Continuous flow synthesis of phosphate binding h-BN@magnetite … · Department of Chemical...

Continuousflowsynthesisofphosphatebindingh-BN@magnetitehybrid

material

AhmedHusseinMohammedAl-antakia,XuanLuoa,b,AlexDuanc,RobertN.Lambc,ElaEroglud,WayneHutchisone,Yi-ChaoZouf,JinZouf,ColinL.Rastona*

a. InstituteforNanoscaleScienceandTechnology,CollegeofScienceandEngineering,FlindersUniversity,Adelaide,SA5042,Australia.

b. CentreforMarineBioproductsDevelopment,CollegeofMedicineandPublicHealth,FlindersUniversity,Adelaide,SA5042,Australia.

c. TraceAnalysisforchemical,EarthandEnvironmentalSciences(TrACEES),theuniversityofMelbourne,Victoria3010,Australia.

d. DepartmentofChemicalEngineering,CurtinUniversity,Perth,Australia.e. SchoolofPEMS,UniversityofNewSouthWales,ADFAcampus,CanberraBC,ACT2610,Australia.f. MaterialsEngineering,andCentre forMicroscopyandMicroanalysis,TheUniversityofQueensland,Brisbane,QLD

4072,Australia.

FigureS1.h-BN@magnetitecompositepreparedusingtheconfinedmodeofoperationoftheVFDfor15min,withpulsedlaseroperatingat1064nmand360mJ,irradiatingapureirontarget. Rotational speed at 7.5k rpm for a 20mmODglass tube, tilt angle 45º andh-BNdispersedinwater(0.1mg/mL).(a-f)SEMimagesand(g)XRDpattern.

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2018

FigureS2.AFMimagesforh-BN@magnetitecompositepreparedinaVFDundercontinuousflowmodewithapulsedlaseroperatingat1064nmand360mJ,irradiatingapureirontarget.Rotationalspeedat7.5krpm,tiltangle45ºandflowrate1mL/min.

FigureS3.SEMimagesofh-BN@magnetitecompositepreparedundercontinuousflowmodewithapulsedlaserirradiatingapureirontarget,operatingat1064nmand360mJ,withthe20mmODglasstuberotatingat7.5krpm,tiltangle45oandflowrateat1mL/min.

FigureS4.BETchart(blue)ofh-BN@magnetitepreparedundercontinuousflowwithapulsedlaserirradiatingapureirontarget,operatingat1064nmand360mJ,withtheVFDtube20mm in diameter rotating at 7.5k rpm, tilt angle 45º and flow rate at 1mL/min; (red) asreceivedh-BN.

FigureS5. (a)EDXdataforelementalanalysis inbandc. (bandc)SEMimagesatvariouslocationsofh-BN@magnetitecompositepreparedundercontinuousflowwithapulsedlaserirradiatingapureirontargetoperatingat1064nmand360mJ,withaglasstube20mmindiameterrotatingat7.5krpm,tiltangle45ºandflowrateat1mL/min.

FigureS6.HRTEMimages(a-c)asreceivedh-BN,(d-f)h-BN@magnetitecompositepreparedusingapulsedlaserirradiatingapureirontargetoperatingat1064nmand360mJ,witha20mmglasstuberotatingat7.5krpm,tiltangle45ºandflowrateat1mL/min.

FigureS7.ATRFTIRspectraforasreceivedh-BNandh-BN@magnetitecompositecomparedwithmagnetitepreparedwithapulsedlaserirradiatingapureirontarget,operatingat1064nmand360mJwitha20mmODtuberotatingat7.5krpm,tiltangle45ºandaflowrateofwaterat0.1mL/min.1Theh-BN@magnetitewaspreparedasforthemagnetitebutwithh-BNdispersedinwater(0.1mg/mL)ataflowrateof1mL/min.

Controlexperiments:Threecontrolexperimentswereundertakentodecoupleanyeffectof

the laser on the h-BN and shear stress in the dynamic thin film in the VFD, with the

characterizationofthematerialusingSEMandXRD,andzetapotential.

1- Processingh-BNintheVFDintheabsenceofapulsedlaser.h-BNdispersedinwater(0.1

mg/mL)wasdeliveredviaajetfeedtothebaseofaglasstube20mmindiameterusing

ajetfeed,withtheflowrateat1mL/min,rotationalspeed7.5krpmandtiltangle45o.

Thecoloroftheprocessedliquidwassimilartothepre-processedsample,withthezeta

potentialsimilarat-19.7mV.

FigureS8.(a,b)SEMimagesforh-BNprocessedintheVFDundercontinuousflowwithaflowrateofadispersionofh-BNinwater(0.1mg/mL)at1mL/min,rotationspeed7.5krpm, tilt angle45o in theabsenceofa laser. (c)Photographof thedispersionofh-BNsolutionafterprocessing.(d)XRDoftheh-BNafterprocessing.

2- Processingwith thepulsed laser irradiating the solutionwithout irradiating the iron

target.Adispersionofasreceivedh-BNinwater(0.1mg/mL)wasdeliveredtothebaseof

a20mmODglasstubeat1mL/min,withthetuberotatingat7.5krpmandatatiltangle

of45o;thepulsedlaserwasoperatedat1064nmand360mJ.Thecoloroftheprocessed

liquidwassimilar to thepre-processedsample,witha similar zetapotentialvalueat -

18.4mV.

FigureS9.(a,b)SEMimagesforh-BNprocessedinaVFD,withadispersionoftheasreceivedmaterialdeliveredtothebaseofa20mmODglasstuberotatingat7.5krpm,ataflowrateofadispersionofh-BNinwater(0.1mg/mL)at1mL/minforatiltangleof45ºandthepulsedlaser operating at 1064 nm and 360 mJ, without the laser irradiating the iron rod. (c)Photographoftheprocesseddispersionofh-BN.(d)XRDofh-BNafterprocessing.

3- Confinedmodeprocessingofamixtureofh-BNwithIONPs(magnetitenanoparticles).

Amixtureofh-BNdispersedinwater(0.1mg/mL)andpreformedmagnetiteparticles(0.5

mg/mL)previouslyprepared in theVFDusingour recently reportedprocedure for the

exclusiveformationofthismaterial.1Thetotalvolumeofliquidinthetubewas1mL,with

therotationalspeedsetat7.5krpm,thetiltangleat45o,andtheprocessingtimeat15

mins,intheabsenceofalaser.Thecoloroftheresultingsolutionwasbrown,asexpected,

andtheSEMimagessimilartoh-BN@magnetitecompositeprepared insitu.However,

the zeta potential had two peaks, -8.03 mV and -17.3mV, presumably the former

corresponding with some of the h-BN particles devoid of surface bound magnetite

particles,notingthatthelatterisclosetozetapotentialforasreceivedh-BN(-19.7mV).

Incontrastthezetapotentialforh-BN@magnetiteprepareddirectlyinthepresenceofa

laseris+or-?37.2mV.

FigureS10.(a,b)SEMimagesforthematerialformedonprocessing1mLofamixtureofh-BN dispersed in water (0.1 mg/mL) and magnetite nanoparticles (0.5 mg/mL), using theconfinedmodeofoperationoftheVFD(15mins,45otiltangle,7.5krpmrotationalspeed,20mmODglasstube),intheabsenceoflaserirradiation.Themagnetitenanoparticles(12nmindiameter)wherepreparedusingourpublishedprocedureintheVFD.1(c)Photographoftheh-BN@magnetitesolutionafterprocessingundertheseconditions.

FigureS11.IndividualamountofPO43-adsorbedinmgL-1byeachsequentialcycle,forthreedifferentloadingsofmagnetich-BNsamples:(1)10mgadsorbent(light-greycolumns);(2)25mgadsorbent(dark-greycolumns);and(3)50mgadsorbent(blackcolumns).

1. X.Luo,A.H.M.Al-Antaki,T.M.D.Alharbi,W.D.Hutchison,Y.-c.Zou,J.Zou,A.Sheehan,W.ZhangandC.L.Raston,

ACSOmega,2018,3,11172-11178.