金属纳米颗粒合成中的还原剂和保护剂

22420104PROGRESSINCHEMISTRYVol.22No.4Apr.20102009520099*No.20871031B108[e-mail]*200433、、。、。、、、、、、。O611.4O614.12A1005-281X201004-0580-13ReducingAgentsandCappingAgentsinthePreparationofMetalNanoparticlesWangLiyingCaiLingjianShenDiFengYonggangChenMengQianDongjinShanghaiKeyLaboratoryofMolecularCatalystsandInnovativeMaterialsDepartmentofChemistryLaboratoryofAdvancedMaterialsFudanUniversityShanghai200433ChinaAbstractMetalnanoparticleshavereceivedmuchattentionduetotheirintriguingopticalelectricalchemicalpropertiesandtheirpotentialapplications.Inrecentyearscontrollingnanoparticles’sizeandshapesimprovingtheirstabilityandmonodispersibilityincreasingtheiryieldandpurityarethecentralchallengesthusdevelopmentandimprovementofthesyntheticmethodsofmetalnanoparticleshavebecomemoreandmoreimportant.Inthispaperseveralchemicalsyntheticroutesincludingreductionbychemicalselectrochemistryandirradiationetcofmetalnanoparticleshavebeensummarized.EspeciallytheinorganicandorganicreducingagentsthecappingagentsincludingN-P-COOH-SH-containingmoleculesandpolymersandthemechanismsinvolvedinthechemicalpreparationarediscussed.KeywordsmetalnanoparticlesreducingagentscappingagentsContents1Introduction2Reducingmethodscommonusedinthepreparationofmetalnanoparticles2.1Reducingagentsandmechanismsinthereductionbychemicals2.2Otherreducingmethods3Cappingagentsandmechanismscommonusedinthepreparationofmetalnanoparticles3.1Thiolsandtheirderivatives3.2Carboxylicacidsandtheirderivatives3.3Aminoandamidecompounds3.4Organicphosphines4·581·3.5Surfactants3.6Polymers3.7Cyclodextrinanditsderivatives4Conclusion1、、、。、、、。。、、、、。。2。、、、、。、。2.1。11—6、7—9、、21011、12、413、1114、815、1216—18、19、14、2021、NN-DMF。。、。。2.1.12.1.1.1、、TBAB、、、、1—6922—26。BH4－+2H2→OBO2－+4H2↑1nBH4－+8Mn++8nOH→－nBO2－+8M+6nH2O2Zukoski27intermediateBH4－+H++2H2→→OintermediateHBO2+4H2↑3Peng9TBABTBAB、、、、。2.1.1.2LiAlH4NaBH4。Groschel2829LiAlH4NaBH42—5nmChernyshov30THFLiAlH4Pd。LiAlH4AlH－4。2.1.1.3N2H4·H2O893132。4Mn++nN2H4·H2O+4nOH→－4M+nN2+5nH2O4pHN2H→4N2+4H++4e－5·582·22N2H4+4OH→－N2+4H2O+4e－62.1.1.4Sarma26nm2021。2Mn++nH2O→22M+2nH++nO272.1.1.5Xie33Ag++η5-C5H52Fe→r.t.Ag+η5-C5H52Fe+82.1.1.6。Ag。15—200nm。、34。2Mn++nH→22M+2nH+92.1.1.7。3—44Mn++nH2PO2－+2nH2→O4M+nH2PO4－+4nH+10。。35。4Ag++H3PO2+2H2→O4Ag↓+H3PO4+4H+1112。Zhang11、POHHOOk1k幑幐帯帯2PHOHOH12Ag。Zhu17CuNPs。16SDBSCuC3H6O3+HPO32－+OH→－Cu+C3H8O3+PO43－132-AOT--2—4nm3637。NaH2PO2·H2ONaOHCo2+、Ni2+、Cu2+。NaOH38Co2++H2PO2－+3OH→－Co+HPO32－+2H2O142.1.1.8AleandriGrignardRuPt39、MCln。nM1MgClm+mM2Cl→nMn1Mm2+mnMgCl2mn=123152.1.22.1.2.11040—46。、。4·583·2.1.2.2122.1.2.3、4。、。Mn++nNR→3M+nNR3+2047。1。AgⅠAgⅠAg、、Nπ、。1-47Fig.1Schematicillustrationoftheproposedformationmechanismofsilvernanoparticlesobtainedinthemixtureofoleylamineandliquidparaffin47Newman13。Au0→Au+HAuCl4→Au0。。Graf48。Nakao49。Chaki50TEADDT2.5nm。Nakamoto51、。Bhargava52L-、、L-KAuBr4。EDTA5354。2.1.2.4NN-DMF。DMFnHCONMe2+2Mn++nH2→O2M+nMe2NCOOH+2nH+21。Kapoor55PVPAg。AM。、、Ag+、Ag。AgAg+Ag+。56。2.1.2.5ascorbicacid23-gulonicacid。·584·2215。。nC6H8O6+2M→+nC6H6O6+2M+2nH+222.1.2.6。。RCHO+2Ag++2OH→－RCOOH+2Ag+H2O23。Yu57HTABAg、、、。CHOHCHOH4CHO。Yu14HTAB55±5nm。Raveendran58β-D-“”20nm。2.1.2.719、EG59。。592HOCH2CH2→OH2CH3CHO+2H2O242CH3CHO+PtCl→2CH3COCOCH3+Pt+2HCl25Swami60Ag+。2.2、。。2.2.1。、、、、。。Met=Mn++ne－Mn++ne－+=Met/Met+=Met/、、、。Yu61Au。Cai62PVPAu1—2μmAg。2.2.2、、γ、-、。、、。。γ、UV-、He－aqOH。H2→Oe－aqH·OH·H2·H2O2H3O+26γ、、H2O2、OH·。。、、、、、。Mirkin6364AgAg。、、。。65—69Au、Ag、Te、Se。4·585·3、、、。、、、、、、DNA、SiO2TiO2。31、、、。2、、。3、、。、、。3.1。、70。He46NaBH41-4.18nmAgAgNPshcpsuperlattice。Shon71buntesaltsSO3AgNPs。AgNPsBH－4AgNPsBH－4AgNPs2。Li7217nmAg。Cliffel73NaBH4。Mandal74212-AgNPs71Fig.2SchematicdiagramofthesynthesisofAgNPsusingsodiumS-dodecylthiosulfateinH2O71S。3AgNPs74Fig.3Cartoonshowingtheassemblyofcysteine-cappedsilverparticlesinsolutionbyhydrogenbondingoftheaminoacidmoleculesondifferentsilverparticlesanddisaggregationofthesuperclustersbyheatingthesolution7460℃AgNPs3。Tan752-MBMZMBMZ·C2H+5Br－AgMBMZ。·586·22NN-DTC1076。DTC10SAg2.5—5nmSET76。3.2Wang23、Ag-TEM。AgAg。Yang77Ag4.7nmAgAg。、、Ag。Ag。。DelaPresa78Auac3。Zhong794。4CuNPs79Fig.4Schematicillustrationofthesynthesisofcoppernanoparticlesinthepresenceofcappingagentsinorganicsolvent79Li80、AgNPsAgNPs。、。X。3.381。Leff81Selvakannan83Aslam84Thomas、TOAB85Py—CH2—NH286Nakao49。Subramaniam822-MA2-PMA52-。PEO—NH2、87。5、AuNPs82Fig.5Schematicillustrationofoxidativepolymerizationofaromaticaminesreductionofauricionsandthepolymerizedaminesencapsulationofgoldnanoparticles82Gandubert88DMAPAuNPs。3.4TOP、PPh3TPPP。、4·587·。Schmid89B2H6M55L12ClxM=RhRuPtAuL=PR3AsR3x=620Ph2Pm-C6H4SO3NaPm-C6H4SO3Na3。Harnack901.5nmTHP-AuNPs。Son9131PNMRTOPTOP。3.56ABFig.6Schematicillustrationofthepreparationofmetalnanoparticlesbymicroemulsion6。Wang61CTAB、TOAB。AOTAgAOTAg、AOTAg9293。Andre94AOT10nm。AOT-2—4nm3637AOTPdPd。Brij92、Brij72、Brij97、Tween80Ag93。。3.6、、。PDADMAC、PVP、block、graft、alternatingrandom。。。95-、、、。3.6.1Liu96AuCl－4PPy。AgNO3PANAgNPs97。γPAMAgNPs98。PAMAg56。。PVA24。PVPEGEGPVP。Sun5999—101PVP·588·22PVP、、。254n