MIL-53 (Al) derived single-atom Rh catalyst for the selective hydrogenation of m-chloronitrobenzene into m-chloroaniline

DOI: 10.1016/S1872-2067(20)63697-X

Source and publish data:

Cuihua Xuebao/Chinese Journal of Catalysis p. 824 - 834 (2021)

Update date:2022-08-16

Topics:

Authors:

Cao, Wenxiu

Chen, Shaohua

Chen, Tiehong

Li, Zhi Li, Zhi

Lin, Lu Lin, Lu

Luo, Wenhao

Qi, Haifeng

Song, Weiyu

Tang, Nanfang

Wang, Aiqin

Wang, Weiyin

Zou, Xiaoxuan

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Article abstract of DOI:10.1016/S1872-2067(20)63697-X

The catalytic hydrogenation of halonitroarenes to haloanilines is a green and sustainable process for the production of key nitrogen-containing intermediates in fine chemical industry. Chemoselective hydrogenation poses a significant challenge, which requ

Full text of DOI:10.1016/S1872-2067(20)63697-X

ChineseꢀJournalꢀofꢀCatalysisꢀ42ꢀ(2021)ꢀ824–834

ꢀ

ꢀ ꢀ ꢀ

ꢀ ꢀ ꢀ ꢀ

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

ꢀ

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

ꢀ

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

TiehongꢀChen ,ꢀNanfangꢀTang ,ꢀWeiyuꢀSong ,ꢀAiqinꢀWang ,ꢀWenhaoꢀLuoꢀ *

ꢀ

^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

^g^ꢀStateꢀKeyꢀLaboratoryꢀofꢀCatalysis,ꢀ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

O @Cꢀsingle‐atomꢀcatalystꢀ(SAC)ꢀwasꢀdevelopedꢀforꢀ

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(Al^V)ꢀ

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‐

2 3

–1

2 3

tronicꢀstructureꢀofꢀhydrogenationꢀmetalꢀbyꢀformingꢀSAC,ꢀtogetherꢀwithꢀanꢀenhancedꢀaccessibilityꢀofꢀ

acidꢀfunctionꢀsites.ꢀ

©ꢀ2021,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.

PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.

ꢀ

^†ꢀ

ꢀCorrespondingꢀauthor.ꢀTel:ꢀ+86‐411‐84379738;ꢀFax:ꢀ+86‐411‐84685940;ꢀE‐mail:ꢀw.luo@dicp.ac.cnꢀ

Correspondingꢀauthor.ꢀE‐mail:ꢀzouxiaoxuan@xtu.edu.cnꢀ

Contributedꢀequallyꢀtoꢀthisꢀwork.ꢀ

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 ꢀ ꢀ

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Chinese Journal of Catalysis, 42 (2021) 824-834. doi:10.1016/S1872-2067(20)63697-X

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