简介:Rhodium-andironphosphate-basedcatalystsarebyfarthemostpromisingcatalystsforoxy-brominationofmethane(OBM)reaction.However,mostliteraturereportedeitherRh-orFePO4-basedcatalysts,andtheresultswererarelystudiedinauniformenvironmentalcondition.Inthisreport,comparativestudywasconductedonsilica-andsiliconcarbide-supportedrhodiumandironphosphatecatalystswiththemainfocusesonstabilityperformanceandcokedeposition.ThecatalyticresultsdemonstratedthatthestabilityofbothRh-andFePO4-basedcatalystswasgreatlyinfluencedbythesupportsused,andsiliconcarbide-supportedcatalystsshowedmuchbetteranti-cokingabilityascomparedwithsilica-supportedones.Temperature-programmedoxidationovertheusedcatalystsfurtherindicatedthatthecokeformationmechanismswerecompletelydifferentbetweensilica-supportedrhodiumandironphosphatecatalysts.WhilecokesmightbecausedbycondensationofCH2Br2oversupportedironphosphate,methanedecompositionmightbethereasonforcokeformationoversilica-supportedrhodiumcatalyst.ThesefindingsmightpavethewayfordesigninghighlyefficientandstablecatalystsoftheOBMreaction.
简介:Twooxo-vanadium(IV)complexes,[VO(C2O4)(2,2′-bipy)(H2O)]·C2H5OH(1)andVO(C2O4)(phen)(H2O)(2),where2,2′-bipy=2,2′-bipyridyl,phen=1,10-phenanthroline,weresynthesizedaspotentialfunctionalmodelsofvanadiumhaloperoxidases(VHPOs)inmixedsolventofethanolandwateratroomtemperature.Thecomplexeswerecharacterizedbyelementalanalysis,infrared(IR),UV-VisandX-raycrystallography.Structuralanalysesshowedthatvanadiumatomwascoordinatedbyaterminaloxygen,oneoxygenatomfromcoordinatedwater,twooxygenatomsfromthecarboxylategroupofoxalicacid,andtwonitrogenatoms(N1andN2)from2,2′-bipy/phen.Centralvanadiumatomsincomplexes1and2werebothinadistorted-octahedralenvironment,andsomeintermolecularhydrogenbondinglinkageswerealsoobservedineachcomplex.BrominationreactionactivityofthetwocomplexeswasevaluatedwithphenolredasorganicsubstrateinthepresenceofH2O2,Br-andphosphatebuffer,indicatingthattheycanbeconsideredasapotentialfunctionalmodelofVHPO.Inaddition,thermalanalysiswasalsoperformedanddiscussedindetail.