evolving Complex of the Photosystem II
Liu J, Yang K, Long Z, Armstrong W, Brudvig G, Batista V. Water Ligands Regulate the Redox Leveling Mechanism of the Oxygen-Evolving Complex of the Photosystem II. Journal Of The American Chemical Society 2024, 146: 15986-15999. PMID: 38833517, DOI: 10.1021/jacs.4c02926.Peer-Reviewed Original ResearchProton-coupled electron transferOxygen-evolving complexWater insertionWater ligandsCatalytic cycleMolecular dynamicsO-O bondQuantum mechanics/molecular mechanicsConformational changesFree energy changeLigand environmentElectron transferLigand exchangePhotosystem IIOxygen evolutionWater binding mechanismsEnergy changeLigandBinding mechanismAqueous environmentRedoxWater bindingLigand bindingCatalystIsomerizationBreaking a Molecular Scaling Relationship Using an Iron–Iron Fused Porphyrin Electrocatalyst for Oxygen Reduction
Nishiori D, Menzel J, Armada N, Cruz E, Nannenga B, Batista V, Moore G. Breaking a Molecular Scaling Relationship Using an Iron–Iron Fused Porphyrin Electrocatalyst for Oxygen Reduction. Journal Of The American Chemical Society 2024, 146: 11622-11633. PMID: 38639470, DOI: 10.1021/jacs.3c08586.Peer-Reviewed Original ResearchOxygen reduction reactionBinuclear catalystsElectrophilic characterDesign of efficient electrocatalystsCatalytic turnover frequencySynthetic design strategiesMacrocyclic ligandCoordination sphereLigand designTurnover frequencyElectronic conjugationEfficient electrocatalystsReduction reactionOxygen reductionMolecular scaffoldsCatalystCatalytic centerIron-ironCharged sitesElectrocatalystsElectrocatalysisLigandBioinspired applicationsDesign strategyScaling relationships
2022
PM-IRRAS and DFT investigation of the surface orientation of new Ir piano-stool complexes attached to Au(111)
Miller C, Brunner F, Kelly H, Cheung P, Torquato N, Gembicky M, Okuno S, Chan T, Batista V, Kubiak C. PM-IRRAS and DFT investigation of the surface orientation of new Ir piano-stool complexes attached to Au(111). Dalton Transactions 2022, 51: 17688-17699. PMID: 36345597, DOI: 10.1039/d2dt02730e.Peer-Reviewed Original ResearchPiano-stool complexesPhenylpyridine ligandsPM-IRRASPolarization modulation infrared reflection absorption spectroscopyInfrared reflection absorption spectroscopySelf-assembled monolayersNew catalytic systemReflection absorption spectroscopyMinimum energy orientationMolecular catalystsOrganometallic catalystsCatalytic systemDFT calculationsSurface immobilizationDFT investigationAbsorption spectroscopyCatalystSurface mechanismBipyridineLigandsHeterogenous surfaceComplexesEnergy orientationSuch hybrid systemsSurface orientationReply To: Confined molecular catalysts provide an alternative interpretation to the electrochemically reversible demetallation of copper complexes
Weng Z, Wu Y, Wang M, Brudvig GW, Batista VS, Liang Y, Feng Z, Wang H. Reply To: Confined molecular catalysts provide an alternative interpretation to the electrochemically reversible demetallation of copper complexes. Nature Communications 2022, 13: 4191. PMID: 35869050, PMCID: PMC9307650, DOI: 10.1038/s41467-022-31662-0.Peer-Reviewed Original ResearchBinding of the substrate analog methanol in the oxygen-evolving complex of photosystem II in the D1-N87A genetic variant of cyanobacteria
Kalendra V, Reiss KM, Banerjee G, Ghosh I, Baldansuren A, Batista VS, Brudvig GW, Lakshmi KV. Binding of the substrate analog methanol in the oxygen-evolving complex of photosystem II in the D1-N87A genetic variant of cyanobacteria. Faraday Discussions 2022, 234: 195-213. PMID: 35147155, DOI: 10.1039/d1fd00094b.Peer-Reviewed Original ResearchConceptsOxygen-evolving complexDensity functional theorySolar water-splitting protein complexTwo-dimensional hyperfine sublevel correlation spectroscopyPhotosystem IIQuantum mechanics/molecular mechanicsHyperfine sublevel correlation spectroscopyWater oxidation reactionWater oxidationCatalytic clustersOxidation reactionSubstrate waterMolecular mechanicsCorrelation spectroscopyFunctional theorySubstrate analoguesLight energyMethanolComplexesReactionIntermediatesDetailed mechanismCatalystSpectroscopyWater
2021
Observation of a potential-dependent switch of water-oxidation mechanism on Co-oxide-based catalysts
Lang C, Li J, Yang K, Wang Y, He D, Thorne J, Croslow S, Dong Q, Zhao Y, Prostko G, Brudvig G, Batista V, Waegele M, Wang D. Observation of a potential-dependent switch of water-oxidation mechanism on Co-oxide-based catalysts. Chem 2021, 7: 2101-2117. DOI: 10.1016/j.chempr.2021.03.015.Peer-Reviewed Original ResearchWater oxidation mechanismWater oxidation reactionWater nucleophilic attack mechanismCo-based catalystsO bond formationNucleophilic attack mechanismKey elementary stepsHeterogeneous catalystsSalt electrolyteElectrode potentialApplied potentialBond formationLow driving forceO couplingElementary stepsMechanistic switchCatalystHigh driving forceDriving forceReactionAttack mechanismWater activityElectrolyteHereinPotential
2018
CO2 Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields
Clark M, Ge A, Videla P, Rudshteyn B, Miller C, Song J, Batista V, Lian T, Kubiak C. CO2 Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields. Journal Of The American Chemical Society 2018, 140: 17643-17655. PMID: 30468391, DOI: 10.1021/jacs.8b09852.Peer-Reviewed Original ResearchInterfacial electric fieldSum frequency generation spectroscopyStark tuning rateReduction catalystAu electrodePotential-dependent frequency shiftNew catalytic electrodesCO2 reduction catalystsGold electrode surfaceFrequency generation spectroscopySite of CODensity functional theoryMolecular catalystsCatalytic electrodesElectrode surfaceCarbonyl ligandsHeterogeneous catalystsTuning rateSemiconductor electrodesGeneration spectroscopyInterfacial fieldSFG spectraCatalystVibrational spectraExperimental frequency shiftsDistinct Binding of Rhenium Catalysts on Nanostructured and Single-Crystalline TiO2 Surfaces Revealed by Two-Dimensional Sum Frequency Generation Spectroscopy
Vanselous H, Videla P, Batista V, Petersen P. Distinct Binding of Rhenium Catalysts on Nanostructured and Single-Crystalline TiO2 Surfaces Revealed by Two-Dimensional Sum Frequency Generation Spectroscopy. The Journal Of Physical Chemistry C 2018, 122: 26018-26031. DOI: 10.1021/acs.jpcc.8b08423.Peer-Reviewed Original ResearchTwo-dimensional sum frequency generation spectroscopySum frequency generation spectroscopyFrequency generation spectroscopyTiO2 surfaceGeneration spectroscopySingle-crystalline TiO2 surfacesCO2 reduction catalystsSelective catalytic performanceDifferent TiO2 surfacesVibrational relaxation pathwaysVibrational relaxation dynamicsAb initio simulationsComplex electronic structureMolecular catalystsCross-peak patternsReduction catalystSolvation environmentCatalytic performanceRhenium catalystsTiO2 electrodeCarbonyl modesCatalystInitio simulationsElectronic structureRelaxation pathwaysCover Feature: Behavior of Ru–bda Water‐Oxidation Catalysts in Low Oxidation States (Chem. Eur. J. 49/2018)
Matheu R, Ghaderian A, Francàs L, Chernev P, Ertem M, Benet‐Buchholz J, Batista V, Haumann M, Gimbert‐Suriñach C, Sala X, Llobet A. Cover Feature: Behavior of Ru–bda Water‐Oxidation Catalysts in Low Oxidation States (Chem. Eur. J. 49/2018). Chemistry - A European Journal 2018, 24: 12736-12736. DOI: 10.1002/chem.201803661.Peer-Reviewed Original ResearchWater-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 findingsDeprotonationDopant-Dependent SFG Response of Rhenium CO2 Reduction Catalysts Chemisorbed on SrTiO3 (100) Single Crystals
Ge A, Videla P, Rudshteyn B, Liu Q, Batista V, Lian T. Dopant-Dependent SFG Response of Rhenium CO2 Reduction Catalysts Chemisorbed on SrTiO3 (100) Single Crystals. The Journal Of Physical Chemistry C 2018, 122: 13944-13952. DOI: 10.1021/acs.jpcc.8b01123.Peer-Reviewed Original ResearchDensity functional theorySFG responseVibrational sum frequency generation spectroscopySum frequency generation spectroscopyCO2 reduction catalystsFrequency generation spectroscopySrTiO3 single crystalsSTO surfaceReduction catalystDFT calculationsSFG resultsGeneration spectroscopySingle crystalsMolecular probesElectronic structureFunctional theoryCl atomsMetallic natureConduction bandSubstrateSurfaceCrystalsCatalystSpectroscopyFac
2017
Electrode-Ligand Interactions Dramatically Enhance CO2 Conversion to CO by the [Ni(cyclam)](PF6)2 Catalyst
Wu Y, Rudshteyn B, Zhanaidarova A, Froehlich J, Ding W, Kubiak C, Batista V. Electrode-Ligand Interactions Dramatically Enhance CO2 Conversion to CO by the [Ni(cyclam)](PF6)2 Catalyst. ACS Catalysis 2017, 7: 5282-5288. DOI: 10.1021/acscatal.7b01109.Peer-Reviewed Original ResearchCO2 conversionTransition metal complexesElectrochemical CO2 conversionDesign of ligandsEnhanced reaction kineticsCell operating conditionsCyclam ligandGold electrodeElectrocatalytic performanceHg surfaceDispersive interactionsReaction kineticsMetallic surfacesCatalystDramatic enhancementLigandsCOConversionSurfaceElectrodeComplexesInteractionKineticsOperating conditions
2016
Heterogenized 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 modelingOxidationPrecursorsKNO3SpectraSurfaceSurface-Induced Anisotropic Binding of a Rhenium CO2‑Reduction Catalyst on Rutile TiO2(110) Surfaces
Ge A, Rudshteyn B, Psciuk B, Xiao D, Song J, Anfuso C, Ricks A, Batista V, Lian T. Surface-Induced Anisotropic Binding of a Rhenium CO2‑Reduction Catalyst on Rutile TiO2(110) Surfaces. The Journal Of Physical Chemistry C 2016, 120: 20970-20977. DOI: 10.1021/acs.jpcc.6b03165.Peer-Reviewed Original ResearchVibrational sum frequency generation spectroscopySum frequency generation spectroscopyCO2 reduction catalystsDensity functional theory levelFrequency generation spectroscopyHigh surface coverageProper hydrogen bondingHydrogen bondingCarboxylate groupsSingle-crystalline TiO2Water moleculesGeneration spectroscopyTheory levelSurface coverageSFG intensityOptical anisotropyIsotropic distributionAnisotropic distributionRing angleCatalystNearest-neighbor effectsMoleculesPlane rotationSurfaceTilt angleOrientation of Cyano-Substituted Bipyridine Re(I) fac-Tricarbonyl Electrocatalysts Bound to Conducting Au Surfaces
Clark M, Rudshteyn B, Ge A, Chabolla S, Machan C, Psciuk B, Song J, Canzi G, Lian T, Batista V, Kubiak C. Orientation of Cyano-Substituted Bipyridine Re(I) fac-Tricarbonyl Electrocatalysts Bound to Conducting Au Surfaces. The Journal Of Physical Chemistry C 2016, 120: 1657-1665. DOI: 10.1021/acs.jpcc.5b10912.Peer-Reviewed Original ResearchSum frequency generation spectroscopyGold surfaceAu surfaceCO2 reduction catalystsFrequency generation spectroscopyReduction of CO2Density functional theoryMolecular catalystsReduction catalystBipyridine ligandsElectrochemical experimentsGeneration spectroscopyCatalytic turnoverSFG spectraElectrocatalystsFunctional theoryCatalystWeak bindingTheoretical methodsSurfaceBipyridineCatalysisSpectroscopyLigandsTriply
2014
Linker Rectifiers for Covalent Attachment of Transition‐Metal Catalysts to Metal‐Oxide Surfaces
Ding W, Negre CF, Palma JL, Durrell AC, Allen LJ, Young KJ, Milot RL, Schmuttenmaer CA, Brudvig GW, Crabtree RH, Batista VS. Linker Rectifiers for Covalent Attachment of Transition‐Metal Catalysts to Metal‐Oxide Surfaces. ChemPhysChem 2014, 15: 1138-1147. PMID: 24668518, DOI: 10.1002/cphc.201400063.Peer-Reviewed Original ResearchInterfacial electron transferElectron transferWater oxidation catalystsTransition metal catalystsElectron transfer propertiesBack electron transferMetal oxide surfacesElectron paramagnetic resonanceAcetylacetonate groupTerpyridyl groupsElectrode surfaceOxidation catalystMolecular linkersElectron reactionsAmide bondTiO2 surfaceParamagnetic resonanceCovalent attachmentAmide linkageTerahertz spectroscopic measurementsSpectroscopic measurementsElectron injectionTransfer propertiesLinkerCatalyst
2013
A Self‐Improved Water‐Oxidation Catalyst: Is One Site Really Enough?
López I, Ertem M, Maji S, Benet‐Buchholz J, Keidel A, Kuhlmann U, Hildebrandt P, Cramer C, Batista V, Llobet A. A Self‐Improved Water‐Oxidation Catalyst: Is One Site Really Enough? Angewandte Chemie 2013, 126: 209-213. DOI: 10.1002/ange.201307509.Peer-Reviewed Original ResearchWater oxidation catalystsRobust water oxidation catalystsTransition metal complexesLarge turnover frequencyDFT computational analysisInterconnected catalytic cyclesMononuclear catalystsHomogeneous catalysisWater oxidationRobust catalystsTurnover frequencyEnergy conversion schemeCatalytic processCatalytic cycleMononuclear systemsCatalystDinuclear systemCatalysisComputational analysisOxidationSpectacular developmentHereinComplexesA Self‐Improved Water‐Oxidation Catalyst: Is One Site Really Enough?
López I, Ertem M, Maji S, Benet‐Buchholz J, Keidel A, Kuhlmann U, Hildebrandt P, Cramer C, Batista V, Llobet A. A Self‐Improved Water‐Oxidation Catalyst: Is One Site Really Enough? Angewandte Chemie International Edition 2013, 53: 205-209. PMID: 24259487, DOI: 10.1002/anie.201307509.Peer-Reviewed Original ResearchWater oxidation catalystsRobust water oxidation catalystsTransition metal complexesLarge turnover frequencyDFT computational analysisInterconnected catalytic cyclesMononuclear catalystsHomogeneous catalysisWater oxidationRobust catalystsTurnover frequencyEnergy conversion schemeCatalytic processCatalytic cycleMononuclear systemsCatalystDinuclear systemCatalysisComputational analysisOxidationSpectacular developmentHereinComplexes
2012
Orientation of a Series of CO2 Reduction Catalysts on Single Crystal TiO2 Probed by Phase-Sensitive Vibrational Sum Frequency Generation Spectroscopy (PS-VSFG)
Anfuso C, Xiao D, Ricks A, Negre C, Batista V, Lian T. Orientation of a Series of CO2 Reduction Catalysts on Single Crystal TiO2 Probed by Phase-Sensitive Vibrational Sum Frequency Generation Spectroscopy (PS-VSFG). The Journal Of Physical Chemistry C 2012, 116: 24107-24114. DOI: 10.1021/jp307406j.Peer-Reviewed Original ResearchVibrational sum frequency generation spectroscopySum frequency generation spectroscopyCO2 reduction catalystsFrequency generation spectroscopyReduction catalystGeneration spectroscopyTiO2 semiconductor surfaceMolecular tilt angleSingle crystal surfacesAverage molecular orientationHeterogeneous electrocatalystsAnchoring groupOverall catalytic efficiencyElectrode surfaceRe centerΣ-bondMolecular linkersCO2 moleculesMolecular conformationMethylene groupMolecular orientationSuch complexesCatalytic efficiencyCatalystCrystal surface