负载型高分子金属配合物的制备及其催化H2O2分解性能研究金碧凤

24　220083()JournalofFujianNormalUniversity(NaturalScienceEdition)Vol.24　No.2Mar.2008:1000-5277(2008)02-0057-06负载型高分子金属配合物的制备及其催化H2O2分解性能研究金碧凤1,王世铭1,王琼生1*,王诣婧2(1.,　350007;2.,　430079)　　:以介孔分子筛MCM-41作载体制备了Cu(Ⅱ)-壳聚糖(CS)高分子金属配合物为活性组分的催化剂Cu-CS/MCM-41,并利用红外光谱和低温N2吸附等手段研究了催化剂的结构特征.结果表明,Cu-CS/MCM-41催化剂的比表面积为208.6m2/g,平均孔径和孔容分别为2.3nm和0.27cm3/g.将Cu-CS/MCM-41用于催化过氧化氢分解反应,当温度为20℃,pH=4.5,反应液体积为60.0mL,H2O2的初始浓度为0.1443mol/L,Cu-CS/MCM-41催化剂用量为0.1000g等条件下,反应24h,H2O2的分解率可达84%.催化剂显示具有模拟过氧化氢酶(CAT)的作用,而且可多次重复使用,并有较稳定的催化活性.同时分别考察了温度、H2O2的浓度、pH值、反应时间及Cu-CS/MCM-41催化剂的用量等对Cu-CS/MCM-41催化性能的影响规律.:铜;壳聚糖;配合物;分子筛;过氧化氢;催化剂:O643　　　:A　:2007-09-21　:(U0650007/2006J0251;Z0513009);(JB05313)　:(1982—　),,,.*:[e-mail]-chitosanComplexSupportedonMCM-41andCatalyticPropertiesforDecompositionofH2O2JINBi-feng1,WANGShi-ming1,WANGQiong-sheng1*,WANGYi-jing2(1.CollegeofChemistryandMaterialsScience,FujianNormalUniversity,Fuzhou350007,China;2.CollegeofChemistry,HuazhongNormalUniversity,Wuhan430079,China)Abstract:Anewheterogeneouscatalyst,Cu(Ⅱ)-chitosan(CS)complexsupportedonmesoporousmolecularsieveMCM-41waspreparedandcharacterizedbyFTIRandN2adsorption-desorptionmeasurements.Thespecificsurfacearea,averageporediameterandporevolumeoftheCu-CS/MCM-41catalystwere208.6m2/g,2.30nm,and0.27cm3/g,respectively.TheCu-CS/MCM-41wasappliedtosimulateH2O2-enzymetocatalyzethedecompositionofH2O2.TherateofH2O2decompositionreached84%at20℃,withasolutionvolumeof60.0mL,containingahydrogenperoxideconcentrationof0.1443mol/L,pH4.5,thecatalystmassof0.1000g,andafterreactionfor24h.Theexperimentalresultsshowthatthecatalystishighlyactiveandreusable.Moreover,theeffectsofreactiontemperature,theconcentrationofH2O2,pH,reactiontime,andthequantityofCu-CS/MCM-41forthedecompositionofH2O2wereinvestigated.Keywords:copper;chitosan;complex;MCM-41molecularsieve;H2O2;catalyst(chitosan,CS)N-,,:U-(1→4)-2--2--D-,1[1].—NH2,—NH2—OH,,.[2-4],,,,、、、[5-6].,(CAT)H2O2H2OO2,HO·DNA[7],,.Cu(Ⅱ)[1],Cu(Ⅱ)-CSH2O2[8-10].,,,.1　Cu(Ⅱ)-CS,,H2O2..MCM-41,Cu(Ⅱ)-CS;,,H2O2,,;,Cu-CS/MCM-41,,,.,MCM-41,Cu-CS/MCM-41,H2O2,、H2O2、pH、Cu-CS/MCM-41Cu-CS/MCM-41.,Cu-CS/MCM-41,H2O2.1　1.1　材料(90.85%,8.5×106,),(30%,AR,),(AR,),(AR,),(AR,),(AR,).MCM-41[11],1000m2·g-1、3～4nm、MCM-41.1.2　Cu-CS/MCM-41催化剂的制备20mL2%0.2g,2.0gMCM-41,,0.5mol/LNaOHpH13.,,50℃CS/MCM-41.1gCu2+48h.,.,Cu-CS/MCM-41.1.3　Cu-CS/MCM-41催化剂的表征MicroAPAS2000,50℃12h.(FTIR)NicoletNEXUS670,KBr.1.4　催化性能实验方法,Cu-CS/MCM-41,.58()　　　　　　　　　　　2008　2.00mL,,[12].(1).ct=5cMnVMnVt,(1)ctH2O2(mol/L),cMn(mol/L),VtH2O2(mL),VMn(mL).H2O2:H2O2=ct/c0×100%,(2)c0H2O2.2　2.1　Cu-CS/MCM-41催化剂的介孔特征,N2、[13].2Cu-CS/MCM-41N2-.MCM-41N2-,Cu-CS/MCM-41N2-LangmuirⅣ;2,Cu-CS/MCM-41.3,Cu-CS/MCM-41,MCM-41[11].BETCu-CS/MCM-41208.6m2/g,2.30nm0.27cm3/g.,、,Cu-CS、MCM-41,,N2.2　Cu-CS/MCM-41N2-3　Cu-CS/MCM-41　4　Cu-CS/MCM-412.2　Cu-CS/MCM-41催化剂的红外光谱4Cu-CS/MCM-41,MCM-41CS.MCM-41(4b),3400cm-1OH,1626.9cm-1OH,1078cm-1,807.73cm-1,464.32cm-1Si—O—Si,Si—OH952.9cm-1[13].MCM-41,Cu-CS(4c),3400cm-13440cm-13358cm-1,,CSN—HO—H;NH、OH1627cm-1,MCM-41、.,MCM-41CS、.,Cu-CS/MCM-41IR,2923cm-1,C—H;1378.7cm-1C—N,569.2cm-1N—H,CS1385.1cm-159　2　　　　　　　:H2O2589.9cm-1(4a),;Cu-CSCS—NH2CuCu-CS[3],Cu-CSMCM-41.2.3　Cu-CS/MCM-41催化剂的催化性能20℃,pH4.5,60.0mL,H2O20.1443mol/L,0.1000gCS、MCM-41、Cu2+、Cu-CS、Cu-CS/MCM-41,24hH2O2,1.1,,H2O2;H2O2;Cu2+、Cu-CSH2O2,;Cu-CS/MCM-41H2O2,84%,.Cu-CSH2O2Cu2+、Cu-CS.:(1),,;(2)H2O2MCM-41、;(3)Cu-CS,Cu-CS/MCM-41,H2O2,Cu-CS.1　%CSMCM-41Cu2+Cu-CSCu-CS/MCM-41H2O299.395.797.969.678.715.5　　　　　:0.1000g2.4　Cu-CS/MCM-41的催化性能的影响因素2.4.1　温度对催化性能的影响pH4.5,60.0mL,H2O20.1443mol/L,Cu-CS/MCM-410.1000g,Cu-CS/MCM-41H2O2,5.5:Cu-CS/MCM-41,,,,H2O2;60℃,2hH2O2.60℃,H2O2(3.6±0.2)%,H2O2,[14],10℃,2～4.5　H2O26　H2O22.4.2　H2O2浓度对催化性能的影响20℃,pH4.5,60.0mL,0.1000g,Cu-CS/MCM-41H2O2,6.6a:,H2O2,H2O2,.6b:H2O2,Cu-CS/MCM-41,H2O270%,H2O20.10mol/L,H2O2,84%;6a,H2O2(2)H2O2,Cu-CS/MCM-41H2O20.10mol/L.60()　　　　　　　　　　　2008　2.4.3　pH值对催化性能的影响,pHH2O2,pH,Cu-CS,Cu-CS,,pH4.2,,[1];,pH,OH-Cu-CS.pH、Cu-CS.pH4～8,pHCu-CS/MCM-41H2O2,:20℃,60.0mL,H2O20.1443mol/L,Cu-CS/MCM-410.1000g.7.7:pH4～8,H2O2,;pH5,24h,H2O2,.[8],Cu(Ⅱ)-CS,,,pH,Cu-CS/MCM-41H2O2,pHH2O2.2.4.4　催化剂用量对催化性能的影响20℃,pH4.5,60.0mL,H2O20.1443mol/L,Cu-CS/MCM-41H2O2,8.8:Cu-CS/MCM-41,H2O2,0.1000g,0.1000g0.2000g,H2O2,H2O2.7　pH8　2.5　Cu-CS/MCM-41催化剂的催化稳定性20℃,pH4.5,60.0mL,H2O20.1443mol/L,Cu-CS/MCM-410.1000g,.3,,H2O270%.,.3　(1)Cu-CS/MCM-41,.,.(2)、、pH.,.参考文献:[1].[M].:,2003.[2],,,.[J].,2001,13(1):21-26.[3],,,.Cu(Ⅱ)[J].,2002,18(1):87-90.61　2　　　　　　　:H2O2[4],,.[J].,2003,5:53-57.[5]BahaY,HirakawaH,KawanoY.Selectiveadsorptionofpreciousmetalsonsulfur-containingchitosanderivatives[J].ChemistryLetter,1994,51(1):117-120.[6]MebrideTJ,PrestonBD,LoebLA.MutagenicspectrumresultingfromDNAdamagebyoxygenradicals[J].Biochemistry,1991,30(1):207-211.[7]KramarevaNV,FinashinaED,KucherovAV,etal.Coppercomplexesstabilizedbychitosans:peculiaritiesofthestructure,redox,andcatalyticproperties[J].KineticsandCatalysis,2003,44(6):793-800.[8],,.-Cu(II)H2O2[J].:,2005,35(3):31-33.[9],,,.-Cu(II)H2O2[J].,2002,36(1):79-81.[10]AnandR,MaheswariR,GoreKU,etal.Selectivealkylationofcatecholwitht-butylal