Mimicking bio-sintering The identification of highly condensed surfaces in bioinspired silica materials - Manning et al. - Unknown - Un

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SUPPORTINGINFORMATIONMimickingbio-sintering:TheidentificationofhighlycondensedsurfacesinbioinspiredsilicamaterialsJosephRHManning1,2,3,BrantWalkley1,4,JohnL.Provis4andSiddharthV.Patwardhan1*1DepartmentofChemicalandBiologicalEngineering,TheUniversityofSheffield,SheffieldS13JD,UK.2DepartmentofChemicalEngineering,TheUniversityofBathBA27AY,UK,3DepartmentofChemistry,UniversityCollegeLondon,WC1E6BT,UK4DepartmentofMaterialsScienceandEngineering,TheUniversityofSheffield,SheffieldS13JD,UK.*s.patwardhan@sheffield.ac.ukTableS1:NMRparametersextractedfromthe29SiMASNMRand1H-29SiCPMASNMRspectraforBISsilica.HeretherelativeintegralareaindicatestherelativeproportionsofeachQnsite,δisoistheisotropicchemicalshiftandFWHMisfullwidthathalfmaximum.Estimatederrorbasedonsignal/noiseis1%.Peakassignmentsweremadewithreferencetotheliterature.1–3Relativeintegralarea(%)FWHMSample1H-29SiCPδiso(ppm)Assignment29SiMAS(ppm)MAS712-91.06.0Q2pH73447-99.97.3Q35941-110.010.0Q458-91.06.0Q2pH53453-99.97.3Q36139-110.010.0Q4513-91.06.0Q2pH23369-99.97.3Q36218-110.010.0Q4S1

1TableS2:NMRparametersextractedfromthe29SiMASNMRand1H-29SiCPMASNMRspectraforthreebatchesofBISsilicaafteragingatca.pH7for24hours.HeretherelativeintegralareaindicatestherelativeproportionsofeachQnsite,δisoistheisotropicchemicalshiftandFWHMisfullwidthathalfmaximum.Estimatederrorbasedonsignal/noiseis1%.Peakassignmentsweremadewithreferencetotheliterature.1–3Relativeintegralarea(%)FWHMSample1H-29SiCPδiso(ppm)Assignment29SiMAS(ppm)MAS24%12%-92.05.0QpH7.2433%65%-100.97.1Q3463%16%-110.29.1Q24%11%-92.05.0QpH7.0832%65%-100.97.1Q3464%18%-110.29.1Q24%12%-92.05.0QpH6.9832%66%-100.97.1Q3465%16%-110.29.1QTableS3:NMRparametersextractedfromthe29SiMASNMRand1H-29SiCPMASNMRspectraofallIPSsilica.HeretherelativeintegralareaindicatestherelativeproportionsofeachQnsite,δisoistheisotropicchemicalshiftandFWHMisfullwidthathalfmaximum.Estimatederrorbasedonsignal/noiseis1%.Peakassignmentsweremadewithreferencetotheliterature.1–3Relativeintegralarea(%)FWHMSample1H-29SiCPδiso(ppm)Assignment29SiMAS(ppm)MAS614-91.44.9Q2pH73977-100.76.7Q3559-109.88.0Q4820-91.44.9Q2pH54271-100.76.7Q3509-109.88.0Q4920-91.44.9Q2pH24372-100.76.7Q3489-109.88.0Q4S2

2AQ4B3Q3Q4Q2highQhighQ2conc.conc.Q33Q4Q4Q2lowQlowQ2conc.conc.-70-80-90-100-110-120-130-140-70-80-90-100-110-120-130-1402929?(Si/ppm)?(Si/ppm)isoisoFigureS1-(A)29Sisingle-pulseMASNMRspectraand(B)1H-29SiCPMASNMRspectraformodifiedIPSmaterialsatdifferentPEHAconcentrations.Top-highconcentration,bottom-lowconcentration.Shownaretheoriginaldata(black),individualresonancecontributions(green),fittedsumofindividualcontributions(red),andresidual(blue).S3

3FigureS2-(A)29Sisingle-pulseMASNMRspectraand(B)1H-29SiCPMASNMRspectraforBISsamplesafter24hoursofaging.Top-pH7.24,Middle-pH7.08,Bottom-pH6.98.Shownaretheoriginaldata(black),individualresonancecontributions(green),fittedsumofindividualcontributions(red),andresidual(blue).TableS4:NMRparametersextractedfromthe29SiMASNMRand1H-29SiCPMASNMRspectraofallPEHA-modifiedIPSsilica.HeretherelativeintegralareaindicatestherelativeproportionsofeachQnsite,δisoistheisotropicchemicalshiftandFWHMisfullwidthathalfmaximum.Estimatederrorbasedonsignal/noiseis1%.Peakassignmentsweremadewithreferencetotheliterature.1–3RelativeintegralareaδisoFWHMAssignme(%)(ppm)(ppm)ntSample29Si1H-29SiCPMASMAS811-91.37.66Q2Highconcentration3959-100.36.91Q35330-110.08.82Q41013-91.37.66Q2Lowconcentration4255-100.36.91Q34831-110.08.82Q4S4

4TableS5:CalculatedionicstrengthsforthesilicasuspensionsusedwithinthisstudyBISIonicstrength*IPSIonicTreatmentpH(mmol/L)strength7130.160.935138.660.342170.2848.5Highconcentration-1121Lowconcentration-19*TypicalvaluesTableS6:CalculatedPEHAcontentinBISsamples,eitherfreshlymadeorafteragingfor24hoursSample*/synthesispHPEHAcontent(mmol/g)Unaged/pH70.64±0.02**Aged-1/7.240.11Aged-2/7.080.098Aged-3/6.980.15Averageofagedsamples0.12±0.03IPS-pH7NilIPS-pH5NilIPS-pH2NilModifiedIPS-High0.28conc.ModifiedIPs-lowconc.0.44*For“Aged”samples,threesamplesweresynthesised,agedfor24hrandanalysedusingCHNanalysis.**Previouslyreportedinreference4.References(1)Sindorf,D.W.;Maciel,G.E.29SiCP/MASNMRStudiesofMethylchlorosilaneReactionsonSilicaGel.J.Am.Chem.Soc.1981,103(14),4263–4265.(2)Zhao,X.S.;Lu,G.Q.;Whittaker,A.K.;Millar,G.J.;Zhu,H.Y.29SiComprehensiveStudyofSurfaceChemistryofMCM-41UsingCP/MASNMR,FTIR,Pyridine-TPAandTGA.J.Phys.Chem.B1997,5647(97),6525–6531.(3)Engelhardt,G.;Michel,D.High-ResolutionSolid-StateNMRofSilicatesandZeolites;Wiley:Chichester,1987.(4)Manning,J.R.H.;Yip,T.W.S.;Centi,A.;Jorge,M.;Patwardhan,S.V.AnEco-Friendly,TunableandScalableMethodforProducingPorousFunctionalNanomaterialsDesignedUsingMolecularInteractions.ChemSusChem2017,10(8),1683–1691.S5