ChineseꢀJournalꢀofꢀCatalysisꢀ42ꢀ(2021)ꢀ824–834
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a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
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j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
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Article
MIL‐53ꢀ(Al)ꢀderivedꢀsingle‐atomꢀRhꢀcatalystꢀforꢀtheꢀselectiveꢀ ꢀ
hydrogenationꢀofꢀm‐chloronitrobenzeneꢀintoꢀm‐chloroanilineꢀ
a,b,†
b,†
b,c
ꢀd
ꢀe
ꢀf
a,#
WeiyinꢀWangꢀ ,ꢀLuꢀLinꢀ ,ꢀHaifengꢀQiꢀ ,ꢀWenxiuꢀCao ,ꢀZhiꢀLi ,ꢀShaohuaꢀChen ,ꢀXiaoxuanꢀZouꢀ ,ꢀ
ꢀf
ꢀb
ꢀe
ꢀb,g
b,
TiehongꢀChen ,ꢀNanfangꢀTang ,ꢀWeiyuꢀSong ,ꢀAiqinꢀWang ,ꢀWenhaoꢀLuoꢀ *
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aꢀCollegeꢀofꢀChemistry,ꢀXiangtanꢀUniversity,ꢀXiangtanꢀ411105,ꢀHunan,ꢀChinaꢀ
bꢀCASꢀKeyꢀLaboratoryꢀofꢀScienceꢀandꢀTechnologyꢀonꢀAppliedꢀCatalysis,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences,ꢀDalianꢀ116023,ꢀ
Liaoning,ꢀChinaꢀ
cꢀUniversityꢀofꢀChineseꢀAcademyꢀofꢀSciences,ꢀBeijingꢀ100049,ꢀChinaꢀ
dꢀCollegeꢀofꢀChemistryꢀandꢀChemicalꢀEngineering,ꢀJishouꢀUniversity,ꢀJishouꢀ416000,ꢀHunan,ꢀChinaꢀ
eꢀStateꢀKeyꢀLaboratoryꢀofꢀHeavyꢀOilꢀProcessing,ꢀChinaꢀUniversityꢀofꢀPetroleum,ꢀBeijingꢀ102249,ꢀChinaꢀ
fꢀInstituteꢀofꢀNewꢀCatalyticꢀMaterialsꢀScience,ꢀSchoolꢀofꢀMaterialsꢀScienceꢀandꢀEngineering,ꢀKeyꢀLaboratoryꢀofꢀAdvancedꢀEnergyꢀMaterialsꢀChemistryꢀ
(MOE),ꢀNankaiꢀUniversity,ꢀTianjinꢀ300350,ꢀChinaꢀ
gꢀStateꢀKeyꢀLaboratoryꢀofꢀCatalysis,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences,ꢀDalianꢀ116023,ꢀLiaoning,ꢀChinaꢀ
A R T I C L E ꢀ I N F O ꢀ
A B S T R A C T ꢀ
Articleꢀhistory:ꢀ
Receivedꢀ8ꢀMayꢀ2020ꢀ
Acceptedꢀ7ꢀJulyꢀ2020ꢀ
Theꢀcatalyticꢀhydrogenationꢀofꢀhalonitroarenesꢀtoꢀhaloanilinesꢀisꢀaꢀgreenꢀandꢀsustainableꢀprocessꢀ
forꢀtheꢀproductionꢀofꢀkeyꢀnitrogen‐containingꢀintermediatesꢀinꢀfineꢀchemicalꢀindustry.ꢀChemoselec‐
tiveꢀhydrogenationꢀposesꢀaꢀsignificantꢀchallenge,ꢀwhichꢀrequiresꢀtheꢀrationalꢀdesignꢀofꢀtheꢀcatalystsꢀ
withꢀproperꢀhydrogenationꢀabilityꢀforꢀnitroꢀgroupꢀandꢀsimultaneouslyꢀpreventingꢀdehalogenationꢀofꢀ
Availableꢀonlineꢀ22ꢀSeptemberꢀ2020ꢀ
halogenꢀgroup.ꢀHerein,ꢀaꢀhighlyꢀeffectiveꢀRh@Al
2
O @Cꢀsingle‐atomꢀcatalystꢀ(SAC)ꢀwasꢀdevelopedꢀforꢀ
3
theꢀ hydrogenationꢀ ofꢀ m‐chloronitrobenzeneꢀ (m‐CNB)ꢀ toꢀ m‐chloroanilineꢀ (m‐CAN),ꢀ throughꢀ anꢀ
in‐situꢀgraftingꢀofꢀmetalꢀduringꢀtheꢀassemblyꢀofꢀMIL‐53ꢀ(Al),ꢀfollowedꢀbyꢀconfinedꢀpyrolysis.ꢀExten‐
Keywords:ꢀ
Single‐atomꢀcatalystꢀ
Rhodiumꢀ
Metal‐organicꢀframeworkꢀ
Hydrogenationꢀ
Chemoselectivity
siveꢀcharacterizationsꢀrevealꢀanꢀexquisiteꢀstructureꢀofꢀtheꢀRh@Al
persedꢀRhꢀsitesꢀontoꢀAl
ꢀconfinedꢀbyꢀtheꢀamorphousꢀcarbon.ꢀTheꢀfive‐coordinatedꢀaluminumꢀ(AlV)ꢀ
speciesꢀareꢀessentialꢀforꢀachievingꢀtheꢀatomicꢀdispersionꢀofꢀRhꢀatoms,ꢀprovidingꢀtheꢀunsaturatedꢀ
coordinativeꢀsitesꢀforꢀmetal.ꢀComparedꢀtoꢀtheꢀbenchmarkꢀRh/γ‐Al ꢀandꢀRh/Cꢀnanocatalysts,ꢀtheꢀ
Rh@Al @CꢀSACꢀaffordsꢀanꢀexcellentꢀturnoverꢀfrequencyꢀofꢀ2317ꢀmolm‐CNB·molRh ·h ,ꢀtheꢀhighestꢀ
valueꢀtoꢀdateꢀinꢀheterogeneousꢀcatalystꢀsystemsꢀforꢀtheꢀhydrogenationꢀofꢀm‐CNBꢀatꢀ313ꢀKꢀandꢀ20ꢀ
barꢀH ,ꢀtogetherꢀwithꢀaꢀsustainedꢀselectivityꢀtoꢀm‐CANꢀ(~98%)ꢀduringꢀfiveꢀconsecutiveꢀruns.ꢀTheꢀ
superiorꢀcatalyticꢀperformanceꢀofꢀtheꢀRh@Al @Cꢀisꢀattributedꢀtoꢀaꢀproperꢀmodulationꢀofꢀelec‐
2 3
O @C,ꢀcontainingꢀatomicallyꢀdis‐
O
2 3
O
2 3
–1
–1
O
2 3
2
O
2 3
tronicꢀstructureꢀofꢀhydrogenationꢀmetalꢀbyꢀformingꢀSAC,ꢀtogetherꢀwithꢀanꢀenhancedꢀaccessibilityꢀofꢀ
acidꢀfunctionꢀsites.ꢀ
©ꢀ2021,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.
PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.
*
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†ꢀ
ꢀCorrespondingꢀauthor.ꢀTel:ꢀ+86‐411‐84379738;ꢀFax:ꢀ+86‐411‐84685940;ꢀE‐mail:ꢀw.luo@dicp.ac.cnꢀ
Correspondingꢀauthor.ꢀE‐mail:ꢀzouxiaoxuan@xtu.edu.cnꢀ
Contributedꢀequallyꢀtoꢀthisꢀwork.ꢀ
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ThisꢀworkꢀwasꢀsupportedꢀbyꢀtheꢀStrategicꢀPriorityꢀResearchꢀProgramꢀofꢀtheꢀChineseꢀAcademyꢀofꢀSciencesꢀ(XDB17020100),ꢀtheꢀNationalꢀNaturalꢀSci‐
enceꢀFoundationꢀofꢀChinaꢀ(21703238,ꢀ21690084,ꢀ21802134),ꢀEducationalꢀCommissionꢀofꢀHunanꢀProvinceꢀ(19B463),ꢀCollaborativeꢀInnovationꢀCenterꢀ
ofꢀManganese‐Zinc‐VanadiumꢀIndustrialꢀTechnologyꢀ(MXF202001),ꢀandꢀResearchꢀStartupꢀFoundationꢀofꢀJishouꢀUniversityꢀ(No.21).ꢀ
DOI:ꢀ10.1016/S1872‐2067(20)63697‐Xꢀ|ꢀhttp://www.sciencedirect.com/science/journal/18722067ꢀ|ꢀChin.ꢀJ.ꢀCatal.,ꢀVol.ꢀ42,ꢀNo.ꢀ5,ꢀMayꢀ2021ꢀ ꢀ ꢀ