Support effects in the selective gas phase ... - Springer Link

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3UPPORTEFFECTSINTHE SELECTIVEGASPHASE HYDROGENATIONOF P CHLORONITROBENZENE OVERGOLD &ERNANDO#fRDENAS ,IZANA 3ANTIAGO'vMEZ 1UERO .OmMIE0ERRET AND-ARK!+EANE

#HEMICAL%NGINEERING 3CHOOLOF%NGINEERINGAND0HYSICAL3CIENCES (ERIOT 7ATT5NIVERSITY %DINBURGH%(!3 3COTLAND

#ORRESPONDINGAUTHOR4EL % MAIL-!+EANE HWACUK

!BSTRACT 4HECATALYTICCONTINUOUSGASPHASEHYDROGENATIONOF P CHLORONITROBENZENE0ATM4+ HASBEEN INVESTIGATEDOVERASERIESOFOXIDE!L/ 4I/ &E/ AND#E/ SUPPORTED!UMOL CATALYSTS4HE APPLICATIONOFTWOCATALYSTSYNTHESISROUTES IE IMPREGNATION)-0 ANDDEPOSITION PRECIPITATION $0 HASBEENCONSIDEREDWHERETHE$0ROUTE GENERATEDSMALLERMEAN!UPARTICLESIZES NM COMPAREDWITHTHE)-0PREPARATION NM 4HECATALYSTSHAVEBEENCHARACTERISEDINTERMS( CHEMISORPTIONAND"%4AREAMEASUREMENTSWHERE THEFORMATIONOFMETALLIC!UPOST ACTIVATIONHAS BEENVERI½EDBYDIFFUSERE¾ECTANCE56 6IS 82$AND (24%-ANALYSESP #HLOROANILINEWASGENERATEDAS THESOLEREACTIONPRODUCTOVERALLTHE!UCATALYSTS WITHNOEVIDENCEOF# #LANDOR# ./BONDSCISSION ANDORAROMATICRINGREDUCTION4HESPECI½C HYDROGENATIONRATEINCREASEDWITHDECREASING !UPARTICLESIZEFROMTONM REGARDLESSOFTHE NATUREOFTHESUPPORT4HISRESPONSEEXTENDSTOA REFERENCE!U4I/CATALYSTPROVIDEDBYTHE7ORLD 'OLD#OUNCIL!DECREASEINSPECI½CRATEISIN EVIDENCEFORSMALLERPARTICLESNM ANDCANBE ATTRIBUTEDTOAQUANTUMSIZEEFFECT4HERESULTS PRESENTEDESTABLISHTHEBASISFORTHEDESIGNAND DEVELOPMENTOFAVERSATILECATALYTICSYSTEMFORTHE CLEANCONTINUOUSPRODUCTIONOFHIGHVALUEAMINO COMPOUNDSUNDERMILDREACTIONCONDITIONS

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+EYWORDS'OLDCATALYSTSP CHLORONITROBENZENE HYDROGENATIONP CHLOROANILINE!UPARTICLESIZECATALYST SUPPORTEFFECT

)NTRODUCTION (YDROGENATIONPROMOTEDBYGOLDHASEMERGEDASONEOFTHE MOSTCHALLENGINGTOPICSINGOLDCATALYSIS ASRE¾ECTEDINTHE REVIEWSBY#LAUS;=AND(ASHMI;=4HELOWERHYDROGENATION ACTIVITYASSOCIATEDWITH!UWHENCOMPAREDWITHTRADITIONAL METALSEG0T 0D ; =ISCOMPENSATEDFORINTERMSOFTHE HIGH SELECTIVITY THAT !U CAN DELIVER IN HYDROGENATION APPLICATIONS;=)NORDERTODEVELOPVIABLEPROCESSESBASED ON !U CATALYSIS AN EXPLICIT CORRELATION OF ACTIVITYSELECTIVITY WITH CATALYST STRUCTURE IS REQUIRED /NE ISSUE THAT MUST BE RESOLVEDISTHEDIFFERENCEINCATALYTICPERFORMANCEOBSERVED FOR !U SUPPORTED ON DIFFERENT OXIDE CARRIERS ; = 4HE NATURE OF THE SUPPORT CAN AFFECT THE MORPHOLOGY AND DISPERSION OF !U PARTICLES VIA METAL SUPPORT INTERACTIONS ; =ANDITISESTABLISHEDTHATSMALLERNM SUPPORTED !U PARTICLES EXHIBIT ELECTRONIC PROPERTIES THAT ARE QUITE DISTINCTFROMBULK!U;=4HISFEATUREISCRITICALINTHATTHE CATALYTICRESPONSEOF!UINHYDROGENATIONREACTIONSMAYBE DEPENDENT ON CHANGES IN THE ELECTRONIC CHARACTER OF THE SUPPORTED METAL ;= &URTHERMORE WHILE THE CARRIER CAN IMPACTONTHEPROPERTIESOFTHE!UCOMPONENT THESUPPORTED !UPHASEHASBEENREPORTEDTOINDUCECHANGESINTHEOXIDE SUPPORT NOTABLYBYPROMOTINGTHEREDUCTIONOFREDUCIBLE OXIDES INCLUDING &E/ ;= #E/ ;= AND 4I/ ; = #ONSIDERINGTHECOMPLEXNATUREOF!U SUPPORTINTERACTIONS IT IS NOT SURPRISING THAT THE EFFECT OF THE SUPPORT ON THE HYDROGENATIONRESPONSESTILLREMAINSLARGELYUNRESOLVED 4HE SELECTIVE REDUCTION OF AROMATIC NITRO GROUP SUBSTITUENTSINTHEPRESENCEOFOTHERFUNCTIONALGROUPSEG CARBONYL CYANO CHLORO OR ALKENIC GROUPS IS DIF½CULT AS THE REDUCTIONSUBSTITUTIONOFTHESEGROUPSBY( CANBEMORE FACILE THAN THE TARGET ./ GROUP ; = )N THE SELECTIVE REDUCTIONOFNITROARENES PROMISINGRESULTSHAVEBEENRECENTLY PUBLISHED FOR SUPPORTED GOLD CATALYSTS IN BATCH LIQUID OPERATION ; = ALTHOUGH THE FORMATION OF HIGHLY TOXIC BY PRODUCTS AZOXY DERIVATES AND THE REQUIREMENT OF HIGH HYDROGEN PRESSURES -0A ARE DRAWBACKS THAT REQUIRE FURTHERCONSIDERATIONP #HLOROANILINETHETARGETPRODUCTIN THIS STUDY IS A HIGH PRODUCTION VOLUME COMPOUND ;= EXTENSIVELY USED AS AN INTERMEDIATE IN THE SYNTHESIS OF A BROAD RANGE OF ½NE CHEMICALS EG PHARMACEUTICALS AND AGROCHEMICALS ;= 4HE TRADITIONAL PRODUCTION ROUTE FROM P CHLORONITROBENZENE INVOLVES THE USE OF &E IN ACID MEDIA "mCHAMP PROCESS BUT THE GENERATION OF LARGE AMOUNTS TIMESGREATERTHANTHATOFTHETARGETPRODUCT OFTOXIC WASTE &E HYDROXIDE SLUDGE AND LOW OVERALL PRODUCT YIELDS HAVELIMITEDITSAPPLICABILITY;=#ATALYTICHYDROGENATIONIN BATCHLIQUIDSYSTEMSOVERTRANSITIONMETALCATALYSTSPROVIDESA CLEANERALTERNATIVE;=(OWEVER THECHALLENGEISTOACHIEVE

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&IGURE

NO2

NO

NHOH

NH2

CI

CI

CI

CI

Nitrobenzene

Nitrosobenzene

Aniline

Benzene

NO2

NO

NH2

CI 2EACTIONPATHWAYSASSOCIATEDWITHTHEHYDROGENMEDIATEDCONVERSIONOFP CHLORONITROBENZENE.OTE4ARGETEDROUTETOP CHLOROANILINEISREPRESENTED BYBOLDARROWS4HEP CHLORONITROBENZENEREACTANTANDP CHLOROANILINEPRODUCTAREFRAMEDINRED

SELECTIVEHYDROGENATIONOFTHENITROGROUPANDAVOIDSCISSION OFTHE# #LBOND; =ANDORCLEAVAGEOF .(;=FROM THE PRODUCT 4HE HYDROGENOLYSIS OF THE #L SUBSTITUENT CAN LEADTOTHEFORMATIONOFANILINEEITHERA VIATHEREDUCTIONOF NITROBENZENEORB ASARESULTOFTHEFURTHERTRANSFORMATION OF P CHLOROANILINE AS SHOWN IN &IGURE WITH BOTH STEPS REPORTEDINTHELITERATUREFORCATALYTICOPERATIONINGASAND ORLIQUIDPHASE OVERSUPPORTEDMETALS; = 7E HAVE RECENTLY DEMONSTRATED EXCLUSIVITY IN THE HYDROGENATION OF A SERIES OF HALONITROCOMPOUNDS TO THE RESPECTIVE HALOGENATED AROMATIC AMINE IN CONTINUOUS GAS PHASE OPERATION OVER SUPPORTED .I ;= AND !U ; = )N THOSESTUDIES WERECORDEDAHIGHERCATALYTICACTIVITYFORTHE .ICATALYSTSBUTSIGNI½CANTTIMEON STREAMDEACTIVATIONWAS INEVIDENCE)NTHISCONTRIBUTION WEHAVEEXTENDEDTHATWORK TOPROBETHEEFFECTOFTHESUPPORTINMODIFYINGTHECATALYTIC ACTIONOFAWELLDISPERSED!UPHASE7EHAVECONSIDEREDFOUR OXIDESUPPORTS!L/ 4I/ #E/AND&E/ THATPRESENTA RANGEOFACID BASEANDREDOXSURFACEPROPERTIES)NADDITION WEHAVECOMPAREDTHECATALYTICBEHAVIOUROFTHESESYSTEMS WITH A !U4I/ REFERENCE CATALYST SUPPLIED BY THE 7ORLD 'OLD#OUNCIL

%XPERIMENTAL #ATALYSTPREPARATIONANDACTIVATION 4HE EFFECT OF THE SUPPORT ON !U CATALYTIC HYDROGENATION PERFORMANCE WAS INVESTIGATED BY SELECTING A GROUP OF REDUCIBLE #E/ 4I/ AND A &E/ AND NON REDUCIBLE G !L/ OXIDES4HE#E/(3! 2HODIA 4I/0 $EGUSSA


ANDG !L/0URALOX #ONDEA6ISTA#O SUPPORTSWEREUSEDAS RECEIVED(EMATITEA &E/ WASPREPAREDBYPRECIPITATION INBASICMEDIAACCORDINGTO; =

CM AQUEOUS .A#/ - WERE PLACED IN A THREE NECKED ROUND BOTTOM ¾ASK AND HEATED IN A WATER BATH TO + UNDER CONSTANT AGITATION RPM !N AQUEOUS SOLUTION OF &E./ À(/ CM - WAS THEN ADDED DROP WISE CM H BY MEANS OF A MICROPROCESSOR CONTROLLEDINFUSIONPUMPKD3CIENTI½C "ASICCONDITIONS P( WERE MAINTAINED DURING PRECIPITATION BY ADDING .A#/ ½VE ADDITIONS OF G 4HE SOLID HYDROXIDE WAS SUBSEQUENTLY AGED FOR H TO ENHANCE THE "%4 AREA ;= WASHED WITH WARM DISTILLED WATER UNTIL THE WASH WATER APPROACHED NEUTRAL P( AND DRIED FOR DAYS AT + + MIN IN ULTRA PURE (E CM MIN TO PRODUCE HEMATITE

4HE 8 RAY DIFFRACTOGRAM PATTERN FOR THE AS PREPARED &E/ NOTSHOWN PRESENTEDSIGNALSATQ ANDCORRESPONDING TOTHE AND CHARACTERISTICS PLANES OF A PHASE &E/ HEMATITE *#0$3 )#$$CARDNUMBER !SERIESOFMOLOXIDE SUPPORTED!UWASPREPAREDBYDEPOSITION PRECIPITATION$0 ANDIMPREGNATION)-0 4HESESYNTHESISROUTESWERECHOSEN AS IT HAS BEEN DEMONSTRATED THAT CATALYST SYNTHESIS CAN

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SIGNI½CANTLY IN¾UENCE METAL DISPERSION WHERE $0 HAS BEEN SHOWN TO GENERATE SMALL !U PARTICLES NM )N CONTRAST EVEN AT LOW !U LOADING WT CATALYSTS PREPARED BY THE LESS CONTROLLED )-0 PROCEDURE NORMALLY EXHIBITLARGER NM !UDIAMETERS )NTHECASEOFTHE $0SAMPLES UREAUSEDASTHEBASI½CATIONAGENT WASADDED CA FOLDUREAEXCESS TOASOLUTIONOF(!U#LCM X - 4HE SUPPORT G G !L/ 4I/ #E/ AND A &E/ WASINTRODUCEDANDTHESUSPENSIONWASSTIRREDAND HEATED TO + FOR H 4HE P( OF THE SUSPENSION PROGRESSIVELYINCREASEDTOREACHCAAFTERHASARESULTOF THETHERMALLY INDUCEDUREADECOMPOSITION;=

4HESOLIDSOBTAINEDWERESEPARATEDBYCENTRIFUGATION WASHED THREETIMESWITHDEIONIZEDWATERANDDRIEDUNDERVACUUMAT +FORH)NTHECASEOFTHE)-0SYNTHESIS THESUPPORT WAS DISPERSED IN APPROPRIATE VOLUMES OF (!U#L SOLUTION !LDRICH X GCM P( ANDTHERESULTINGSLURRYWAS VIGOROUSLYSTIRREDRPM ANDHEATED+MIN TO+ INA(EPURGE4HESOLIDRESIDUEWASDRIEDINA¾OWOF(EAT +FORH!FTERPREPARATION THESAMPLESWERESIEVEDTO M AVERAGE PARTICLE DIAMETER AND STORED IN THE DARK AT + 4HE !U LOADING WAS DETERMINED TO WITHIN BY INDUCTIVELY COUPLED PLASMA OPTICAL EMISSIONSPECTROMETRY)#0 /%3 6ISTA 02/ 6ARIAN)NC FROM THEDILUTEDEXTRACTOFAQUAREGIA4HECATALYTICBEHAVIOUROFA MOL !U4I/ REFERENCE CATALYST SUPPLIED BY THE 7ORLD 'OLD #OUNCIL TYPE ! LOT NUMBER !U 4I/ SAMPLE NUMBER WAS ALSO INVESTIGATED 4HE PREPARATION AND CHARACTERIZATIONDETAILSOFTHISREFERENCESAMPLEHAVEBEEN RECORDED ELSEWHERE ; = 0RIOR TO USE IN CATALYSIS THE SAMPLESWEREACTIVATEDINCMMIN (AT+MIN TO +ANDMAINTAINEDAT½NALREDUCTIONTEMPERATUREFOR H4HEREQUIREMENTSFORTHEREDUCTIONOFTHE!UPRECURSORTO METALLIC !U FOR CATALYSTS PREPARED BY )-0 ANDOR $0 HAVE BEENESTABLISHEDELSEWHERE; =3AMPLESFOROFF LINE ANALYSIS WERE PASSIVATED IN VV /(E AT ROOM TEMPERATURE #ATALYSTCHARACTERIZATION ( CHEMISORPTION AND "%4 SURFACE AREA WERE DETERMINED USINGTHECOMMERCIAL#(%- "%41UANTACHROME UNIT 4HESAMPLESWEREACTIVATEDASABOVE SWEPTWITHACM MIN ¾OWOF.FORH COOLEDTOROOMTEMPERATUREAND SUBJECTEDTO(CHEMISORPTIONUSINGAPULSEL TITRATION PROCEDURE "%4 AREAS WERE RECORDED WITH A VV .(E ¾OW USING PURE . AS INTERNAL STANDARD !T LEAST CYCLESOF.ADSORPTION DESORPTIONINTHE¾OWMODEWERE EMPLOYED TO DETERMINE TOTAL SURFACE AREA USING THE STANDARDSINGLEPOINTMETHOD"%4SURFACEAREAAND(UPTAKE VALUES WERE REPRODUCIBLE TO WITHIN 0OWDER 8 RAY DIFFRACTOGRAMS WERE RECORDED ON A "RUKER3IEMENS $ INCIDENT 8 RAY DIFFRACTOMETER USING #U +A RADIATION 4HE


SAMPLESWERESCANNEDATSTEP OVERQ SCANTIMESSTEP $IFFRACTOGRAMSWEREIDENTI½EDUSING THE *#0$3 )#$$ REFERENCE STANDARDS IE G !L/ AND !U $IFFUSE RE¾ECTANCE $23 56 6IS MEASUREMENTSWERECONDUCTEDUSINGA0ERKIN%LMER,AMBDA 56 6IS 3PECTROMETER WITH "A3/ POWDER AS REFERENCE ABSORPTIONPRO½LESWERECALCULATEDFROMTHERE¾ECTANCEDATA USING THE +UBELKA -UNK FUNCTION !U PARTICLE MORPHOLOGY AND SIZE WERE DETERMINED BY TRANSMISSION ELECTRON MICROSCOPYANALYSIS*%/,*%-(24%-UNITWITHA547 ENERGY DISPERSIVE 8 RAY DETECTOR /XFORD )NSTRUMENTS OPERATED AT AN ACCELERATING VOLTAGE OF K6 3PECIMENS WEREPREPAREDBYDISPERSIONINACETONEANDDEPOSITEDONA HOLEYCARBON#UGRID-ESH 5PTOINDIVIDUAL!U PARTICLES WERE COUNTED FOR EACH CATALYST AND THE SURFACE AREA WEIGHTEDMETALDIAMETERD4%- WASCALCULATEDFROM

WHERE NIISTHENUMBEROFPARTICLESOFDIAMETER D I4HESIZE LIMITFORTHEDETECTIONOF!UPARTICLESISCANM #ATALYSISPROCEDURE 2EACTIONS WERE CARRIED OUT UNDER ATMOSPHERIC PRESSURE AT 4+ INSITUIMMEDIATELYAFTERACTIVATION INA½XEDBED VERTICALPLUG ¾OWGLASSREACTORLMMIDMM 4HE CATALYTIC REACTOR AND OPERATING CONDITIONS TO ENSURE NEGLIGIBLE HEATMASS TRANSPORT LIMITATIONS HAVE BEEN FULLY DESCRIBED ELSEWHERE ;= BUT SOME FEATURES PERTINENT TO THIS STUDY ARE GIVEN BELOW ! LAYER OF BOROSILICATE GLASS BEADS SERVED AS PREHEATING ZONE ENSURING THAT THE P CHLORONITROBENZENE REACTANT WAS VAPORIZED AND REACHED REACTION TEMPERATURE BEFORE CONTACTING THE CATALYST )SOTHERMAL CONDITIONS + WERE ENSURED BY DILUTING THE CATALYST BED WITH GROUND GLASS M ;= 4HE REACTANT WAS DELIVERED TO THE REACTOR VIA A GLASSTE¾ON AIR TIGHT SYRINGE AND TE¾ON LINE USING A MICROPROCESSOR CONTROLLED INFUSIONPUMP-ODELKD3CIENTI½C ATA½XEDCALIBRATED ¾OW RATE ! CO CURRENT ¾OW OF P CHLORONITROBENZENE AND ULTRA PURE ( VV ./( WAS MAINTAINED AT A '(36XH WITHANINLET ./MOLAR¾OW& INTHE RANGEX ¯X MMOL ./H WHERETHE(CONTENT WAS UP TO TIMES IN EXCESS OF THE STOICHIOMETRIC REQUIREMENT 0( ATM THE ¾OW RATE OF WHICH WAS MONITOREDUSINGA(UMONICS-ODEL DIGITAL¾OWMETER 4HEMOLARMETALN!U TOINLETMOLAR ./FEEDRATE& RATIO SPANNED THE RANGE X ¯X H )N A SERIES OF BLANK TESTS PASSAGE OF P CHLORONITROBENZENE IN A STREAM OF ( THROUGHTHEEMPTYREACTOROROVERTHESUPPORTALONE IEIN THEABSENCE!U DIDNOTRESULTINANYDETECTABLECONVERSION 4HEREACTOREF¾UENTWASFROZENINALIQUIDNITROGENTRAPFOR SUBSEQUENT ANALYSIS WHICH WAS MADE USING A 0ERKIN %LMER !UTO 3YSTEM 8, GAS CHROMATOGRAPH EQUIPPED WITH A PROGRAMMED SPLITSPLITLESS INJECTOR AND A ¾AME IONIZATION

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DETECTOR EMPLOYINGA$" MXMMID M ½LMTHICKNESSCAPILLARYCOLUMN*73CIENTI½C ASDESCRIBED ELSEWHERE;=!NYPOSSIBLE(#LPRODUCEDWASMONITOREDBY PASSING THE EF¾UENT GAS THROUGH AN AQUEOUS .A/( TRAP X MOL DM KEPT UNDER CONSTANT AGITATION AT RPM WITHCONTINUOUSP((ANNA()0ROGRAMMABLE0RINTING P( "ENCH -ETER ANALYSIS P #HLORONITROBENZENE !LDRICH WW PURITY AND THE BUTANOL SOLVENT 2IEDEL DE (iEN WERE USED WITHOUT FURTHER PURI½CATION (YDROGENATION PERFORMANCE IS QUANTI½ED IN TERMS OF THE DEGREEOFNITRO GROUPREDUCTIONX ./

CATALYSTSWASCONSIDERABLYLOWERMOLG!U THANTHAT OBTAINEDFORCONVENTIONALTRANSITIONMETALSONOXIDESUPPORTS EG0D!L/MOLG0D ;= .I3I/MOLG.I ;= AND .I4I/ MOL G.I ;= (YDROGENGOLD INTERACTIONISSTILLNOTWELLUNDERSTOODBUTITAPPEARSTHAT!U COORDINATION NUMBER IS A CRITICAL FACTOR IN DETERMINING ADSORPTIONCAPABILITY;=7HILEMOLECULARHYDROGENDOESNOT CHEMISORB ON BULK !U AT ROOM TEMPERATURE ;= THERE IS EVIDENCEFORDISSOCIATIVECHEMISORPTIONON!U½LMSCONTAINING &IGURE

4HE PERCENTAGE SELECTIVITY WITH RESPECT TO P CHLOROANILINE 3P #!. ISGIVENBY XRD Signal (a.u.)

2EPEATED REACTIONS WITH SAMPLES FROM THE SAME BATCH OF CATALYST DELIVERED ACTIVITY VALUES THAT WERE REPRODUCIBLE TO WITHIN

(A)

(B) (311)

(440)

(400) (222)

(C) (111) (200)

(311)

(220)

(D)

2ESULTANDDISCUSSION

20

#ATALYSTCHARACTERIZATION (YDROGEN CHEMISORPTION "%4 SURFACE AREAS AND SURFACE WEIGHTEDMEAN !UPARTICLESIZEOBTAINEDBY4%-D4%- FOR THECATALYSTSCONSIDEREDINTHISSTUDYARERECORDEDIN4ABLE (YDROGEN UPTAKE POST ACTIVATION FOR ALL THE SUPPORTED !U

30

40

50

60

70

90

2 82$PATTERNSASSOCIATEDWITH! !U!L/ $0 " !U!L/ )-0AND *#0$3 )#$$REFERENCEDIFFRACTOGRAMSFOR# G !L/ AND$ !U

&IGURE

4ABLE 'OLD PARTICLE SIZE OBTAINED FROM 4%- D4%- ANALYSIS ( UPTAKE "%4 SURFACEAREAANDPSEUDO ½RSTORDERP CHLORONITROBENZENEHYDROGENATION RATECONSTANTK OBTAINEDFOROXIDESUPPORTED!UMOL PREPAREDBY DEPOSITION PRECIPITATION$0 ANDIMPREGNATION)-0

D4%-NM (UPTAKE MOLG!U

"%4AREA MGCAT

KH

!U!L/ $0

!U#E/ $0

!U&E/ $0

!U4I/ $0

!U4I/ 2EF

!U!L/ )-0

!U&E/ )-0

!U4I/ )-0


(A)

Intensity (a.u.)

#ATALYST

80

(B)

(C)

400

500

600

700

800

Wavelength (nm) $2356 6ISSPECTRAFOR! G !L/ " !U!L/ $0AND# !U!L/ )-0

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")

NM

NM

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NM

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2EPRESENTATIVE4%-IMAGESOF! !U!L/ $0AND" !U!L/ )-0 ) LOWMAGNI½CATIONIMAGES)) HIGHMAGNI½CATIONIMAGEOFASINGLE !UPARTICLEWITHASSOCIATEDDIFFRACTOGRAMPATTERN)))

DEFECTSITES; =)NDEED SOMECONSENSUSEMERGESFROM THELITERATURETHATSMALLER!UPARTICLES; =WITHAHIGHER NUMBER OF DEFECTS STEPS EDGES AND CORNERS EXHIBIT A GREATER FACILITY FOR DISSOCIATIVE HYDROGEN UPTAKE 8 RAY DIFFRACTION ANALYSIS CAN PROVIDE IMPORTANT BULK STRUCTURAL CHARACTERISTICS &IGURE SHOWS THE DIFFRACTION PATTERNS FOR TWOREPRESENTATIVESAMPLES IE!U!L/ $0PRO½LE! AND !U!L/ )-0 PRO½LE " 4HE MARKERS INCLUDED ILLUSTRATE THE POSITION AND RELATIVE INTENSITY OF THE 82$ PEAKS FOR G !L/PRO½LE# ANDCUBIC!UPRO½LE$ TAKENFROMTHE *#0$3 )#$$STANDARDSCARDNUMBERS AND RESPECTIVELY 4HE 82$ PATTERNS FOR BOTH CATALYSTS EXHIBIT SIGNALSOVERTHERANGEQ THATCANBEASSOCIATED WITH THE AND PLANES OF CUBIC G !L/SEEPRO½LE# WHERETHEBROADNESSOFTHEPEAKSIS INDICATIVEOFSHORTRANGEORDER)NADDITION THE82$PATTERN FOR!U!L/ )-0SEEPRO½LE" ALSOSHOWSSTRONGRE¾ECTIONS AT Q AND CORRESPONDING TO AND PLANESOF!UMETALSEEPRO½LE $ WITH AN EXTRACTED FROM STANDARD LINE BROADENING ANALYSIS MEAN !U PARTICLE SIZE NM )N CONTRAST THEREARENODISTINGUISHABLEPEAKSCHARACTERISTICOFMETALLIC GOLDINTHE!U!L/ $0SPECTRUMSEEPRO½LE! SUGGESTING AHIGHLYDISPERSED!UPHASE4HE$2356 6ISSPECTRAOFTHE


ALUMINASUPPORT !U!L/ $0AND!U!L/ )-0 INTHERANGE NM ARE PRESENTED IN &IGURE 4HE SPECTRUM FOR !L/ PRO½LE ! IS FEATURELESS CONSISTENT WITH RESULTS PRESENTED ELSEWHERE ;= 4HE ABSORPTION BAND BETWEEN NMPRESENTINTHESPECTRUMOF!U!L/ $0PRO½LE " IS CHARACTERISTIC OF METALLIC GOLD ; = 4HE SIGNAL ASSOCIATED WITH !U!L/ )-0 PRO½LE # EXHIBITS A GREATER INTENSITY WITH A DISPLACEMENT TO A HIGHER WAVELENGTH A RESPONSETHATHASBEENASCRIBEDINTHELITERATURE;=TOTHE PRESENCEOFLARGER!UPARTICLES WHICHISINAGREEMENTWITH THE82$ANALYSIS 2EPRESENTATIVE 4%- IMAGES OF !U!L/ $0 !) AND !U!L/ )-0 ") AND ")) ARE PRESENTED IN &IGURE WHICH SHOWQUASI SPHERICAL!UPARTICLESDISPERSEDONTHESUPPORT 4HEDIFFRACTOGRAMPATTERNFORANISOLATEDSINGLEGOLDPARTICLE INTHECASEOF!U!L/ )-0ISSHOWNINIMAGE")))WHERETHE D SPACINGS ARE CONSISTENT WITH THE AND PLANESOFMETALLICGOLD*#0$3 )#$$ CON½RMING PRECURSOR REDUCTION TO !U POST ACTIVATION IN AGREEMENT WITH82$AND$2356 6ISDATA4HEIMAGESINDICATETHAT!UIS PRESENTASSMALLERPARTICLESIN!U!L/ $0WHENCOMPARED WITH!U!L/ )-0 ATRENDTHATEXTENDSTOTHEOTHERSAMPLES IEFORTHESAMESUPPORT THE)-0SAMPLESEXHIBITLARGER!U PARTICLESNM SEE4ABLE 4HESEQUENCEOFINCREASING MEAN !U PARTICLE SIZE FOR THE SAMPLES PREPARED BY $0 !U#E/ $0 !U4I/ $0 !U&E/ $0 !U!L/ $0 SUGGESTS A DEPENDENCY ON THE REDUCIBILITY OF THE CARRIER WHERETHELARGEST!UPARTICLESIZEISASSOCIATEDWITHTHELEAST REDUCIBLE SUPPORT !L/ !LUMINA IS WELL ESTABLISHED AS AN IRREDUCIBLESUPPORTANDANINSULATORMATERIALDUETOITSWIDE BAND GAP E6 ; = WHEREAS #E/ 4I/ AND &E/ ARE REDUCIBLECARRIERSWITHSEMICONDUCTORNATURE E6 ; = 4HESAMETRENDISALSOINEVIDENCEFORTHE)-0SAMPLESWHERE THE!UPARTICLESIZEON!L/ISAPPRECIABLYHIGHERTHANTHAT FOR REDUCIBLE 4I/ OR &E/ SEE 4ABLE /UR OBSERVATIONS ½ND SOME SUPPORT IN THE LITERATURE WHERE A PARTIAL REDUCTION OF THE OXIDE CARRIER HAS BEEN SHOWN TO RESULT IN METAL SUPPORT INTERACTIONS THAT IMPACT ON !U DISPERSION )NDEED -INETAL USINGSCANNINGTUNNELLINGMICROSCOPY DEMONSTRATEDTHATREDUCIBLEOXIDESPROVIDEMORENUCLEATION SITES LEADINGTOTHEFORMATIONOF!UCLUSTERSWITHASMALLER PARTICLESIZE #ATALYSTACTIVITYSELECTIVITY 4HEGASPHASEHYDROGENATIONOF P CHLORONITROBENZENEOVER EACHSUPPORTED!UCATALYSTGENERATEDP CHLOROANILINEASTHE SOLEPRODUCT IEEXCLUSIVEREDUCTIONOFTHENITRO GROUPWITH NO EVIDENCE OF HYDRODECHLORINATION HYDRODENITROGENATION ORAROMATICRINGREDUCTION)TISSIGNI½CANTTHATTHEEXCLUSIVE FORMATIONOF P CHLOROANILINEWASAFEATUREOFEACHCATALYST DEMONSTRATING THAT THE SUPPORT DID NOT IN¾UENCE REACTION SELECTIVITY WHICH WAS GOVERNED BY THE !U PHASE )N CONTRAST IN THE HYDROGENATION OF CHLORONITROBENZENE OVER CONVENTIONAL TRANSITION METALS SUPPORT EFFECTS HAVE BEEN DEEMEDRESPONSIBLEFORDIFFERENCESINSELECTIVITY8IONGAND

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CO WORKERS;=STUDIEDTHEREACTIONOFO CHLORONITROBENZENE OVERASERIESOFOXIDE3I/ :R/ 4I/AND!L/ SUPPORTED .I CATALYSTS AND ATTRIBUTED THE HIGHEST SELECTIVITY TO O CHLOROANILINEOVER.I4I/TOSTRONGPOLARIZATIONOFTHE./ BANDINDUCEDBYTHEOXYGENVACANCIESOF4I/X(ANETAL;= INVESTIGATED THE HYDROGENATION OF P CHLORONITROBENZENE OVER0TON4I/ G !L/AND:R/ANDASSOCIATEDTHEHIGHEST P CHLOROANILINE YIELD OBTAINED USING 0T4I/ WITH STRONG METALSUPPORT INTERACTIONS 7HILE (UGON ET AL ;= HAVE RECENTLY REPORTED THAT THE SELECTIVITY RESPONSE IN THE HYDROGENATIONOF BUTADIENEOVER!USUPPORTEDON4I/ !L/ #E/AND:R/WASINDEPENDENTOFTHENATUREOFTHE SUPPORT THEREISEVIDENCEINTHELITERATURE OFSUPPORT EFFECTS IN TERMS OF HYDROGENATION SELECTIVITY FOR SUPPORTED !U SYSTEMS #AMPO AND CO WORKERS HAVE REPORTED THAT !U#E/ISHIGHLYSELECTIVEINTHEGASPHASEHYDROGENATIONOF CROTONALDEHYDE TO CROTYL ALCOHOL WHEREAS !U.B/ IS NON SELECTIVEANDPROPOSEDTHATNIOBIAPROMOTEDTHEFORMATION OF NON SELECTIVE !U PARTICLES WITH A DISTINCT MORPHOLOGY -ILONEETAL REPORTEDASTRONGSUPPORTEFFECTWITHRESPECT TO#/HYDROGENATIONINTHECASEOFBENZALACETONEWHERE ELECTRON ENRICHED!UPARTICLESGENERATEDVIAELECTRONTRANSFER FROM A REDUCIBLE SUPPORT IRON OXIDE RESULTED IN HIGHER SELECTIVITIES TO THE CORRESPONDING A B UNSATURATED ALCOHOL 4HELEVELOFREACTIONEXCLUSIVITYREPORTEDINOURSTUDY NOTABLY THE AVOIDANCE OF # #L BOND SCISSION IS UNIQUE WHEN COMPARED WITH THE CATALYTIC BATCH LIQUID SYSTEMS TESTED TO DATE AND REPRESENTS A CRITICAL ADVANCEMENT IN THE DEVELOPMENT OF A SUSTAINABLE CONTINUOUS PRODUCTION OF AROMATICHALOAMINES

4HE ACTIVITY OF THESE CATALYSTS WAS ASSESSED BY ½TTING THETEMPORALX ./ SEE&IGURE RESPONSETOANEMPIRICAL RELATIONSHIP DESCRIBED IN DETAIL ELSEWHERE ;= IN ORDER TO OBTAINAMEASUREOFINITIALACTIVITY!SAGENERALOBSERVATION SMALLER !U PARTICLES NM GENERATED HIGHER INITIAL ACTIVITIESBUTEXHIBITEDATEMPORALDECLINE WHEREASCATALYSTS WITH A LOWER !U DISPERSION DID NOT SHOW ANY SIGNI½CANT TIME ON STREAMVARIATIONINCONVERSION4HISISDEMONSTRATED BY THE TWO REPRESENTATIVE CASES PRESENTED IN &IGURE !U!L/ )-0D4%-NM DELIVEREDANINVARIANTCONVERSION WITHTIME ON STREAMUPTOH WHILEADECLINEINCONVERSION ISOBSERVEDFOR!U&E/ $0 WHICHBEARSSMALLER!UPARTICLES D4%-NM 4HESERESULTSSUGGESTAHIGHERACTIVITYBUTA SUSCEPTIBILITY TO DEACTIVATION FOR SMALLER !U CLUSTERS -ETAL CATALYST DEACTIVATION IS A FEATURE OF GAS PHASE ¯./ GROUP REDUCTION AS A RESULT OF (/ FORMATION ;= ANDOR COKE DEPOSITION ; = 4HE LATTER HAS BEEN SUGGESTED AS RESPONSIBLE FOR THE LOSS OF ACTIVITY DURING HYDROGENATION OVER SUPPORTED !U ; = 7E HAVE PREVIOUSLY ESTABLISHED THE APPLICABILITY OF A PSEUDO ½RST ORDER KINETIC TREATMENT ; = WHERE N!U &HASTHEPHYSICALMEANINGOFCONTACTTIME4HE LINEAR RELATIONSHIP BETWEEN LN X ./ AND N!U &FORCEDTHROUGHTHEORIGIN ISSHOWNIN&IGURE TAKING !U&E/ $0 AS A REPRESENTATIVE CASE 4HE RESULTANT RAW PSEUDO ½RSTORDERRATECONSTANTSK AREGIVENIN4ABLE)N ORDERTOEXPLICITLYDEMONSTRATESTRUCTURESENSITIVITYINTERMS

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AFFECTTHECATALYTICRESPONSEINHYDROGENATIONREACTIONS ANDFORPARTICLESSUF½CIENTLYSMALLNM ATRANSITIONINTHE ELECTRONIC STATE OF GOLD FROM METAL TO NON METAL HAS BEEN SUGGESTED ; = -OREOVER #LAUS AND CO WORKERS ;= STUDYING THE GAS PHASE HYDROGENATION OF ACROLEIN OVER NANOSIZED !U4I/ CATALYSTS ASSOCIATED THE DECREASE IN ACTIVITY¡MMOLG!U S WITHDECREASING!UPARTICLE SIZE¡NM TOTHELOSSOFMETALLICCHARACTERFORTHE SMALLER !U PARTICLES )N THIS STUDY WE HAVE ESTABLISHED A SIGNI½CANT!UPARTICLESIZEEFFECTFORTHEGASPHASESELECTIVE HYDROGENATION OF P CHLORONITROBENZENE WITH AN OPTIMUM MEAN!UPARTICLESIZEOFCANMTHATISINDEPENDENTOFTHE NATURE OF THE OXIDE SUPPORT &UTURE WORK WILL FOCUS ON ALTERNATIVE POLYFUNCTIONAL NITROARENES WITH THE GOAL OF ACHIEVINGTHEPRODUCTSELECTIVITYTHATWEREPORTINTHISSTUDY

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#ONCLUSIONS 2ELATIONSHIPBETWEENSPECI½CRATECONSTANTK` AND!UPARTICLESIZE D4%- FORREACTIONOVER!U!L/ $0 !U#E/ $0 !U&E/ $0 !U4I/ $0 !U4I/ 2EF !U!L/ )-0 !U&E/ )-0 AND!U4I/ )-0 $0CATALYSTSREPRESENTEDBYOPENCIRCLES)-0 CATALYSTSREPRESENTEDBYSOLIDCIRCLES

OF!UPARTICLESIZE ITISNECESSARYTODETERMINETHERELATIONSHIP BETWEEN!USIZEANDTHESPECI½CRATECONSTANTK` INTERMSOF THEEXPOSED!USURFACEAREAASESTIMATEDFROMMEAN4%- PARTICLESIZE SEE4ABLE 4HERESULTSARESHOWNIN&IGURE WHICHREVEALSTHATTHECATALYSTSPREPAREDBY$0WITHSMALLER !U PARTICLES NM DELIVERED HIGHER SPECI½C ACTIVITIES WHEN COMPARED WITH THE )-0 SAMPLES THAT BEAR LARGER !U PARTICLES 4HEOBSERVEDDECREASEINK´WITHINCREASING !UPARTICLESIZEISCONSISTENTWITHSTRUCTURESENSITIVITYWHERE !U PARTICLES NM ARE INTRINSICALLY MORE ACTIVE FOR NITRO GROUP REDUCTION 4HE PARTICLE SIZESPECI½C RATE RESPONSE FOR SEVEN CATALYST SYSTEMS LABORATORY SYNTHESISED AND THE 7ORLD 'OLD #OUNCIL 2EFERENCE SAMPLE FALL ON A COMMON TRENDLINE4HISSUGGESTSTHATTHENATUREOFTHESUPPORTDOES NOT IMPACT SIGNI½CANTLY ON HYDROGENATION RATE WHICH IS CONTROLLEDBYTHE!UPARTICLESIZE)NDEED TAKINGACOMMON SUPPORT!L/ SEEPOINTSANDIN&IGURE !U!L/ $0 D4%- NM DELIVERED A SPECI½C RATE THAT WAS OVER TIMES GREATER THAN THAT OBTAINED FOR !U!L/ )-0 D4%-NM REPRESENTINGTHEUPPERANDLOWERRATEVALUES RECORDED IN THIS STUDY -OREOVER SYSTEMS WITH SIMILAR !U DISPERSION ON DIFFERENT OXIDES PRESENT SIMILAR ACTIVITY AS ILLUSTRATED BY POINTS !U&E/ $0 D4%- NM AND !U4I/ $0 D4%-NM IN&IGURE)TSHOULDBENOTED THAT !U#E/ $0 WHICH PRESENTED THE SMALLEST !U PARTICLE SIZENM DEVIATESSOMEWHATFROMTHEGENERALTREND7E TENTATIVELYATTRIBUTETHISRESPONSETOTHESMALL!UPARTICLESIZE WHICHFALLSINTOTHEREGIONNM WHERECATALYTICACTIVITYIS SEVERELY MODI½ED BY ELECTRONIC AND QUANTUM SIZE EFFECTS ;= )NDEED THE ELECTRONIC CHARACTER OF !U CAN


4HE RESULTS PRESENTED IN THIS STUDY SUPPORT THE FOLLOWING CONCLUSIONS I 4HE CONTINUOUS GAS PHASE HYDROGENATION OF P CHLORONITROBENZENEOVER!USUPPORTEDON!L/ 4I/ &E/ AND #E/ UNDER MILD REACTION CONDITIONS 0 ATM 4 + RESULTS IN THE EXCLUSIVE FORMATION OF P CHLOROANILINE II ! TACOMMON!ULOADINGMOL CATALYSTPREPARATION BY$0GENERATESSMALLERSURFACEAREAWEIGHTED MEAN!U PARTICLESIZESNM WHENCOMPAREDWITH)-0 NM -OREOVER !UPARTICLESIZEWASGREATERONTHENON REDUCIBLE!L/ CARRIERFORBOTHPREPARATIONMETHODS III 4 HE NATURE OF THE SUPPORT DOES NOT IMPACT DIRECTLY ON THERATEOFNITRO GROUPREDUCTION WHICHISGOVERNEDBY !U PARTICLE SIZE !N INCREASE IN SPECI½C HYDROGENATION RATE IS OBSERVED WITH A DECREASE IN MEAN !U SIZE FROM TO NM ! LOWER SPECI½C RATE RECORDED FOR SMALLER PARTICLESNM CANBEATTRIBUTEDTOAQUANTUMSIZE EFFECT ! TEMPORAL LOSS OF ACTIVITY WAS OBSERVED FOR REACTIONOVERSMALLER!UPARTICLESWHEREASTHOSECATALYSTS WITHAMEANPARTICLESIZENMDISPLAYEDATIMEINVARIANT CONVERSION IV / URRESULTSCANSERVEASAPROOFCONCEPT DEMONSTRATING THE FEASIBILITY OF GOLD CATALYSIS AS A VIABLE SUSTAINABLE ROUTEFORTHEPRODUCTIONOFAROMATICAMINES

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