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  • CenterforDirectCatalyticConversionofBiomasstoBiofuels(C3Bio)

    RESEARCHPLANANDDIRECTIONSWewillmaximizetheenergyandcarbonefficienciesofadvancedbiofuelsproductionbythedesignofboththermalandchemicalconversionprocessesandthebiomassitself.Impactsaretomorethandouble thecarboncapturedintofuelmoleculesandexpandtheproductrangetoalkanesandotherenergyrichfuels.

    C3Biodevelopstransformationalknowledgeandtechnologiesforthedirectconversionofplantlignocellulosicbiomasstoadvanced(dropin)biofuelsandotherbiobasedproducts,currentlyderivedfromoil,bytheuseofnewchemicalcatalystsandthermaltreatments.

  • SamplePreparationforBiomassBiomaterialsMicroscopy

    ScientificAchievementOptimizedandstandardizedasetofhybridbiologicalandmaterialssciencesamplepreparationtechniquestoenableconsistentlyhighqualitymultiscalemicroscopyanalysisofbiomass.

    SignificanceandImpactProvidesasinglegotoreferenceforthefieldthatsharesdetailsandtipsthatarenotpossibletofullyconveyinthetypicalmanuscriptmethodssection.

    Facilitatesdirect,quantitativecomparisonbetweensamplespreparedandimagedbythesemethods.

    Donohoe,B.S.;Ciesielski,P.N.;andVinzant,T.B.PRESERVATION AND PREPARATION OF LIGNOCELLULOSIC

    BIOMASS SAMPLES FOR MULTISCALE MICROSCOPYANALYSIS,In:MichaelE.Himmel(ed.),Biomass

    Conversion:MethodsandProtocols,MethodsinMolecularBiology,908,3147(2012).

    [10.1007/9781617799563_4]

    WorkwasperformedatNREL

    ResearchDetails NRELsBiomassSurfaceCharacterizationLaboratory(BSCL)isaleaderin

    multiscalemicroscopicstructuralanalysisofbiomassconversionprocesses. C3BioenabledacriticaltransitionintheBSCLworkflowtoinclude

    quantitativeimageanalysisasthefinalgoalofallimagingefforts. Theimpactquantitativeimageanalysishashadoninformingsampleprep

    andimageacquisitionisreflectedinthischapter.

    staining'solu+on'

    deionized'water' mul+2grid'

    holder'

    staining'bath'''

    a" bcba

    water(convec, on(pla/ orm(

    vacuumchamber

    thermocouplesample

    chambers

    dryingchamber

    hot(and(cold(water(controllers

    CO2cylinder

    water(chiller

    water(heater

    condenser(chamber

  • TandemMassSpectrometricAnalysisofDegradedCellulose

    ScientificAchievementDemonstratedthatchlorideanionattachment/atmosphericpressureionizationgeneratesonlyoneionforeachcarbohydrateinamixtureandthatmultistagetandemmassspectrometrycanbeusedtodeterminetheionsstructures.

    SignificanceandImpactAllowsmoredetailedcharacterizationofmixturesofpyrolyzed andotherwisedegradedcellulosethanbefore.

    Vinueza,N.R.,Gallardo,V.A.,Klimek,J.F.,Carpita,N.,andKenttmaa,H.I.ANALYSISOFCARBOHYDRATESBYATMOSPHERICPRESSURECHLORIDEANIONATTACHMENTTANDEMMASSSPECTROMETRY,Fuel,105,235246(2013).

    WorkwasperformedatPurdueUniversity

    ResearchDetails Usedlinearquadrupole iontrapandavarietyof

    ionizationmethodstoionizepurecarbohydrates Afteridentificationofthebestionizationmethod,

    examinedknownmixturesofcarbohydrates MeasuredtandemmassspectrauptoMS4 to

    gatherusefulstructuralinformationfromthefragmentationpatternsofthecarbohydrates

    140 160 180 200 220 240 260 280 300 320 340 360 380 400m/z

    0

    10

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    100377

    215

    185

    379217

    187161

    [M+ 35Cl]

    [M+ 35Cl][M+ 35Cl]

    Fructose

    CellobioseXylose

    Rel

    ativ

    e A

    bund

    ance

    [C6H9O5]

    Isolationofionofm/z377followedbyfragmentation

    Chlorideanionattachmentmassspectrumforamixtureofthreecompounds(35Cland37ClIsotopesfacilitateIdentification)

    Fructose

  • FeIII(POP) Catalyst for HMF Oxidation to FDCAScientificAchievementAporphyrinbasedporousorganicpolymer(POP)loadedwithFe3+catalystisathermallystableandrecyclablecatalystforoxidationofhydroxymethylfurfural (HMF)to2,5furandicarboxylicacid(FDCA)inwaterusingmolecularoxygen.SignificanceandImpact InC3Bio,wehaveshownthatmaleic acidcatalysisconvertsglucoseinnoncrystallinepolymersinbiomasstoHMF.

    Saha etalachievedquantitativeconversionofHMFwith>85%selectivityinwaterundermildreactionconditions.

    ThecatalystretainedFe(III)oxidationstateaftercatalysisandmetaldoesnotleachintosolution.

    FDCAisapromisingreplacementforpetroleumderivedterephthalic acidforpolyesterproduction.

    Saha,B.;Gupta,D.;AbuOmar,M.M.;Modak,A.;andBhaumik,A.PORPHYRINBASED POROUS ORGANIC POLYMER SUPPORTEDIRON(III)CATALYST FOR EFFICIENT AEROBICOXIDATION OF 5HYDROXYMETHYLFURFURALINTO 2,5FURANDICARBOXYLIC ACID.JournalofCatalysis,299,316320(2013).[10.1016/j.jcat.2012.12.024]WorkwasperformedatPurdueUniversityandUniversityofDelhi.CatalystwaspreparedbycollaboratoratIndianAssociationfortheCultivationofScience.

    ResearchDetails

    Beforecatalysis

    Aftercatalysis0

    20

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    120

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    F co

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    and

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    n, %

    Time, h

    O COOHHOOC

    O CHOHOOC

    O CHOHO

    O

    CHO

    CHO

    Characterizationofthecatalystshoweduniformnanospheres ofdimension50100nmwhichselfassembletolargersizes.

    Hydroxymethyl group(CH2OH)ofHMFoxidizedfirstfollowedbyoxidationofCHOgroup. Thedatasupportahypothesisthatthereactionprogressesviaafreeradicalchainmechanismwiththeformationofperoxyl radicalinthecatalyticcycle.

  • 3D Electron Tomography of Pretreated Biomass Informs Atomic Modeling of Cellulose Microfibrils

    ScientificAchievement Using3Delectrontomographyandnovelcomputationalanalysistools,wemodeledandquantifiedthemacromoleculararchitectureofthermochemicallytreatedbiomass.

    Significance and Impact Thisstudyproducedthefirstmeasurementsofcellulosemicrofibrilcurvature.Weinvestigatedthesignificanceofthisparameterbyconstructionandevaluationofatomicmodelsthatexhibitedthegeometryobtainedfromthemicroscopydata.

    Ourresultsandanalyseshaveelucidatednewrelationshipsbetweenthenanostructureandenergeticsofplantcellulosethatmaybeexploitedincatalyticconversionprocesses.

    Ciesielski,P.N.;Matthews,J.F.;Tucker,M.P.;Beckham,G.T.;Crowley,M.F.;Himmel,M.E.;Donohoe,B.S.3DELECTRON TOMOGRAPHY OF PRETREATEDBIOMASS INFORMS ATOMIC MODELING OF CELLULOSE MICROFIBRILS.ACSNano,7,80118019.2013.DOI: 10.1021/nn4031542.WorkperformedattheNationalRenewableEnergyLaboratory

    Theradiusofcurvatureofthemicrofibrilswasmeasuredfromthefittedcurves.Atomisticmodelswereconstructedusingtheextractedgeometricparameters.Kinkdefectswerepredictedintheatomicmodelswhenthefibrilwasbentaboutcertaincrystallographicdirections.

    Tomographicsubvolumesshowingspacecurvesfittocellulosemicrofibrils(scalebars10nm)

    Averagae

    radiusofcurvature(nm

    )

    Originalatomiccoordinates

    Energyminimizedatomiccoordinates

  • Catalyticcleavageandhydrodeoxygenationofligninmodels

    ScientificAchievementAcombinedZn/Pd/CcatalysteffectivelycleavedtheligninO4linkageandsubsequentlyhydrodeoxygenated thearomaticfragmentswithoutlossofaromaticfunctionalgroups.Thecatalystisrobustandfullyrecyclablewithouttheneedforadditionalzinc.SignificanceandImpactTheO4linkageisthemostabundantrepeatingsubunitoftheligninmacromolecule.Devisingacatalystthatcanselectivelycleavethistypeofetherlinkageandundergohydrodeoxygenationprovidesameansofunzippingtheverycomplexpolymericstructureintosmaller,manageablemoleculesthathavehigherenergyvalue. ParsellTH,OwenBC,KleinI,JarrellTM,

    MarcumCL,HaupertLJ,AmundsonLM,KenttmaaHIRibeiroF,MillerJT,AbuOmarMM.Cleavageandhydrodeoxygenation(HDO)ofCObondsrelevanttoligninconversionusingPd/Znsynergisticcatalysis.Chem.Sci.,4,806813(2013).[10.1039/C2SC21657D]

    WorkwasperformedatPurdueUniversityandArgonneNationalLab

    ResearchDetails Inatypicalexperiment:substrate,5wt%Zn/Pd/C,andmethanol(15mL)wereaddedtoadryglasssleeve,placedintoastainlesssteelParrreactorandsealed.Whilestirring,themixturewaspurgedwithUHPgradeH2 forca.12min.,pressurizedwithH2 (30300psi,220.4bar),andheatedto150C.

    Themonomericligninsurrogatesubstrateswere4(hydroxymethyl)2methoxyphenol,4hydroxy3methoxybenzaldehyde,and4(methoxymethyl)2methoxyphenol.Thedimeric ligninsurrogatewasguaiacylglycerolguaiacyl.

    ReactionproductswerecharacterizedusingHPLCcoupledtoanLQITmassspectrometerequippedwithanESIsourceusingnegativeionmode.

  • CobaltCatalyzedOxidativeCleavageofLigninModels

    ScientificAchievementGmodelsofligninareslowtoreact.However,wedevelopedanewcatalystthattransformsbothSandGsubunitsligninmodelsintobenzoquinonesinhighyields.SignificanceandImpactLignin,amacromoleculeofsyringyl(S)andguaiacyl (G)subunits,isanunderusedproductofbiorefinery operations.Optimalreactionconditionsfortheconversionofligninmodelstoquinones weredetermined.Internalligandandaliphaticbaseontheligandallowforamuchstrongercatalyticactivity.Thismethodology ishighlyapplicabletotheoxidativecleavageoflignin.

    Cedeno,D.;Bozell,J.J.;TetrahedronLett.2012,53,23802383. Biannic,B.;Bozell,J.J.manuscriptinpreparation

    Workwasperformedat:UniversityofTennessee,CenterforRenewableCarbon

    ResearchDetails PreviousstudiesfromourlaboratoryshowedthatGligninmodelsundergooxidationinpresenceofCosalen catalystandahinderedbasein50%yield.

    ThisnewunsymmetricalCosalen catalystoxidizeseachoftheligninprimaryunits. Thecatalystcontainsaninternalnitrogenligand(neededforSandGsubunits)andaninternalbulkybase(neededforGsubunit).

    Anefficientprotectinggroupfreestrategyforthesynthesisofligninmodelshasalsobeendeveloped.

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    H i g h V a l u e C h e m i c a l s

  • Selective cobalt catalyzed oxidations of biorefinery lignin

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    DianaC,andBozellJJ.Catalyticoxidationofparasubstit

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