硫化钯催化剂的合成及其应用研究进展-徐伟

20133213INDUSTRIALCATALYSISMar．2013Vol．21No．32013－01－102013－02－24NSFC－209761649732011CB7108001985。。[e-mail]*310032:在非均相催化反应中，硫化钯作为催化剂的应用具有重要意义。综述了负载型和非负载型硫化钯的合成方法，重点讨论在气相或液相条件下前驱体、反应温度、反应气氛及载体对合成硫化钯晶相的影响，初步分析硫化钯在催化领域中的应用及未来的发展趋势。:催化剂工程;硫化钯催化剂;非均相催化;晶相doi:10．3969/j．issn．1008-1143．2013．03．001TQ426．6O643．36A1008-1143201303-0001-08ResearchdevelopmentinsynthesisandapplicationofpalladiumsulfidecatalystsXUWeiLIXiaonian*InstituteofIndustrialCatalysisofZhejiangUniversityofTechnologyStateKeyLaboratoryBreedingBaseofGreenChemistrySynthesisTechnologyHangzhou310032ZhejiangChinaAbstractPalladiumsulfideshavebeenattractedmuchattentionduetoitsapplicationinheterogeneouscatalysis．Inthispaperthedifferentmethodsusedforthesynthesisofsupportedorunsupportedpalladiumsulfideswerereviewed．Theeffectsoftheprecursorreactiontemperaturereactionatmosphereandthesupportsontheformationofcrystallinephaseofpalladiumsulfidesinliquidorgas-phasewerediscussed．Theapplicationanddevelopmenttrendsofpalladiumsulfidesincatalysisfieldinthefuturewerealsooutlined．Keywordscatalystengineeringpalladiumsulfidecatalystheterogeneouscatalysiscrystallinephasedoi10．3969/j．issn．1008-1143．2013．03．001CLCnumberTQ426．6O643．36DocumentcodeAArticleID1008-1143201303-0001-08Ni－Mo－SCo－Mo－S1。RuS2、PtSRh2S32－5。6、N－7－910－11。1SPdPd4S、Pd3S、Pd16S7、PdS、PdS2Pd2．8S2。、、220133。11．1。12－13。。TaylorJR14PdS、Pd16S7、Pd3SPd4SPd4S1。11417Table1Gibbsenergyandenthalpyofformationofpalladiumsulfides1417△G0T/kJ·mol－1△fH0m25℃/kJ·mol－1PdS－184400+84．10T－78．1±11．0Pd16S7－182340+105．66T－580．1±36．2Pd3S－172430+83．68T－96．5±10．5Pd4S－145180+88．12T－99．2±11．2MorrealeBD15100μmPd0．1%H2S－10%He－H2350℃、450℃635℃120hPd4SPdPd4S。HensenEJM16Pd－SH2SH2280～360℃H2SH20．008H2SH20．008～0．025Pd4SH2SH20．025～9PdS。ZubkovA17PdS、Pd16S7、Pd3SPd4SPdSPd－S1。PanP18450±20℃168hXRDPdS。FerrerIJ19Pd40±4nm323℃32hPdS。PabloDC20PdPdSPd16S7PdSPd4S1PdPd4SPdPd16S7ΔGPd16S7ΔGPd4S4%Pd16S72Pd4SPd4SPd16S7XRDPd4SPdSSPdS212PdS20。H2SH2S/H216Pd4S18－19PdSPd4S。H2SNa2SPd。DovellFS21H2SH2PdCl4PdS。SchultzM2210mL·min－1Na2PdCl4Na2SPdS。20～30nm2～5nm。SH－OH－。ChenHS23H2PdCl4S2－SO2－4Pd4SPdS。YamamotoT24－25PdOCOCH32H2SPdSPdS。CdSPd。YanHJ26H2PdCl4Na2S201333CdSPdS－CdS。ShemeshY27Pdacac29－CdS200℃CdS－Pd4S。。1．2。/。2。2Table2EffectofreactionconditionsontheformationofPdxSyphases/℃PdS2CNEt22475ArPd4S28PdS2CNMeEt2450ArPd16S7majorPdSminor28PdS2CNMenBu2450ArPd16S728PdS2CNMenBu2475～525ArPd16S7majorPd4Sminor28PdS2CNMenBu2550ArPd28PdS2COCHMe223501．33PaPdS29PdS2CNMeHex2400～5001．33PaPdS30Pdη3－C3H5PdS2CNMeHex3501．33PaPd2．8SmajorPd3SPd4SPd2．2SPd2．5Sminor31PdSC8H172250ArPd16S732－33Pd16S7250SPdS32－33PdSC8H172250H2Pd4S32－33PdSpySPOPrj2PPh3357*PdS234PdSC12H2526298AirPd35PdSC12H2526430ArPdS35PdSC12H2526425AirPd@PdOcore－shell35Pd2μ－SMes2η3－C4H72300～350*Pd16S7Pd2．8S36PdSC12H2526198H2PdS37PdS2CNMeHex2250N2PdS30PdSC12H252∞220ArPdS38Pd2SC12H256192ArPd16S739PdSC12H2526192ArPdⅡthiolatecluster39PdSC12H2526259ArPdS39PdSC12H252150AirPd40Pd2μ－SBut2η3－C4H72157N2Pd4S41Pd2μ－SC6F52η3－C4H72148N2Pd4S41Pd2μ－SPh2η3－C4H72140N2Pd4S41Pd2μ－EMes2η3－C4H72175*Pd4S36*2283541。O’BrienP28PdS2CNMenBu2450℃PdSPd16S7475～525℃Pd16S7Pd4S550℃Pd。Pd—SC—SPd—S。。RadhaB32KulkarniGU33PdSC8H172250℃H2420133Pd4SArPd16S7Pd16S7PdS。283028475～525℃Pd16S730400～500℃PdS。JoseD35Pd@PdOArPdS。。YangZQ39PdSC12H2526PdSPd0．5192℃Pd16S7SPd2259℃PdS。O’BrienP28PdPdS2CNMeEt2PdS2CNMenBu2n＞1。/、。H2S。2H2S。YoshimuraY420．05%H2S/H2Pd－Pt/Al2O3280℃1h300℃H2PdSx－PdPtSx－Pt。YoungDA4350%H2S/H2Pd/SiO2－Al2O3260℃1hH2455℃8h。44455℃O2SO2PdO。MashkinaAV45－4715%H2S/H2ArPd/Al2O3、Pd/TiO2Pd/C250～300℃1hH21hEDXSSPdPdS/Al2O3、PdS/TiO2PdS/CXRD。Vfizquez－ZavalaA4820%H2S/H2250℃、350℃450℃1h250℃HRTEMPdSPdS。20%H2S/H2Pd/SiO2EDXS350℃SPd1．11PdS220PdS2。49250℃350℃Pd/SiO2SPd0．610．71。ShabtaiJ5010%H2S/H2Pd/Al2O3480℃SPd1．3。51－52Al2O3EDXS。YamadaM53－555%H2S/H2Pd－Ca/SiO2Pd－La/SiO2PdMxOyM=MgAlSiCaZrLaCeNdPdS、XRD。PdSQianEW5610%H2S/H2Pd2%～20%Pd/Al2O3250～300℃SPd0．25。ItoK57SimonLJ58PdBPd。PaalZ59H2S/H2PdMoOx/Al2O3400℃PdPd16S7。MoPdPd。MenegazzoF60Pd/CNa2SSPd0．33200℃H23hXRDPd4S/CPd/C。31201335Pd4SPdSPd243261。RadhaB32Pd4SHCl、KMnO4/KOHNH4OH/H2O2。200℃Pd2Pd47Cu53Pd62－63350℃0．1%H2SPd47Cu5364－65。O’BrienCP66Pd4SH2H2Pd47Cu5315%H2S。MillerJB67Pd4SH2368－69。1YoungDA43Pd－Pt/Al2O3PdSx－PtSx0．03%46－。YamadaM70COCu/Zn/AlH2SPd16S7。Pd/SiO2Pd16S710～30582175871Pd/Al2O3250～300℃H2S/H2。MashkinaAV464772Pd/Al2O3H2S/H2300℃3N－73－76。MalzJR74NN－94%100%。ErlenbchMB754－N－13－－N'－93%98%76。4、、PdSPd4SPd3SPd16S7。Pd。。。1PecoraroTAChianelliRR．HydrodesulfurizationcatalysisbytransitionmetalsulfidesJ．JCatal198167430－445．2DeySJainVK．PlatinumgroupmetalchalcogenidesJ．PlatinumMetRev20044816－29．3LacroixMBoutarfaNGuillardCetal．HydrogenatingpropertiesofunsupportedtransitionmetalsulphidesJ．JCatal1989120473－477．4PerlaCVRamírezaJMaugéF．StructurestabilityandactivityofRuS2supportedonaluminaJ．JCatal200826065－74．5Castillo-VillalónPRamírezJCuevasRetal．TPR-Sanaly-sisofthecatalyticbehaviorofRu/Al2O3catalystsinindus-trialconditionsJ．CatalToday2005107－108913－620133919．6BroadbentHLSlaughLHJarviaNL．Rheniumsulfidesasliquid-phasehydrogenationcatalysts．Acomparisonwithmo-lybdenumsulfideandco