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Catalysis
Today
jou rn al h om ep a g e :w w w . e l s e v i e r . c o m / l o c a t e / c a t t o d
Effect
of
chlorine
on
performance
of
Pd
catalysts
prepared
via
colloidal
immobilization
Yingnan
Zhao
a,c,
Wanwei
Liang
a,
Yongdan
Li
b,
Leon
Lefferts
a,∗aCatalyticProcessesandMaterials,FacultyofScienceandTechnology,MESA+InstituteforNanotechnology,UniversityofTwente,Enschede,7500AE,
TheNetherlands
bSchoolofChemicalEngineering,TianjinUniversity,Tianjin,300072,China
cDepartmentofBiotechnologyandChemicalTechnology,SchoolofChemicalTechnology,AaltoUniversity,P.O.Box16100,00076Aalto,Finland
a
r
t
i
c
l
e
i
n
f
o
Articlehistory:
Received8November2016 Receivedinrevisedform 28December2016 Accepted17January2017 Availableonline22January2017 Keywords: Pdcatalysts Nitritehydrogenation Chlorine Colloid Selectivity
a
b
s
t
r
a
c
t
ThiscontributionshowstheeffectofresidualchlorineonthecatalyticperformanceofaPd-basedcatalyst
inthehydrogenationofnitriteforcleaningofdrinkingwater.Thecatalystwaspreparedvia
immobiliza-tionacolloidalPdnanoparticlesusingactivatedcarbonassupport.Differentamountofhydrochloric
acid(HCl)wasaddedtoimmobilizethePdcolloidonthecarbonsupport,facilitatingtheremovalof
theresidualstabilizer,polyvinylalcohol(PVA),fromthesurfaceofthePdnanoparticles(NPs).The
cat-alystswerecharacterizedbyTEM,CO-chemisorption,XRF,N2physisorption,UV–visspectroscopy,and
XPS.Theactivityandselectivityofthecatalystsweremeasuredfornitritehydrogenationinsemi-batch
operation.TheresultsshowthatPVAcanberemovedcompletelyatpHbelow2.Theresidualchlorine
onthecatalystscanberemovedbyreductioninH2/N2atamildtemperature,i.e.200◦C,regardlessthe
amountofHClused.Nevertheless,highconcentrationofHClduringimmobilization(pH1)causes
par-tialPdre-dissolutionaccordingtoUV–visspectroscopy,resultinginformationofhighlydispersedPd
clustersthatcouldnotbedetectedwithTEM.Reductionofthiscatalystwithhighchlorinecontentin
H2at200◦CisresultinginformationofrelativelylargePdparticlesviasintering.Withoutpre-reduction
at200◦C,residualchlorinecanalsoberemovedalmostcompletelyduringthehydrogenationreaction
atroomtemperature.TheactivityofthePdcatalystisinsensitivetothechlorineconcentrationbelow
30molL−1intheaqueousreactionmixture.Interestingly,theselectivitytoN2isimprovedbyadding
chlorinetothereactionmixture,independentofthewaychlorineisadded,i.e.viathecatalystoradded
directlytothereactionsolution.
©2017TheAuthors.PublishedbyElsevierB.V.ThisisanopenaccessarticleundertheCCBYlicense
(http://creativecommons.org/licenses/by/4.0/).
1. Introduction
Nitrateandnitritecontaminationingroundwaterhasbecome arisingriskforsupplyingofdrinkingwater,especiallyin agricul-turalareaswheresyntheticnitrogenfertilizersareextensivelyused [1–3].Catalytichydrogenationofnitrate/nitrite(Eqs.(1)–(3))using Pd-basedcatalystshasbeendevelopedsincethelate1980s,asa highlyefficientmethodoperatedundermildconditions(typically around25◦Candambientpressure)[4,5].Thismethodprevents formationofanycontaminatingbrinesasinion-exchange
proce-∗ Correspondingauthor.
E-mailaddress:l.lefferts@utwente.nl(L.Lefferts).
dures,andisabletoconvertnitrateandnitriteinwaterlackingany organiccontamination,asisrequiredforbiologicaltreatment[6,7]. 2NO3-+2H2 Pd-Cu −−−−→ 2NO2+2H2O (1) 2NO2-+3H2+2H+ Pd −→ N2+4H2O (2) NO2-+3H2+2H+ Pd −→ NH4++2H2O (3)
Colloidalmethodhasbeendevelopedextensivelyfor prepara-tionofmetalnanoparticles(NPs)forcatalytic applicationinthe lastfewdecades[8,9].Theadvantageofthemethodiswell-known: thesizesoftheNPscanbewellcontrolledandmanipulated, facil-itatingstudiesonstructure-performancerelationships.Advanced methodsallowformationofNPswithwell-definedshapes, offer-inginterestingopportunitiesonevenmoredetailedstudiesonthe influenceofsurfacestructureoncatalysis[10,11].
http://dx.doi.org/10.1016/j.cattod.2017.01.028
Pdbasedcatalystsfornitrate/nitritehydrogenationhavebeen studiedusingcolloidpreparationmethods[11–16],reportingthat therateofnitritehydrogenationisindependentonPdparticlesize [14,17,18].Nevertheless,itisalsowellreportedthatresidual sta-bilizers,suchaspolyvinylalcohol(PVA)andpolyvinylpyrrolidone (PVP),can blockpartoftheactivesitesby coveringthe major-ityofthemetalsurface[14,19–22].Stabilizersandcappingagents canalsomanipulateadsorbedreactivespeciesonmetalsurface, influencingtheactivityaswellastheselectivityofPdcatalysts [14,22–25].Asaresult,itisgenerallypreferredtoremovethe resid-ualstabilizersonmetalsurface.
Removal of the residual stabilizers is challenging, normally includingoxidationandthermaltreatment,makingitdifficultto maintainparticlesizeandcrystalstructureoftheNPs,andstill,the removalcanbeincomplete[26–30].Inourpreviouswork[13],the Pdcolloidwasimmobilizedonactivated-carbon(AC)inaqueous HClsolutionatpH2.ItwasobservedthatPVAcouldbecompletely removedfromthePdsurface,accordingtoTEMandCO chemisorp-tionresults.ItwasproposedthatextensivechemisorptionofClon thePdsurface,promotedbythepresenceofO2accordingto
reac-tionsinEqs.(4)and(5),isweakeningtheinteractionbetweenPVA andtheNPs[13].
2Pd+O2→2PdO
G=−186.82kJ (4)
PdO+2Cl−+2H+→PdCl2+H2O(l)
G=−41.38kJ (5)
AfterthePVA removal,thecatalystswerereduced mildlyin H2/N2 atmosphere at 200◦C, in order to reduce PdCl2 to Pd0,
removingchlorinefromthePdsurface.Ontheotherhand, chlo-rineremovalisnotcompleteandasmallbutsignificantamountof chlorineremainsoncatalystsupporti.e.activatedcarbon.
ThiscontributionaimsatoptimizationoftheHClconcentration duringimmobilizationofPd-PVAcolloidonactivatedcarbon.The effectofresidualchlorineinfluencingtheactivityandtheselectivity innitritehydrogenationwillalsobeshown.
2. Experimental
2.1. Chemicals
Sodium tetrachloropalladate(II) (Na2PdCl4≥99.995% (metal
basis)), polyvinyl alcohol (PVA, average MW=13000–23000, 87%–89% hydrolyzed), sodium borohydride (NaBH4,≥96%
(gas-volumetric)),andformic acid(98%–100%)werepurchasedfrom Sigma-Aldrich.Sodiumnitrite(>99%)waspurchasedfromMerck. Activatedcarbon(AC,SBET=1000m2g−1)wassuppliedbyNorit.
ACwassievedintherangeof38–45mindiameterbeforeused ascatalystsupport.Alltheaqueoussolutionswerepreparedusing ultrapurifiedwaterobtained(Millipore,Synergy).
2.2. Pdcolloidpreparation
Thepreparationofpalladiumnanoparticlesviacolloidalmethod hasbeendescribedpreviously,whichcanbesummarizedasfollows [13].PVAwasdissolvedinwaterat70◦Cwithstirringforatleast2h. Thesolution(2wt%)wasthencooleddowntoroomtemperature. AqueoussolutionofNa2PdCl4(20mL,containing0.086mmolPd)
and1.76mLoffreshlypreparedPVAsolutionwereaddedto240mL water,obtainingayellow-brownsolution.After3min,NaBH4
solu-tion(1.72mL,0.172mmol)wasaddedundervigorousstirring.The
brownPdcolloidsolutionwasimmediatelyformed.ThefinalpH wastypically8–8.5.
2.3. Colloidimmobilization
Typically,0.75gACorgraphitewasaddedtothePdcolloid solu-tion (260mL,3.3×10−4molL−1)immediatelyafterpreparation. Hydrochloricacid(HCl)wasaddedtoadjustpHtoeither1,2or 3.Theslurrywasstirredinairwithamechanical6-blade-stirrer (44mm,1000rpm)withthepropellerpositionedatthecentreof liquidfor2hatroomtemperature,filteredandthoroughlywashed withwater.Afterthat,thecatalystsweredriedinvacuumat40◦C overnight.
2.4. Catalystreduction
Catalystspreparedasdescribedabovewerecarefullytreatedin atubefurnace.Inatypicalprocedure,thetemperaturewasraised to200◦Catarateof5◦Cmin−1,thenkeptfor1hat200◦C,in10 vol%H2/90vol%N2.ThenthesamplewasflushedinN2for30min
at200◦C,andcooleddownatarateof20◦Cmin−1toroom temper-atureinthesameatmosphere.ThecatalystswereflushedinN2for
24hbeforeexposuretoair.Inthefollowing,thesamplenotation willbeusedasshowninTable1.
2.5. Characterization
PdparticlesizedistributionwasdeterminedusingTEM(Philips CM300ST-FEG)allowingreliabledetectionofmetalnanoparticles of1nmandlageronAC.TheACsupportedcatalystswerefirstly groundintosub-micronfragmentsanddispersedinethanol.Then thesuspensionwasdroppedonacoppergridcoveredwithhollow carbonforTEMimagetaking.Atleastfiveofthesefragmentswere randomlyselectedfordeterminationofPdparticlesizes,and typi-cally300Pdparticlesweremeasured.Notethatinformationonthe spatialdistributionofnanoparticlesthroughthesupportcannotbe obtainedasthesampleswereground.Themetalloadingonthe sup-portswereanalyzedbyXRF.Thetotalsurfaceareaofsampleswere calculatedbasedonN2physisorptiondata,usingtheBETmethod
forp/p0valuesbetween0.03and0.13forcatalystspreparedwith
ACfollowingtherecommendationsofRouqueroletal.[31],witha typicalerrormarginof5%.
Re-dissolutionofPdbyHClwasmeasuredwithUV–vis spec-troscopyofthecolloidalsuspensioninaUV-spectrometer(Perkin Elmer Lambda 850, wavelength from 200 to 800nm, scanning speed266.75nmmin−1)atroomtemperature.ThepHoffreshly prepared unsupportedPd-PVA colloidsuspension wasadjusted to 1, 2 and 3 by adding HCl solution,followed by stirring the suspensioninairatmospherefor2h.Then500Lofthetreated suspensionwasintroducedinaquartzcell(QS1000)forperforming themeasurement.
COchemisorptionatroomtemperaturewasusedtodetermine themetalsurfaceareathatis accessibleingasphase.Typically, thesample waspre-reducedat roomtemperature in hydrogen and thenflushed inHeat thesametemperature.ThenCO was Table1
Samplenotationsanddetailsofcorrespondingpreparationprocedure.
Sample PreparationProcedure
PdAC1A Pd-PVAcolloidimmobilizedonACusingHCltoadjustpHto1 PdAC2A Pd-PVAcolloidimmobilizedonACusingHCltoadjustpHto2 PdAC3A Pd-PVAcolloidimmobilizedonACusingHCltoadjustpHto3 PdAC1R PdAC1AreducedinH2/N2at200◦C
PdAC2R PdAC2AreducedinH2/N2at200◦C
introducedaspulsesandtheresponsewasrecordedusingaTCD detector.Weassumedthatthestoichiometricratioofnumberof adsorbedCOmoleculesandnumberofaccessiblePdsurfaceatoms is1:1.ThePddispersion(Pddisp.)wasdefinedas
Pddisp.=numbernumberofPdatomsofPdatomsinthesurfaceintotalofNPs (6) The surface composition of the catalysts was analyzed by X-ray photoelectron spectroscopy (XPS, Quantera SXM, Al K␣ (1486.6eV)). The powder samples were stored in air without anyfurtherpretreatmentbeforeanalysis.Typically,afew micro-gram sample was pressed into an indium foil, and four spots (600×300m2)onthesamplewererandomlyselectedfor
mea-surementstoaverageoutanyinhomogeneityinthecatalysts.The accuracyof theresultingpeak positionswaswithin 0.2eV.The spectrawerefittedusingthesoftware“Multipakv.9.4.0.7”. Typi-cally,thebindingenergyinallspectrawasfirstcalibratedusing thecarbon1speakat284.8eVasaninternalreference.The spec-tradetectedatfourspotsofonesamplewereaveragedinorder toimprovethesignal-to-noiseratio,followedwithShirley back-groundsubtraction.ThePdpeakswerefittedusinganasymmetric model,necessarybecauseofinteractionofthephotoelectronswith thevalencebandelectrons[32],whereastheSandClpeakswere fittedusing mixed Gaussian-Lorentzianmodel, assuggested by HandbookofX-rayPhotoelectronSpectroscopy[33].Thepeaksfor eachsample(Pd5d,Cl2pandS2p)werefittedwithsetsofdoublets withidenticalFHWM.Bothwidthandpeakpositionwereallowed tooptimize.Thedistancewithinthedoubletswasfixed,according tothedatasuggestedinthehandbook[33].
2.6. Nitritehydrogenation
Thereactionwasperformedinahome-buildapparatus includ-ingaglasstankreactor(98mmwithfour5mmbaffles),equipped withamechanical6-blade-stirrer(44mm,1000rpm)withthe propellerpositionedatthecentreofliquid.Typically,50mg cat-alystwasaddedto300mLH2O.Themixedsuspensionwasthen
stirredvigorously,whileaH2/He/CO2gasmixturewasintroduced
viaadippedpipe(H2/He/CO2=6/3/1byvolumeflowrate,totalflow
rate=100mLmin−1,totalpressure=1bar)foratleast1h.CO2was
usedasabufferaccordingtoreactionshowninEqs.(7)and(8)to partlycompensatefortheprotonsconsumedbynitrite hydrogena-tion.
CO2+H2O→HCO3−+H+ (7)
Table2
SummaryofXRFelementalanalysis,TEMandCOchemisorption.
Sample CCl(wt%)a dTEM(nm) Pddisp.(%)
CO chemisorptionb TEMc PdAC1A 1.1 3.0±1.2 12±3 30 Pd AC 2 A 0.8 2.8±0.9 12±2 32 Pd AC3A 0.6 3.1±1.2 8±2 29 PdAC1R n.d.d 4.1±1.1 32±5 22 PdAC2R n.d. 3.0±1.0 30±4 30 PdAC3R n.d. 3.2±1.2 18±4 28
aChlorinecontentinthecatalystsaccordingtoXRF.
bCOchemisorptioningasphase.ThesamplesreducedinH
2flowfor1hat
21±1◦C.
c EstimatedassumingcleansphericalPdNPs.
d ThecontentisunderXRFdetectivelimitation(<0.05wt%).
HCO3−+H2O→CO32−+H+ (8)
Then3mL4.2mmolL−1NaNO2solutionwasintroduced,
start-ingthereaction.Samplesof1mLweretakenwithasyringeevery 5min.Catalystswereremovedusingasyringefilter(PTFE,0.2m) beforeinjecting intoion chromatograph(DIONEX,ICS 1000)to determinethecontentofnitriteandammonium.
3. Results
3.1. Elementalanalysisandphysicalproperties
XRFresultsin Table2shows thatthechlorineconcentration decreased with increasing pH (less HCl used) for as-prepared catalysts. Chlorine content was below the XRF detection limit (<0.05wt%)afterreductioninH2/N2at200◦C.ThePdcontentof
allcatalystswas1.2±0.1wt%.
TEMresultsinTable2andFig.1andS-1showPdparticlesizes ofabout3nmonaverageinallcatalysts,exceptforPdAC1Rwith 4nmaveragedparticlesize,preparedusingthehighestHCl con-centrationandreducedat200◦C.
COchemisorptionwasusedtodeterminetheaccessibilityof Pdsurfaceingasphase.AsshowninTable2,theapparent disper-sionswereaslowas10%forallas-preparedcatalysts.Notethatthe sampleswerefirstreducedinH2flowatroomtemperaturebefore
CO waschemisorbed fromgas phase. Afterreduction in H2/N2
at 200◦C, the apparent dispersion was significantly increased, agreeingwithourpreviousobservations[13].Nevertheless,the
200
250
300
350
400
450
500
278
236
222
Absorbance (a. u.)
Wavelength (nm)
pH =
1
pH =
2
pH =
3
As-prepared (pH = 8.3)
207
Fig.2.UV–visspectraofunsupportedPd-PVAcolloidsuspensionafterstirringinair for2hatdifferentpHadjustedwithHCl.Theabsorptionpeaksat207nmand236nm canbeattributedto[PdCl3(H2O)]−andpeaksat222nmand278nmto[PdCl4]2−
[34,35].Notethereisnoactivatedcarbonsupportaddedinthecolloidsuspension.
Table3
XPSresultsofPdandCloxidation-statesandsurfaceconcentration.
Sample Pd2+/Pd Cl(Pd)/Cla Cl(Pd)/Pd2+ PdAC1A 0.38 0.75±0.04 1.7 PdAC2A 0.38 0.79±0.05 1.8 PdAC3A 0.07 0.72±0.04 3.0 Pd AC 1R 0.12 0.37±0.11 2.1 PdAC2R 0.03 0.43±0.12 3.1 PdAC3R 0.03 0.36±0.11 1.7
aCl(Pd)standsforchlorinebondedonPdsurface.
persionofthecatalystpreparedwithpH3wasonly18%afterthe reduction,muchlowerascomparedwithcatalystspreparedwith pH1and2(about30%).
FigureS-2showsthatPVAisblockingmicro-poresexclusively inallcatalysts,withoutinfluencingmeso-poreswherethePdNPs aremostprobablylocated,agreeingwiththepreviousstudy[13]. 3.2. UV–visspectroscopy
Fig.2showspartialre-dissolutionofPdforunsupportedPd-PVA colloidstirredinairatdifferentpHcontrolledbyHClconcentration. NoPd-Clcomplexwasdetectedinas-preparedcolloidsuspension, indicatingnoPd-containingionsexistrightaftercolloid prepara-tion.Afterstirringinairfor2h,[PdCl3(H2O)]−(207nmand236nm)
wastheonlydetectedPd-Clcomplexinthecolloidsuspensionat lowHClconcentration(pH3).Incontrast,[PdCl4]2−(278nm)is
detectedinthesuspensionatpH2,becomingthemajorityPd-Cl complex(222nmand278nm)whenthepHwasfurtherdecreased to1byaddingmoreHCl.
3.3. XPS
XPSresultsaresummarizedinTable3,andtypicalspectraare shown in Fig.3 and Figure S-3 in SupportingInformation.The resultsagreewithpreviousobservationsingeneral:thesurfaceof PdNPswasoxidizedbyformationofPdCl2; reductioninH2/N2
at200◦C reducesPd2+toPd0,while removingchlorine[13].In
addition,theresultsshowthattheseeffectdependontheHCl con-centration:whileonly7%Pdisoxidizedintheas-preparedcatalyst preparedwithlowHClconcentration(pH3),muchhighervalues areobserved(upto38%)forcatalystspreparedwithlowerpH.Itis
alsoshownthatashighas12%Pdisoxidizedincatalystprepared withpH1afterreductioninH2/N2at200◦C.
Ontheotherhand,twotypesofchlorineweredetectedwith formalchargeCl−,asshowninFig.3andTable3,whichcanbe attributedtoClbondedtoPd(ca.198eV)andClinorganic com-poundspresumablypresentonAC(ca.200eV),respectively[36]. Theamountsofbothtypesofchlorinedecreasedsignificantlyafter reduction at 200◦C in H2/N2, whereasthe signalofchlorine in
organiccompoundsdecreasedtolesserextentascomparedto chlo-rineonPd.Furthermore,themolarratioofCl(Pd)/Pd2+wasinthe
rangeof2–3forallsamples,bothbeforeandafterreduction.
3.4. Nitritehydrogenation
Fig.4(a)and(b)presentconcentrationsofnitriteand ammo-nium as function of time. The initial rate per total Pd can be estimatedusingthePdloadingasdeterminedbyXRFinTable1,as showninFig.4(c).Alternatively,Fig.4(d)showstheinitialrateper surfacePd,wheretheamountofsurfacePdwasdeterminedbyXRF resultstogetherwithCOchemisorptionresultsinTable2.Inboth cases,thereactionrateshowednosignificantchangewithvariation ofthepHduringcolloidimmobilizationforas-preparedPd-PVA/AC catalystsinFig.4(d).Forthereducedcatalysts,anincreaseof reac-tionratewasobservedwithincreasingthepH-value.Additionally, ammoniumformationcontinuedafternitritewasconverted com-pletely.Thiswasexplainedinpreviousworkbythepresenceof residual N-containing species on Pd surface, probably nitrogen atoms,reactingveryslowlywithhydrogenatclose-to-complete conversionlevel[15].Consequently,theselectivityofthecatalysts toammoniumcanonlybecomparedatconversionlevelsbelow 100%.
Fig. 5 shows that selectivity to ammonium decreased with increasingpHduringcolloidimmobilization,forbothas-prepared andreducedcatalysts.Thereductiontreatmentat200◦CinH2/N2
resultedinhigherselectivitytoammonium,regardlesstheamount ofHClusedforimmobilization.
The amountof Cl introducedby adding thecatalyststo the batchreactor(MCl,cata)canbecalculatedusingtheXRFresultsin
Table2,asshowninTable4.Cl−isreleasedfromthecatalysttothe solutionduringthe1hpre-reductiontreatment,beforethe reac-tionisinitiatedbyinjectionofthenitritesolution.Theamounts ofCl−inaqueousphasedetectedbyIC(MCl,solu)arealsoshownin
Table4.Inallcases,thevaluesofMCl,cataandMCl,soluareingood
agreement,indicatingthatchlorineonthecatalystindeeddissolves completely.InordertorevealtheinfluenceofthefreeCl−inthe reactionsolutiononcatalystperformance,NaClwasaddedtothe reactionslurrywithPdAC3R,asshowninTable4.Thecatalyst activityremainedconstantwithinexperimentalerrorasaresultof addingNaCl;surprisingly,theselectivitytoammoniumdecreased significantly.
4. Discussion
4.1. InfluenceofHClontheaccessibilityofPdsurface
COchemisorptionresultsinTable2showsignificantincrease ofaccessiblePdsurfaceafterreductioninH2/N2at200◦Cforthe
catalystpreparedatpH1and2,resultinginPddispersions sim-ilartotheobservationswithTEM.ThisconfirmsthatPVAcanbe removedcompletelyusingHClatpH2inthepresenceofair,as reportedpreviously[13].AfterPVAremovalviawashingand sub-sequentdrying,H2reductionat200◦Cremovedchlorinefromthe
PdsurfaceviaformationofgaseousHCl,asconfirmedbyXRFresults inTable2.
210 208 206 204 202 200 198 196 194
(eV)
Banding energy
Inte
nsity (a. u.)
Pd_
AC
_2_A
350
348
346
344
342
340
338
336
334
332
330
Banding energy (eV)
Intensity (a. u.)
Pd_
AC
_2_A
Pd_
AC
_2_R
Pd_
AC
_2_R
Pd
0Pd
2+Cl (C) Cl (Pd)
(a)
(b)
Fig.3. XPSspectraofactivatedcarbonsupportedPd-PVAcolloidspreparedatpH2:(a)Pd3dspectra,(b)Cl2pspectra.Originaldata(hollowdots)wassubtractedwithShirley background(blackline)andfittedusingmethoddescribedinSection2.5.ThefittedPd3d5/2peaks,andCl2p3/2peaksarehighlighted(blueandorange)forcomparison.The fittedPd3d3/2peaksandCl2p1/2peaksarekeptingray.Thesumofallfittedpeaksshowedasredlinewitherrorshowedasdashline.Cl(C)andCl(Pd)standforchlorine inorganiccompoundsandchlorinebondedonPdsurface,respectively.(Forinterpretationofthereferencestocolourinthisfigurelegend,thereaderisreferredtotheweb versionofthisarticle.)
Table4
Summaryofreactionrateandselectivitytoammoniumrelatedtochlorineconcentration.
Sample MCl,cata
(mol)a
MCl,solu
(mol)b
Initial ratepertotalPd
(molnitritemolPd−1L−1min−1)
Initialrateper surfacePd
(molnitritemolPd−1L−1min−1)
NH4+selectivityat80% conversion(%) Pd AC1A 16 16 7.7±1.5 62.6±12.5 9.1±0.5 PdAC2A 11 11 6.0±1.5 51.3±12.8 3.6±0.4 PdAC3A 8.4 8.0 4.2±1.5 50.7±17.8 0.8±0.2 PdAC3R – 0.3 12.6±1.5 71.9±8.5 2.3±0.3
PdAC3RwithextraNaCl 9.2 13.3±1.5 76.1±8.5 1.1±0.2
aAmountofClintroducedbyaddingthecatalystinthereactor,accordingtoXRFresultsinTable2. b AmountofClinaqueousphaseduringreactiondetectedbyIC.
Ontheotherhand,COchemisorptiondatainTable2alsoshow arelativelylowPddispersionof18%onthereducedcatalyst pre-paredwithlowHClconcentration(pH3).Thisapparentdispersion islowerthanwhatwouldbeexpectedbasedonTEMandwe sug-gestthatthisiscausedbythepresenceofPVA.XRFresultsinTable2 showarelativelylowchlorineconcentrationintheas-prepared cat-alyst,inagreementwithXPSresultsinTable3.Inthisas-prepared catalystsonly 7%ofthePdis oxidizedascanbeseen inFigure S-3(a);furthermore,thePd2+:Cl(Pd)molarratiois1:2,
indicat-ingthatthechlorinecoverageiswellbelowonemonolayer(about 30%),muchlowerascomparedtocatalystpreparedusinghigher HClconcentration(pH1and2).Obviously,boththelowchlorine andPd2+contentarecausedbythelowHClconcentrationused
dur-ingthepreparation.WesuggestthatthesmallamountofCl−isnot sufficienttoinducedesorptionofPVAtothesameextentathigh Cl−concentration.
Interestingly,thedatainTable4revealsthatalmostall chlo-rinepresent onthecatalyst desorbedand dissolvedduringthe reaction,basedonthesimilaritybetweentheamountofCl− intro-duced,according XRF,and Cl− contentinaqueousphase inthe
batchreactorasdetectedbyIC.Apparently,themajorityof chlo-rinecanberemovedfromthecatalystsurfaceduringreductionin H2inaqueousphase,beforenitritewasintroduced,byreducingthe
PdClxspeciestoPdmetalandproducingHCl.However,thisdoes
notruleoutsmallamountofchlorineonPdcanstillinfluencethe catalyticreactions,asdiscussedbelowinSection4.3and4.4. Addi-tionally,theproducedHClisinsuchalowconcentration(lower than54molL−1ascalculatedbasedondatainTable4),and can-notinfluencethepHinthereactorsignificantly,especiallyinthe presenceofCO2.
In short, a critical amount of chlorine is necessary for PVA removalfromthePdsurface.Thechlorineconcentrationinthe cat-alystisdeterminedbytheHClconcentrationintheaqueousphase duringimmobilizationofPd-colloidonthecarbonsupport. 4.2. InfluenceofHClonPdoxidationstateandparticlesize
UV-visspectrainFig.2showthepresenceofCl-containingPd complexanionsintheunsupportedcolloidsuspensionafter stir-ringin airwithdifferentHCl concentration,and thecomplexes
Fig.4.ActivityofPd-PVAsupportedonACbeforeandafterreductionat200◦CinH2/N2:concentrationofnitrite(solidsymbols)andammonium(opensymbols)with(a)as
preparedand(b)reducedcatalysts;initialreactionrate(c)pertotalPdor(d)persurfacePd(inunitofmolnitritemolPd−1L−1min−1)withcatalystspreparedatdifferentpH.
Theerrorbarsrepresentstandarddeviation.
converted from[PdCl3(H2O)]− to[PdCl4]2− withincreasing HCl
concentration(i.e.,decreasingpH).Apparently,thesePdcomplex anionsoriginatefrompartiallyre-dissolutionofthePdNPs, accord-ingtoEq.(9). Pd+Cl→− O2H+ PdCl2 +Cl− → +H2O [PdCl3(H2O)]− +Cl − → -H2O [PdCl4]2− (9)
XRFresultsinTable2clearlyshowverysimilarPdloadingsfor allthecatalystsupportedonAC,independentoftheHCl concen-tration.ThisindicatesthatthemajorityofdissolvedPdClx·(H2O)4-x
anions(2<x≤4)re-adsorbonAC.Inthisstudy,thePddispersion determinedbyCOchemisorption,afterreductionat200◦Cfor2h inordertoremovechlorinefromthePdnanoparticles,is32%forthe catalystpreparedwiththehighestHClconcentration(pH1), signif-icantlyhigherthanthedispersionestimatedbasedonTEM(22%). ThisindicatestheexistenceofextremelysmallPdNPs,which can-notbedetectedwiththeTEMusedinthisstudy.Simonovetal. reportedthat[PdCl4]−caneitherform-complexesofPdCl2with
C C fragments of thecarbonmatrix, or bereduced tometallic Pdparticlesbyspontaneousreductiononcarboninthepresence ofHCl[36–38].Probably,extremelysmallPdandPdCl2particles
areformedinthesamewayhere.Ontheotherhand,TEMshows evenlargerPdparticleswithanaveragesizeof4nminthesample PdAC1R,indicatingsomesinteringduringreductioninH2/N2at
200◦C.
Surprisingly,ashighas12%ofPdatomsremainedoxidizedafter reductioninH2/N2at200◦Cfor2hwithcatalystpreparedwith
thehighestHClconcentration(pH1),accordingtoXPSresultsin Table3andFigureS-3.Ascomparison,only3%ofPdwasoxidized inreducedcatalystspreparedatpH2and3.Allcatalystswerekept
inambientovernightbeforeXPSperformed.Thehighamountof oxidizedPdinthereducedcatalystpreparedwithpH1is support-ingthesuggestionthatverysmallPdparticlesarepresent,asthese aremoresusceptibleforoxidationinambient.
Insummary,excessamountofHClcausespartialre-dissolution ofPdNPs,causingincreasingPdparticlesizesaswellasresidual PdCl2afterreductionbyH2.ThusamoderateamountofHClshould
beusedtoremovePVAfromPdsurfacecompletely,atthesame timeminimizingside-effectscausedbyextraHCl.
4.3. InfluenceofHClonactivity
4.3.1. Influenceofchlorineontheactivityofas-preparedcatalysts AsshowninFig.4(c)and(d),allas-preparedcatalystsshowed similaractivitywithinexperimentalerror,regardlessthedifferent chlorineconcentrations.Accordingly,XRFresultsinTable2and ICresultsinTable4 showthemajorityof chlorinere-dissolved inaqueousphaseduringthereductiontreatmentinthereactor, immediatelybeforethecatalyticexperiment,cleaningthePd sur-face and making thesurface Pd atoms accessible for reactants. Furthermore,nosignificantchangeinactivityforPdAC3Rwas foundwhenaddingchlorineupto9.2mol(30molL−1)asshown inTable4.Apparently,chlorinedissolvedinthereactionmixture attheconcentrationsinthisstudyhasnosignificantinfluenceon theapparentactivity.
Atfirstsightthisseemstodisagreewithresultsreportedby Pintar,etal.onnitratehydrogenationonPd/Al2O3[39]andChaplin
etal.onnitritehydrogenation[40].Inbothstudiesreactionrates decreasewithchlorineaddition;itshouldbenotedthoughthat thechlorineconcentrationinthisstudyis atleasttwoorderof
0
20
40
60
80
100
0
10
20
30
40
(a)
As-prepared catalysts
Pd_AC_1_A
Pd_AC_2_A
Pd_AC_3_A
NH
Selectivity (%
)
4 +Conversion (%)
0
20
40
60
80
100
0
10
20
30
40
(b) Reduced catalysts
Pd_AC_1_R
Pd_AC_2_R
Pd_AC_3_R
NH
Selectivity (%
)
4 +Conversion (%)
1
2
3
0 4 8 12 16 As-prepared ReducedNH4+ selectivity
at 80% conversion (
%
)
pH
(c)
Fig.5.SelectivitytoammoniumfornitritehydrogenationwithPd-PVAsupportedonAC:(a)selectivitytoammoniumasfunctionofnitriteconversionwithas-prepared catalysts;(b)selectivitytoammoniumasfunctionofnitriteconversionwithcatalystsreducedat200◦CinH2/N2;(c)comparisonofammoniumselectivityat80%nitrite
conversionwithcatalystpreparedatdifferentpH.
magnitudelower,explainingwhytheeffectoncatalystactivityis negligible.
4.3.2. Activityafterreduction
TheactivityofthecatalystsafterreductioninH2/N2 at200◦C
iscomparedinFig.4(c)and(d).Theinitialratesofthereaction increasewithincreasingpH,usinglessHClduringimmobilization ofthecolloid.Itisclearfromthediscussionabovethatdissolution andre-depositionofPdislikely tooccurduringimmobilization ofthecolloid,probablyinfluencingtheparticlesizedistributionof PdNPsonthesupport,especiallyinthecaseofhighHCl concentra-tion(lowpH).Possibly,extremelysmallPdparticlesinducealower activityperactivesite,asparticlesizeeffecthavebeen experimen-tallyexcludedexclusivelyformetalparticleslargerthan 2.5nm [14,17,18].Thishypothesisneedstobefurthertestedusingcatalyst withnarrowparticlesizedistributionbelow2nmtoevenatomic level.
Insummary,catalystpreparedwithlowestHClconcentration (pH 3) resultsin the highest activity afterreduction in H2/N2,
despiteincompleteremovalofPVAfromthePdsurface.Instead, there-dissolutionofPdinpresenceofhighHClconcentrationinair maycausethedecreaseoftheactivitydespitecompleteremovalof thepolymer.
4.4. EffectofHClontheselectivitytoammonium
ReductioninH2/N2at200◦Cincreasestheselectivityto
ammo-nium as shown in Fig. 5(c), together with removal of chlorine contentasdetectedbyXRFinTable2andXPSinTable3.Onthe otherhand,Table4showstheselectivitydecreaseswithadding extraNaClinPdAC3Rcatalyst.Clearly,Cl−decreasesthe selec-tivitytoammonium,nomatterwhetherCl−isreleasedfromthe catalystduringthereactionorisaddedtotheaqueousphase
reac-tionmixture.Areliablecomparisontosimilareffectsreportedin literatureisnotpossible,againbecausetheconcentrationof chlo-rineinthisstudyismuchlowerthaninliterature[39,40].
Surprisingly, the selectivity to ammonium increased with increasingHCl concentrationduring colloidimmobilization, for bothas-preparedandreducedcatalysts,asshowninFig.5.Table4 confirms thatcatalysts preparedwithhigher HClconcentration inducedhigherchlorineconcentrationduringthecatalytic reac-tion.Clearly,thisdisagreeswiththeeffectoftheCl−concentration inthereactionmixtureasdiscussedaboveandthereforeanother effectonselectivityapparentlycontributes.
Itwasfoundinourpreviouswork[14]thatPVAisnot influenc-ingtheselectivitywhereastheselectivitytoammoniumincreases withincreasingPd particlesize.Therefore, wesuggest thatthe selectivityisinfluencedviathemetalparticlesizeastheparticle size distributions might bedifferent,as discussed above, influ-encedbythedissolution andre-depositionofPd inpresenceof HCl.Clearly,moreworkwouldbeneededtotestthishypothesis.
Inshort,theselectivitytoammoniumdecreaseswithadding lowconcentrationofchlorineinthereactionmixture,whereasthe selectivitytoammoniumincreaseswithincreasingconcentration ofHClduringcolloidimmobilization.
5. Conclusion
Pd-PVAcolloidshavebeenimmobilizedonACwithdifferent HClconcentrationinthepresenceofair.HighconcentrationofHCl (pH1)usedduringcolloidimmobilizationcausespartialdissolution ofPd,decreasingactivityfornitritehydrogenationandincreasing selectivitytoammonium.Incontrast,highactivityandlow selec-tivitytoammoniumcanbeachievedbyusinglowconcentrationof HCl(pH3)duringcolloidimmobilization,despitethefactthatPVA canonlybepartlyremovedfromthePdparticles.Finally,low
con-centrationoffreeCl−inthereactionmixtureinducesadecreasing selectivitytoammonium,withoutinfluencingthereactionrate.
AppendixA. Supplementarydata
Supplementarydataassociatedwiththisarticlecanbefound, intheonlineversion,athttp://dx.doi.org/10.1016/j.cattod.2017.01. 028.
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