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:1995-09-22。 。*。 **。 :,,31,,:。杨宇翔* 吴介达 王 鹏**(同济大学化学系,上海 200092)陈荣三 戴安邦(南京大学配位化学研究所,配位化学国家重点实验室,南京 210093)、,,;BL;NH4ClHCl、。,,。: ,。Kachanovskaya[1]Uridya[2]、NH3-TPD,,,、B、L、、。、NH3-TPDpy-TPD、,L、B,NH4Cl,、、。 1 L、Bpy-IR。(100℃),,。2 NH3-TPDpy-TPDTPD:150mg20～40,50℃NH3py;SP2305,,100℃,、100℃,100mA,N2,30ml/min,50℃,550℃,10℃/min,4199612 JOURNALOFINORGANICCHEMISTRY Vol.12,No.4Dec.,1996NH3-TPD,0.1mlNH3,py-TPD0.35μl。3 9310。 1 BLSiO2,Al2O3,,BL。AlO2-Si[3,4]。FTIR,、BL,1543、1446cm-1(1)。1,:B,,;L,,,。1 、Table1 RelationshipbetweenAcidSitePropertiesofVariousLocalDiatomites,SilicaGelandItsStructureitemdiatomspeciesstructureofdiatombodyporesizedistributionpeaktemperature(K)peakarea(cm2)NH3desorptionamount(ml)(STPstate)ZhejiangbluesoilZhejiangwhitesoilMelosiraAgardhsinglecylindricalordoublejointcylindrical1.34～2.81μm115～147nmandcontain6～7.6nm432.531.20.392424.832.00.403658.44.30.054JilingdiatomiteCosoinodisousEhrenbergdisoshaped50～700nmandcontain5～20nm424.827.80.350YunnandiatomiteCyclotellaKutzingCocconeisEhrenbergdisoshapedovalshaped0.15～0.30μm0.50～1.0μm10～20nm440.127.80.350GuangdongdiatomiteFragilariaLyngbyeSurirellaTurpinpoleshapedovalshaped0.05～0.1μm10～20nm450.325.20.317silicagel412.130.40.382631.83.90.049,,[6],6～7.6nm115～147nm;,,[6],50～700nm5～20nm;,,,NH3,TPD432.5K,424.8K(1),B。·357·4 1 IR-Fig.1 IRspectraofdiatomitesampleadsorbedpyridina.Jilingdiatomite b.Zhejiangdiatomite c.acidwashedZhejiangdiatomite2 NH3-TPDFig.2NH3-TPDspectraofdiatomitea.spectralineofJilingdiatomitedesorbedNH3b.spectralineofZhejingdiatomitedesorbedNH3c.lineoftemperaturerisingrate,30.4nm6000nm[5],,,B,Si-O-Si,SiOH-,Si5,L[3]。SiOOOH+OH-H+H2OSiOOH-+H3O+OHO2 NH3-TPD2.1 2、NH3-TPD。、、NH3-TPD。2,NH3(1)。、、,[5],NH3SiOH←∶NH3[3],,412.1～450.3K;3[5],NH3Si(OH)2←∶NH3,[4],,,630～660K,。、,,1412.1～450.3K,:≈。,,,;,,[6],NH3,,,。,,,[5,6],,,。2.2 NH4ClHClNH3-TPDNH4ClHCl、NH3[7]。5%HCl,,,、·358· 12,;NH4Cl,,,,。。,[3],≡SiOH,,,;,,,,,;HCl,SiO2Fe、Al,,2。SiOHOHHOSiOOSiOSiOHOHHSiOHOSiOHOSiOHOSiOHOHH2 ()Table2 ElementContentofDiatomite(ActivatedorUnactivated)SiO2FeAlaverageporediameterZhejiangdiatomite62.51.422.7030.4nmacid-washedZhejiangdiatomite86.900.201.206000nmJilingdiatomite92.750.542.85120nmacid-washedJilingdiatomite93.960.121.40140nm,Fe、Al,。HCl,=Si(OH)2,H3O+,500℃,L[4],。HCl,。,[8],,,,,;Fe、Al,。NH4Cl,,。3 ,;,600℃,950℃,(3)。600℃,,,,,,[9],NH3,、;800℃,,,H2O,,,,L[9],;950℃,5.87～300μm,[8],。1150℃,α-,0.5～1nm,[8],。·359·4 3 Table3 AcidSitePropertiesVariationsofZhejiangDiatomiteRoastedatHighTemperatureroastedtemperatureporesizedistributiondesorptiontemperature(K)peakarea(cm2)NH3desorptionamount(ml)(STPstate)unroasteddiatomite1.34～2.81μm115～147nm6～7.6nm432.531.20.392600℃2.81～9.50μm446.534.00.428800℃3.95～35.0μm474.523.20.292950℃5.87～300μm474.52.40.0301150℃0.5～1nm474.51.00.0134 py-TPDpy-TPD、()(),4。,424.8783.5K,。,[10],,,,。,,;,,。,,。4 py-TPDTable4 py-TPDresultsofZhejiangbluesoilandJilingdiatomiteitemdesorptiontemperature(K)peakarea(cm2)pydesorptionamount(STPstate)Zhejiangdiatomiteunactivated424.829.31.316783.512.30.552activated424.825.41.141783.53.50.157Jilingdiatomiteunactivated412.113.60.611activated405.712.70.570py-TPD,,,[8];,,,。·360· 12 [1]Kachanovshaya,L.D.,Dokl.Akad.Nauk.SSSR,250(5),1178(1980).[2]Uridya,L.Ya.,Izv.Akad.Nauk.Gruz.SSR,Ser.Khim.,13(4),282(1987).[3]Iler,R.K.,TheChemistryofSilica,NewYork;JohnWiley&Sons,630,649(1979).[4][], ,,,210(1989).[5],化学学报,54(1),57,(1996).[6]YangYuxiang,ChenRongsan,DaiAnbang,SilicatesIndustriels,CeramicScienceandTechnology,TomeLⅤIII-N3-4,65(1993)(Belgian).[7],(1991.10)[8],南京大学学报(自然科学版),27(4),706(1991).[9],,,305(1978).[10],,,116(1978).ASTUDYONSURFACEACIDSITEPROPERTIESOFLOCALDIATOMITESYangYuxiang WuJieda WangPeng(ChemistryDepartment,TongjiUniversity,Shanghai200092)ChenRongsan DaiAnbang(CoordinationChemistryInstitute,StateKeyLaboratoryofCoordinationChemistry,NanjingUniversity,Nanjing210093)Inthispaper,surfacestructure,porestructureandsurfaceacidsitepropertiesofseveralkindsdiatomitewerestudied.ItwasfoundthattherewasjoinedhydroxylgroupsinZhejiangwhitesoil,onlyisolatedandadjacenthydroxylgroupswerefoundinotherdiatomite.AlsotherewassomeLacidandBacidindiatomite.Theacidsitepropertiesofdiatomitesuntreat-edaswellastreatedwithNH4Clorhydrochloricacidwereallconcernedwithporestructure,surfacestructureofdiatomite.Asroasttemperatureincreased,theacidsitestrengthofdi-atomiteincreased,andtheacidsiteamountgraduallydecreased.Keywords: diatomite acidsiteproperty structure·361·4