Modifying the acidity of H-MOR and its catalytic carbonylation of dimethyl ether

Article abstract of DOI:10.1016/S1872-2067(16)62484-1

Among the reactions catalyzed by zeolites there are some that exhibit high selectivity due to the spatial confinement effect of the zeolite framework. Tailoring the acidity, particularly the distribution and location of the Br?nsted acid sites in the zeolite is effective for making it a better catalyst for these reactions. We prepared a series of H-mordenite (H-MOR) samples by varying the composition of the sol-gel, using different structure directing agents and post-treatment. NH₃-TPD and IR characterization of adsorbed pyridine were employed to determine the amount of Br?nsted acid sites in the 8-membered ring and 12-membered ring channels. It was shown that controlled synthesis was a promising approach to improve the concentration of Br?nsted acid sites in MOR, even with a low Al content. Using an appropriate composition of Si and Al in the sol-gel favored a higher proportion of Br?nsted acid sites in the 8-membered ring channels. HMI as a structure-direct agent gave an obvious enrichment of Br?nsted acid sites in the 8-membered ring. Carbonylation of dimethyl ether was used as a probe reaction to examine the modification of the acid properties, especially the Br?nsted acid sites in the 8-membered ring channels. There was a linear relationship between methyl acetate formation and the number of Br?nsted acid sites in the 8-membered ring channels, demonstrating the successful modification of acid properties. Our results provide information for the rational design and modification of zeolites with spatial constraints.

Full text of DOI:10.1016/S1872-2067(16)62484-1

ChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1530–1537
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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
ModifyingꢀtheꢀacidityꢀofꢀH‐MORꢀandꢀitsꢀcatalyticꢀcarbonylationꢀofꢀ
dimethylꢀetherꢀ
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MeixiaꢀWang, ShouyingꢀHuang*,ꢀJingLü,ꢀZaizheꢀCheng,ꢀYingLi, ShengpingꢀWang,ꢀXinbinꢀMa
ꢀ
KeyꢀLaboratoryꢀforꢀGreenꢀChemicalꢀTechnologyꢀofꢀMinistryꢀofꢀEducation,ꢀSchoolꢀofꢀChemicalꢀEngineeringꢀandꢀTechnology,ꢀTianjinꢀUniversity;ꢀ ꢀ
CollaborativeꢀInnovationꢀCenterꢀofꢀChemicalꢀScienceꢀandꢀEngineeringꢀ(Tianjin),ꢀTianjinꢀ300072,ꢀChinaꢀ
A R T I C L E ꢀ I N F O ꢀ
A B S T R A C T ꢀ
Articleꢀhistory:ꢀ
Amongꢀtheꢀreactionsꢀcatalyzedꢀbyꢀzeolitesꢀthereꢀareꢀsomeꢀthatꢀexhibitꢀhighꢀselectivityꢀdueꢀtoꢀtheꢀ
spatialꢀconfinementꢀeffectꢀofꢀtheꢀzeoliteꢀframework.ꢀTailoringꢀtheꢀacidity,ꢀparticularlyꢀtheꢀdistribu‐
tionꢀandꢀlocationꢀofꢀtheꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀzeoliteꢀisꢀeffectiveꢀforꢀmakingꢀitꢀaꢀbetterꢀcatalystꢀ
forꢀtheseꢀreactions.ꢀWeꢀpreparedꢀaꢀseriesꢀofꢀH‐mordeniteꢀ(H‐MOR)ꢀsamplesꢀbyꢀvaryingꢀtheꢀcomposi‐
Receivedꢀ13ꢀAprilꢀ2016ꢀ
Acceptedꢀ30ꢀMayꢀ2016ꢀ
Publishedꢀ5ꢀSeptemberꢀ2016ꢀ
tionꢀofꢀtheꢀsol‐gel,ꢀusingꢀdifferentꢀstructureꢀdirectingꢀagentsꢀandꢀpost‐treatment.ꢀNH ‐TPDꢀandꢀIRꢀ
3
characterizationꢀofꢀadsorbedꢀpyridineꢀwereꢀemployedꢀtoꢀdetermineꢀtheꢀamountꢀofꢀBrönstedꢀacidꢀ
sitesꢀinꢀtheꢀ8‐memberedꢀringꢀandꢀ12‐memberedꢀringꢀchannels.ꢀItꢀwasꢀshownꢀthatꢀcontrolledꢀsynthe‐
sisꢀwasꢀaꢀpromisingꢀapproachꢀtoꢀimproveꢀtheꢀconcentrationꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀMOR,ꢀevenꢀwithꢀ
aꢀlowꢀAlꢀcontent.ꢀUsingꢀanꢀappropriateꢀcompositionꢀofꢀSiꢀandꢀAlꢀinꢀtheꢀsol‐gelꢀfavoredꢀaꢀhigherꢀpro‐
portionꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀ8‐memberedꢀringꢀchannels.ꢀHMIꢀasꢀaꢀstructure‐directꢀagentꢀ
gaveꢀanꢀobviousꢀenrichmentꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀ8‐memberedꢀring.ꢀCarbonylationꢀofꢀdime‐
thylꢀetherꢀwasꢀusedꢀasꢀaꢀprobeꢀreactionꢀtoꢀexamineꢀtheꢀmodificationꢀofꢀtheꢀacidꢀproperties,ꢀespecial‐
lyꢀtheꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀ8‐memberedꢀringꢀchannels.ꢀThereꢀwasꢀaꢀlinearꢀrelationshipꢀbetweenꢀ
methylꢀacetateꢀformationꢀandꢀtheꢀnumberꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀ8‐memberedꢀringꢀchannels,ꢀ
demonstratingꢀtheꢀsuccessfulꢀmodificationꢀofꢀacidꢀproperties.ꢀOurꢀresultsꢀprovideꢀinformationꢀforꢀ
theꢀrationalꢀdesignꢀandꢀmodificationꢀofꢀzeolitesꢀwithꢀspatialꢀconstraints.ꢀ
Keywords:ꢀ
Zeoliteꢀ
H‐mordeniteꢀ
Modificationꢀofꢀacidityꢀ
Hydrothermalꢀsynthesisꢀ
Structure‐directꢀagentꢀ
Postꢀtreatmentꢀ
Carbonylationꢀofꢀdimethylꢀetherꢀ
©ꢀ2016,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.
PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.
1
.ꢀ ꢀ Introductionꢀ
acceptedꢀ thatꢀ theꢀ strengthꢀ andꢀ amountꢀ ofꢀ acidꢀ sitesꢀ areꢀ keyꢀ
parametersꢀthatꢀinfluenceꢀtheꢀcatalyticꢀperformanceꢀforꢀmanyꢀ
reactions.ꢀOnꢀtheꢀotherꢀhand,ꢀtheꢀporeꢀstructureꢀplaysꢀanꢀim‐
portantꢀroleꢀnotꢀonlyꢀinꢀdiffusionꢀlimitationꢀbutꢀalsoꢀinꢀtheꢀreac‐
tionꢀmechanism.ꢀInꢀaddition,ꢀtheꢀsitingꢀandꢀdistributionꢀofꢀtheꢀ
frameworkꢀAlꢀatomsꢀwithꢀtheꢀconcurrentꢀchangesꢀinꢀtheꢀdistri‐
butionꢀofꢀBrönstedꢀacidꢀsitesꢀhaveꢀbeenꢀrecognizedꢀtoꢀinfluenceꢀ
theꢀ catalyticꢀ activityꢀ andꢀ selectivity.ꢀ Becauseꢀ itꢀ offersꢀ varyingꢀ
stericꢀaccessꢀtoꢀreactantꢀmolecules,ꢀspatialꢀconstraintsꢀforꢀtheꢀ
Zeolitesꢀhaveꢀbeenꢀextensivelyꢀappliedꢀasꢀsolidꢀacidꢀcatalystsꢀ
inꢀaꢀvarietyꢀofꢀpetrochemicalꢀprocessesꢀandꢀchemicalꢀsynthesisꢀ
dueꢀ toꢀ theirꢀ uniqueꢀ acidityꢀ andꢀ well‐definedꢀ microporousꢀ
frameworkꢀ[1,2].ꢀInꢀaluminosilicateꢀzeolites,ꢀtheꢀBrönstedꢀacidꢀ
sitesꢀwhichꢀfunctionꢀasꢀactiveꢀcentersꢀareꢀtheꢀprotonsꢀthatꢀbal‐
anceꢀtheꢀnegativeꢀchargeꢀofꢀtheꢀtetrahedrallyꢀcoordinatedꢀalu‐
minumꢀ(Al)ꢀatomsꢀinꢀtheꢀframeworkꢀ[3].ꢀItꢀhasꢀbeenꢀgenerallyꢀ
*
ꢀ
ꢀCorrespondingꢀauthor.ꢀTel:ꢀ+86‐22‐27409880;ꢀFax:ꢀ+86‐22‐87401818;ꢀE‐mail:ꢀhuangsy@tju.edu.cnꢀ ꢀ
Correspondingꢀauthor.ꢀTel:ꢀ+86‐22‐27409880;ꢀFax:ꢀ+86‐22‐87401818;ꢀE‐mail:ꢀxbma@tju.edu.cnꢀ ꢀ
#
ThisꢀworkꢀwasꢀsupportedꢀbyꢀtheꢀNationalꢀNaturalꢀScienceꢀFoundationꢀofꢀChinaꢀ(21325626,ꢀ21406120)ꢀandꢀtheꢀPostdoctoralꢀScienceꢀFoundationꢀofꢀ
Chinaꢀ(2014M560181,ꢀ2015T80214).ꢀ
DOI:ꢀ10.1016/S1872‐2067(16)62484‐1ꢀ|ꢀhttp://www.sciencedirect.com/science/journal/18722067ꢀ|ꢀChin.ꢀJ.ꢀCatal.,ꢀVol.ꢀ37,ꢀNo.ꢀ9,ꢀSeptemberꢀ2016ꢀ ꢀ

ꢀ
MeixiaꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1530–1537ꢀ
1531ꢀ
reactionꢀ intermediatesꢀ orꢀ transitionꢀ statesꢀ asꢀ wellꢀ asꢀ subtleꢀ
differencesꢀinꢀacidꢀstrengthꢀareꢀdueꢀtoꢀtheꢀbondꢀanglesꢀofꢀtheꢀ
tetrahedralꢀ[4].ꢀToꢀdate,ꢀmanyꢀworksꢀhaveꢀ exploredꢀtheꢀrela‐
tionshipꢀbetweenꢀtheꢀcatalyticꢀpropertiesꢀandꢀAlꢀdistributionꢀinꢀ
zeolites.ꢀForꢀexample,ꢀBellꢀandꢀhisꢀcoworkersꢀ[5]ꢀcontrolledꢀtheꢀ
fractionꢀ ofꢀ Alꢀ inꢀ theꢀ intersectionsꢀ ofꢀ H‐MFIꢀ byꢀ varyingꢀ theꢀ Alꢀ
contentꢀ ofꢀ theꢀ zeoliteꢀ frameworkꢀ andꢀ foundꢀ thatꢀ terminalꢀ
crackingꢀandꢀdehydrogenationꢀofꢀn‐butaneꢀhappenedꢀpreferen‐
tiallyꢀ onꢀ theꢀ Brönstedꢀ acidꢀ sitesꢀ locatedꢀ atꢀ channelꢀ intersec‐
tions.ꢀDavis’sꢀgroupꢀ[6]ꢀdemonstratedꢀthatꢀtheꢀlocationꢀofꢀacidꢀ
sitesꢀcanꢀbeꢀtailoredꢀbyꢀusingꢀdifferentlyꢀsizedꢀcyclicꢀaminesꢀasꢀ
theꢀstructureꢀdirectingꢀagentꢀ(SDA),ꢀwhichꢀinfluencedꢀtheꢀper‐
formanceꢀofꢀcarbonylationꢀofꢀdimethylꢀetherꢀ(DME).ꢀPinarꢀetꢀal.ꢀ
samples.ꢀDueꢀtoꢀtheꢀincreasedꢀnumberꢀofꢀBrönstedꢀacidꢀsites,ꢀ
theꢀcarbonylationꢀofꢀDMEꢀwasꢀfacilitated.ꢀTheꢀrelationshipꢀbe‐
tweenꢀtheꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀ8‐MRꢀchannelꢀofꢀH‐MORꢀ
andꢀ theꢀ MAꢀ formationꢀ rateꢀ revealedꢀ thatꢀ weꢀ achievedꢀ aꢀ con‐
trollableꢀmodificationꢀofꢀtheꢀacidꢀpropertiesꢀinꢀMOR.ꢀ
2.ꢀ ꢀ Experimentalꢀ
2.1.ꢀ ꢀ PreparationꢀofꢀMORꢀzeoliteꢀ
2.1.1.ꢀ ꢀ Hydrothermalꢀsynthesisꢀ
MORꢀzeoliteꢀwithꢀdifferentꢀSi/Alꢀratiosꢀwasꢀpreparedꢀbyꢀhy‐
drothermalꢀ synthesis.ꢀ First,ꢀ sodiumꢀ hydroxide,ꢀ silicaꢀ solꢀ (30ꢀ
[7]ꢀdiscoveredꢀthatꢀtheꢀaccessibilityꢀofꢀtheꢀacidꢀsitesꢀdeterminedꢀ
wt%ꢀSiO
2
,ꢀ70ꢀwt%ꢀH O)ꢀandꢀsodiumꢀaluminateꢀwereꢀmixedꢀandꢀ
2
byꢀtheꢀAlꢀpositionꢀhadꢀaꢀgoodꢀcorrelationꢀwithꢀtheꢀcatalyticꢀre‐
sultsꢀofꢀm‐xyleneꢀandꢀ1‐buteneꢀisomerisation.ꢀThereꢀareꢀseveralꢀ
strategiesꢀtoꢀmodifyꢀtheꢀdistributionꢀandꢀlocalꢀenvironmentꢀofꢀ
theꢀAlꢀatoms:ꢀchoosingꢀanꢀappropriateꢀSDAꢀandꢀsynthesisꢀcon‐
ditions,ꢀ controllingꢀ theꢀ compositionꢀ ofꢀ theꢀ reactionꢀ mixtures,ꢀ
andꢀ adoptingꢀ post‐treatmentꢀ (includingꢀ acidicꢀ orꢀ alkalineꢀ
leaching,ꢀ otherꢀ chemicalꢀ treatment,ꢀ steamꢀ orꢀ thermalꢀ treat‐
ment,ꢀetc.)ꢀ[8].ꢀ
TheꢀcarbonylationꢀofꢀDMEꢀtoꢀmethylꢀacetateꢀ(MA)ꢀoverꢀzeo‐
litesꢀisꢀaꢀtypicalꢀspatiallyꢀconfinedꢀreaction.ꢀIglesiaꢀandꢀhisꢀcol‐
leaguesꢀ[9]ꢀcomparedꢀdifferentꢀtypesꢀofꢀzeolitesꢀ(e.g.ꢀFER,ꢀMOR,ꢀ
ZSM‐5,ꢀUSY)ꢀandꢀfoundꢀthatꢀH‐MORꢀexhibitedꢀexcellentꢀselec‐
tivityꢀ(>99%)ꢀtoꢀMA.ꢀTheꢀreactionꢀproceededꢀasꢀfollows:ꢀDMEꢀ
stirredꢀatꢀambientꢀtemperatureꢀforꢀ4ꢀh.ꢀThen,ꢀcommercialꢀMORꢀ
(YangzhouꢀZhongheꢀPetroleumꢀChemicalsꢀInstituteꢀCo.,ꢀLtd.)ꢀasꢀ
seedꢀ (1ꢀ wt%ꢀ relativeꢀ toꢀ SiO )ꢀ andꢀ tetraethylammoniumꢀ hy‐
2
droxideꢀsolutionꢀ(TEAOH,ꢀ25ꢀwt%,ꢀGuangfuꢀFineꢀChemicalꢀCo.,ꢀ
Ltd.)ꢀasꢀSDAꢀwereꢀaddedꢀtoꢀtheꢀSi‐Al‐Naꢀmixtureꢀandꢀstirredꢀforꢀ
1ꢀ h.ꢀ Theꢀ reactionꢀ gelꢀ hadꢀ theꢀ followingꢀ molarꢀ composition:ꢀ
1.0SiO
2
:xNaAlO :0.2NaOH:0.23TEAOHꢀ (xꢀ =ꢀ 0.1,ꢀ 0.083,ꢀ 0.067,ꢀ
2
0.056,ꢀcorrespondingꢀtoꢀSi/Alꢀratioꢀ=ꢀ10,ꢀ12,ꢀ15,ꢀ18).ꢀTheꢀmix‐
tureꢀwasꢀtransferredꢀintoꢀaꢀTeflon‐linedꢀ100ꢀmLꢀautoclaveꢀandꢀ
heatedꢀatꢀ443ꢀKꢀforꢀ3ꢀdꢀunderꢀstaticꢀconditionꢀandꢀautogenousꢀ
pressure.ꢀAfterꢀtheꢀautoclaveꢀwasꢀcooledꢀdown,ꢀtheꢀsolidꢀwasꢀ
recoveredꢀ byꢀ filtrationꢀ andꢀ washedꢀ withꢀ distilledꢀ waterꢀ andꢀ
driedꢀinꢀanꢀovenꢀatꢀ373ꢀKꢀforꢀ12ꢀh.ꢀTheꢀsolidꢀwasꢀcalcinedꢀatꢀ823ꢀ
Kꢀ forꢀ 5ꢀ hꢀ withꢀ aꢀ heatingꢀ rateꢀ ofꢀ 1ꢀ K/minꢀ toꢀ removeꢀ organicꢀ
compounds.ꢀInꢀorderꢀtoꢀgetꢀH‐MOR,ꢀtheꢀcalcinedꢀNa‐MORꢀzeo‐
reactedꢀwithꢀBrönstedꢀacidꢀsitesꢀtoꢀformꢀ–CH
3
,ꢀacetylꢀformationꢀ
byꢀCOꢀinsertionꢀintoꢀ–CH ,ꢀthen,ꢀtheꢀacetylꢀreactedꢀwithꢀanotherꢀ
3
DMEꢀmoleculeꢀtoꢀproduceꢀMA.ꢀAꢀfurtherꢀstudyꢀrevealedꢀthatꢀtheꢀ
stabilizationꢀofꢀtheꢀcarbocationicꢀtransitionꢀstatesꢀ(producedꢀbyꢀ
liteꢀwasꢀdispersedꢀinꢀNH
4
NO ꢀaqueousꢀsolutionꢀ(0.2ꢀmol/L,ꢀ1ꢀgꢀ
3
sampleꢀinꢀ50ꢀmLꢀsolution)ꢀatꢀ353ꢀKꢀforꢀ6ꢀh,ꢀfollowedꢀbyꢀfilteringꢀ
andꢀwashing.ꢀAfterꢀrepeatingꢀtheꢀionꢀexchangeꢀonce,ꢀtheꢀresult‐
ingꢀsolidꢀwasꢀdriedꢀatꢀ373ꢀKꢀovernightꢀandꢀthenꢀcalcinedꢀatꢀ773ꢀ
Kꢀforꢀ4ꢀhꢀwithꢀaꢀheatingꢀrateꢀofꢀ2ꢀK/min.ꢀWhenꢀxꢀ=ꢀ0.083ꢀinꢀtheꢀ
composition,ꢀ theꢀ Na‐MORꢀ wasꢀ labeledꢀ asꢀ NaM.ꢀ Theꢀ H‐MORꢀ
samplesꢀ wereꢀ labeledꢀ asꢀ HM1,ꢀ HM2,ꢀ HM3ꢀ andꢀ HM4ꢀ withꢀ de‐
creasingꢀxꢀvalues.ꢀ
3
COꢀ insertionꢀ intoꢀ –CH )ꢀ resultedꢀ inꢀ theꢀ specificityꢀ ofꢀ theꢀ
8‐memberedꢀringꢀ(8‐MR)ꢀchannelsꢀinꢀH‐MORꢀ[10].ꢀAnꢀinvesti‐
gationꢀ byꢀ quantumꢀ chemicalꢀ methodsꢀ suggestedꢀ thatꢀ theꢀ
T3–O33ꢀpositionꢀwasꢀselectiveꢀnotꢀonlyꢀdueꢀtoꢀtheꢀchannelꢀsizeꢀ
butꢀ alsoꢀ theꢀ unusualꢀ orientationꢀ ofꢀ –OCH3ꢀ[11].ꢀ Shen’sꢀ groupꢀ
[12]ꢀ discoveredꢀ thatꢀ H‐ZSM‐35ꢀ withꢀ aꢀ 10‐MRꢀ channelꢀ inter‐
sectedꢀperpendicularlyꢀbyꢀanꢀ8‐MRꢀchannelꢀshowedꢀaꢀsimilarlyꢀ
highꢀinitialꢀselectivityꢀtoꢀMAꢀandꢀmuchꢀbetterꢀstability.ꢀRecently,ꢀ
carbonylationꢀofꢀDMEꢀhasꢀattractedꢀmuchꢀattentionꢀforꢀitsꢀatomꢀ
economy,ꢀ mildꢀ reactionꢀ conditionsꢀ andꢀ inexpensiveꢀ catalysts.ꢀ
Moreꢀimportant,ꢀitꢀisꢀanꢀimportantꢀstepꢀinꢀtheꢀdirectꢀrouteꢀofꢀ
ethanolꢀproductionꢀfromꢀsyngasꢀ[13].ꢀTherefore,ꢀregulatingꢀtheꢀ
distributionꢀofꢀtheꢀAlꢀatomsꢀinꢀaꢀzeoliticꢀframeworkꢀandꢀeluci‐
datingꢀitsꢀimpactꢀonꢀtheꢀcatalyticꢀactivityꢀwouldꢀhelpꢀtoꢀunder‐
standꢀtheꢀstructure‐functionꢀmechanismꢀofꢀzeolitesꢀandꢀfacili‐
tateꢀethanolꢀproductionꢀandꢀsyngasꢀutilization.ꢀ
Inꢀpreviouslyꢀpublishedꢀworks,ꢀchemicalꢀdealuminationꢀandꢀ
cation‐exchangeꢀ wereꢀ employedꢀ toꢀ exploreꢀ theꢀ confinementꢀ
effectꢀofꢀMORꢀforꢀDMEꢀcarbonylation.ꢀBothꢀofꢀtheseꢀwereꢀbasedꢀ
onꢀtheꢀreductionꢀofꢀBrönstedꢀacidꢀsitesꢀ[14,15].ꢀHere,ꢀweꢀregu‐
latedꢀ theꢀ distributionꢀ ofꢀ Alꢀ atomsꢀ inꢀ theꢀ MORꢀ frameworkꢀ inꢀ
bothꢀpositiveꢀandꢀnegativeꢀways,ꢀsuchꢀasꢀcontrollingꢀtheꢀcom‐
positionꢀofꢀtheꢀsol‐gel,ꢀusingꢀdifferentꢀSDAsꢀandꢀusingꢀanꢀacidicꢀ
post‐treatment.ꢀ Ammoniaꢀ temperature‐programmedꢀ desorp‐
Whenꢀusingꢀhexamethyleneimineꢀ (HMIꢀ 99ꢀ wt%,ꢀ Sigma‐Al‐
drichꢀCo.ꢀLLC.)ꢀasꢀtheꢀSDA,ꢀtheꢀsynthesisꢀprocedureꢀwasꢀalmostꢀ
theꢀsame.ꢀExtraꢀdistilledꢀwaterꢀwasꢀneededꢀtoꢀdiluteꢀHMI.ꢀTheꢀ
ꢀ
molarꢀ ratioꢀ ofꢀ H
usingꢀTEAOHꢀasꢀtemplate.ꢀTheꢀcompositionꢀofꢀtheꢀfinalꢀmixtureꢀ
wasꢀ 1.0SiO :0.083NaAlO :0.2NaOH:0.35HMIꢀ [16].ꢀ Theꢀ H‐MORꢀ
2 2
O/SiO ꢀ wasꢀ 13.3ꢀ inꢀ accordanceꢀ withꢀ theꢀ gelꢀ
2
2
obtainedꢀwasꢀmarkedꢀasꢀHM5.ꢀ
2.1.2.ꢀ ꢀ Post‐treatmentꢀbyꢀacidꢀ
TheꢀcommercialꢀH‐MORꢀ(labeledꢀasꢀHM)ꢀwasꢀusedꢀasꢀaꢀpar‐
entꢀsample.ꢀAcidꢀtreatmentꢀwasꢀappliedꢀtoꢀregulateꢀtheꢀcontentꢀ
andꢀ distributionꢀ ofꢀ theꢀ Alꢀ atomsꢀ inꢀ HM.ꢀ Post‐treatmentꢀ withꢀ
citricꢀacidꢀwasꢀcarriedꢀoutꢀatꢀ353ꢀKꢀunderꢀrefluxingꢀforꢀ24ꢀhꢀ(1ꢀgꢀ
zeoliteꢀinꢀ20ꢀmLꢀsolution).ꢀTheꢀsampleꢀwasꢀthenꢀfilteredꢀoffꢀandꢀ
washedꢀwithꢀdistilledꢀwaterꢀuntilꢀtheꢀpHꢀ=ꢀ7ꢀandꢀcalcinedꢀatꢀ823ꢀ
Kꢀforꢀ4ꢀh.ꢀTheꢀsamplesꢀtreatedꢀwithꢀcitricꢀacidꢀwereꢀlabeledꢀasꢀ
C1ꢀandꢀC2ꢀforꢀtheꢀconcentrationꢀofꢀtheꢀsolutionꢀwithꢀ0.2ꢀandꢀ0.5ꢀ
mol/L,ꢀ respectively.ꢀ Theꢀ parentꢀ sampleꢀ wasꢀ treatedꢀ withꢀ
phosphoricꢀacidꢀasꢀfollows:ꢀincipientꢀimpregnationꢀwithꢀphos‐
phoricꢀacidꢀ(0.15ꢀmol/L)ꢀatꢀroomꢀtemperatureꢀovernight,ꢀthenꢀ
tionꢀ(NH
3
‐TPD)ꢀandꢀinꢀsituꢀFourierꢀtransformꢀinfraredꢀ(FTIR)ꢀ
wereꢀappliedꢀtoꢀcharacterizeꢀtheꢀacidꢀpropertiesꢀofꢀtheꢀH‐MORꢀ

1532ꢀ
MeixiaꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1530–1537ꢀ
dryingꢀtheꢀsolidꢀproductꢀatꢀ373ꢀKꢀandꢀcalciningꢀatꢀ823ꢀKꢀforꢀ4ꢀh.ꢀ
TheꢀresultingꢀsampleꢀwasꢀlabeledꢀasꢀP.ꢀ
2.3.ꢀ ꢀ Catalyticꢀperformanceꢀ
CarbonylationꢀofꢀDMEꢀtoꢀMAꢀwasꢀevaluatedꢀinꢀaꢀfixed‐bedꢀ
stainlessꢀsteelꢀreactorꢀatꢀ1.5ꢀMPa.ꢀInꢀaꢀtypicalꢀrun,ꢀ1ꢀmLꢀofꢀcata‐
lystꢀ(0.5ꢀg,ꢀ40–60ꢀmesh)ꢀwasꢀplacedꢀinꢀtheꢀreactor.ꢀPriorꢀtoꢀtheꢀ
2.2.ꢀ ꢀ Characterizationꢀ
X‐rayꢀdiffractionꢀ(XRD)ꢀpatternsꢀofꢀtheꢀzeoliteꢀsamplesꢀwereꢀ
reaction,ꢀ theꢀ catalystꢀ wasꢀ pre‐treatedꢀ inꢀ N ꢀ atmosphereꢀ
2
recordedꢀ byꢀ aꢀ Rigakuꢀ D/max‐2500ꢀ diffractometerꢀ withꢀ Cuꢀ K
radiationꢀ(λꢀ=ꢀ0.154056ꢀnm,ꢀ40ꢀkVꢀandꢀ200ꢀmA)ꢀinꢀtheꢀ2θꢀrangeꢀ
ofꢀ3˚–50˚.ꢀ
ElementalꢀanalysisꢀofꢀNa,ꢀAl,ꢀandꢀSiꢀinꢀtheꢀsamplesꢀwasꢀper‐
formedꢀ onꢀ anꢀ ICP‐OESꢀ (VISTA‐MPX,ꢀ Varian).ꢀ Theꢀ sampleꢀ (20ꢀ
mg)ꢀwasꢀdigestedꢀinꢀHFꢀaqueousꢀsolution,ꢀfollowedꢀbyꢀtheꢀaddi‐
α
ꢀ
(99.99%,ꢀTianjinꢀSixonꢀGasꢀCo.,ꢀLtd)ꢀatꢀ473ꢀKꢀforꢀ9ꢀh.ꢀTheꢀreac‐
tantꢀmixtureꢀ(DME/COꢀ=ꢀ1/49,ꢀmol/mol)ꢀwasꢀintroducedꢀintoꢀ
theꢀreactorꢀatꢀaꢀtotalꢀflowꢀrateꢀofꢀ100ꢀmL/min.ꢀTheꢀproductꢀgasꢀ
wasꢀanalyzedꢀbyꢀanꢀonlineꢀgasꢀchromatographꢀ(Agilentꢀ7890Bꢀ
GC)ꢀ whichꢀ wasꢀ equippedꢀ withꢀ bothꢀ flameꢀ ionizationꢀ detectorꢀ
(FID)ꢀandꢀTCD.ꢀTheꢀselectivityꢀandꢀspaceꢀtimeꢀyieldꢀ(STY)ꢀofꢀMAꢀ
wereꢀcalculatedꢀbyꢀEqs.ꢀ(1)ꢀandꢀ(2),ꢀrespectively.ꢀ ꢀ
tionꢀofꢀexcessꢀboricꢀacidꢀ(H
3
BO )ꢀtoꢀformꢀaꢀcomplexꢀwithꢀHF.ꢀ
3
AꢀMicromeriticsꢀASAP‐2020ꢀanalyzerꢀwasꢀemployedꢀtoꢀgetꢀ
detailedꢀ informationꢀ aboutꢀ theꢀ poreꢀ distributionꢀ andꢀ specificꢀ
surfaceꢀ areaꢀ ofꢀ theꢀ samples.ꢀ Nitrogenꢀ adsorptionꢀ wasꢀ carriedꢀ
outꢀatꢀ77ꢀK.ꢀPriorꢀtoꢀtheꢀanalysis,ꢀtheꢀsampleꢀwasꢀdegassedꢀatꢀ
S
MAꢀ=ꢀMAꢀ/ꢀ(CH
3
OH/2ꢀ+ꢀMAꢀ+ꢀCH
3
COOH)ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ (1)ꢀ
STYMAꢀ=ꢀXDMEꢀꢀSMAꢀꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ (2)ꢀ ꢀ
Dueꢀ toꢀ cokeꢀ formation,ꢀ theꢀ conversionꢀ ofꢀ DMEꢀ onꢀ allꢀ theꢀ
H‐MORꢀsamplesꢀdecreasedꢀgraduallyꢀandꢀrapidlyꢀwithꢀtimeꢀonꢀ
stream.ꢀ Therefore,ꢀ theꢀ initialꢀ catalyticꢀ performanceꢀ (reactionꢀ
timeꢀ1.5ꢀh)ꢀwasꢀdiscussedꢀinꢀthisꢀwork.ꢀ
4
73ꢀKꢀforꢀ24ꢀh.ꢀTheꢀporeꢀvolumeꢀwasꢀcalculatedꢀbyꢀtheꢀHorvath‐
ꢀ
Kawazoeꢀ equation.ꢀ Theꢀ surfaceꢀ areaꢀ wasꢀ obtainedꢀ byꢀ theꢀ
Brunauer‐Emmett‐Tellerꢀ (BET)ꢀ method.ꢀ Theꢀ microporeꢀ vol‐
umeꢀ andꢀ theꢀ externalꢀ surfaceꢀ areaꢀ wereꢀ obtainedꢀ fromꢀ theꢀ
t‐plotꢀmethod.ꢀ
3.ꢀ ꢀ Resultsꢀandꢀdiscussionꢀ ꢀ
3
NH ‐TPDꢀ wasꢀ performedꢀ onꢀ aꢀ Micromeriticsꢀ Autochemꢀ IIꢀ
3.1.ꢀ ꢀ Compositionꢀanalysisꢀandꢀtexturalꢀpropertiesꢀ
2920ꢀinstrumentꢀequippedꢀwithꢀaꢀthermalꢀconductivityꢀdetec‐
torꢀ(TCD).ꢀTheꢀ40–60ꢀmeshꢀcatalystꢀ(10ꢀmg)ꢀwasꢀplacedꢀinꢀaꢀ
quartzꢀtube.ꢀInꢀeachꢀexperiment,ꢀtheꢀsampleꢀwasꢀpre‐treatedꢀatꢀ
ICP‐OESꢀwasꢀappliedꢀforꢀelementꢀanalysis.ꢀTheꢀmolarꢀratiosꢀ
ofꢀsiliconꢀandꢀaluminumꢀinꢀtheꢀdifferentꢀsamplesꢀareꢀdisplayedꢀ
inꢀTableꢀ1.ꢀTheyꢀvariedꢀwithinꢀaꢀsmallꢀrangeꢀfromꢀ7.9ꢀtoꢀ11.8.ꢀ
Forꢀtheꢀsynthesizedꢀsample,ꢀweꢀnoticedꢀthatꢀtheꢀSi/Alꢀratiosꢀinꢀ
theꢀsamplesꢀwereꢀmuchꢀlessꢀthanꢀtheꢀcompositionꢀofꢀtheꢀrawꢀ
materialsꢀinꢀtheꢀmixedꢀsol‐gel,ꢀindicatingꢀaꢀlossꢀofꢀsilicaꢀinꢀtheꢀ
hydrothermalꢀ synthesis.ꢀ Withꢀ increasingꢀ Si/Alꢀ ratioꢀ inꢀ theꢀ
sol‐gel,ꢀtheꢀgapꢀcontinuedꢀtoꢀwiden.ꢀGenerally,ꢀmostꢀofꢀtheꢀdi‐
rectꢀsynthesisꢀmethodsꢀofꢀMORꢀyieldedꢀaꢀproductꢀwithꢀaꢀSi/Alꢀ
ratioꢀ ofꢀ 10ꢀ unlessꢀ someꢀ specialꢀ SDAꢀ orꢀ fluorideꢀ additionꢀ wasꢀ
employedꢀ [18,19].ꢀ Comparedꢀ withꢀ HM1–HM4,ꢀ HM5ꢀ hadꢀ aꢀ
higherꢀcontentꢀofꢀsilicon,ꢀwhichꢀwasꢀveryꢀcloseꢀtoꢀtheꢀvalueꢀinꢀ
theꢀ synthesisꢀmixture.ꢀThisꢀ suggestedꢀthatꢀHMIꢀasꢀ aꢀtemplateꢀ
favoredꢀtheꢀformationꢀofꢀhighꢀsilicaꢀMORꢀzeoliteꢀinꢀcomparisonꢀ
toꢀ TEAOHꢀ [18].ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ itꢀ wasꢀ alsoꢀ reportedꢀ thatꢀ
moreꢀamorphousꢀsiliconꢀspeciesꢀwereꢀdepositedꢀonꢀtheꢀnucleiꢀ
becauseꢀ ofꢀ theꢀ weakꢀ structure‐directingꢀ abilityꢀ ofꢀ HMIꢀ [20].ꢀ
Post‐treatmentꢀwithꢀchemicalsꢀisꢀconsideredꢀaꢀsimpleꢀandꢀprac‐
ticalꢀ strategyꢀ toꢀ adjustꢀ theꢀ compositionꢀ ofꢀ theꢀ zeoliteꢀ frame‐
work.ꢀ Asꢀ shownꢀ inꢀ Tableꢀ 1,ꢀ theꢀ Si/Alꢀ ratioꢀ ofꢀ commercialꢀ
H‐MORꢀ increasedꢀ afterꢀ theꢀ treatmentꢀ withꢀ citricꢀ acidꢀ andꢀ
4
73ꢀKꢀforꢀ1ꢀhꢀandꢀcooledꢀdownꢀtoꢀ423ꢀKꢀunderꢀArꢀflow.ꢀAfterꢀ
exposureꢀtoꢀexcessꢀNH ,ꢀtheꢀsampleꢀwasꢀpurgedꢀbyꢀArꢀflowꢀ(30ꢀ
mL/min)ꢀforꢀ1ꢀhꢀtoꢀremoveꢀphysicallyꢀadsorbedꢀNH .ꢀThen,ꢀtheꢀ
sampleꢀ wasꢀ heatedꢀ fromꢀ 373ꢀ toꢀ 1000ꢀ Kꢀ (10ꢀ K/min).ꢀ Theꢀ re‐
leasedꢀNH ꢀwasꢀdetectedꢀbyꢀaꢀTCD.ꢀ
3
3
3
FTIRꢀspectraꢀwereꢀrecordedꢀonꢀaꢀThermoꢀScientificꢀNicoletꢀ
700ꢀconnectedꢀtoꢀanꢀevacuationꢀsystem.ꢀPyridineꢀwasꢀappliedꢀ
6
asꢀ aꢀ probeꢀ moleculeꢀ toꢀ determineꢀ theꢀ concentrationꢀ ofꢀ
Brönstedꢀacidꢀsitesꢀinꢀtheꢀ12‐MRꢀchannelsꢀofꢀH‐MOR.ꢀTheꢀcata‐
lystꢀ(16ꢀmg)ꢀwasꢀpressedꢀintoꢀaꢀ13ꢀmmꢀself‐supportedꢀwaferꢀ
andꢀloadedꢀintoꢀanꢀinꢀsituꢀcellꢀwithꢀCaF ꢀwindows.ꢀSubsequent‐
2
ly,ꢀtheꢀsampleꢀwasꢀpre‐treatedꢀatꢀ723ꢀKꢀforꢀ30ꢀminꢀunderꢀvac‐
uum.ꢀWhenꢀtheꢀwaferꢀhadꢀcooledꢀdownꢀandꢀstabilizedꢀatꢀ423ꢀK,ꢀ
theꢀ backgroundꢀ spectrumꢀ wasꢀ recorded.ꢀ Afterꢀ saturationꢀ byꢀ
pyridineꢀ vaporꢀ forꢀ 30ꢀ min,ꢀ theꢀ sampleꢀ wasꢀ evacuatedꢀ forꢀ 30ꢀ
minꢀtoꢀremoveꢀphysicallyꢀadsorbedꢀpyridine.ꢀAllꢀspectraꢀwereꢀ
–1
collectedꢀinꢀtheꢀrangeꢀofꢀ650–4000ꢀcm ꢀbyꢀaveragingꢀ32ꢀscansꢀ
–1
atꢀaꢀresolutionꢀofꢀ4ꢀcm .ꢀ Theꢀ concentrationꢀ ofꢀ Brönstedꢀ acidꢀ
–1
sitesꢀ(1540ꢀcm )ꢀwasꢀcalculatedꢀaccordingꢀtoꢀRef.ꢀ[17].ꢀ
Tableꢀ1ꢀ
CompositionꢀanalysisꢀandꢀtexturalꢀpropertiesꢀofꢀtheꢀH‐MORꢀsamples.ꢀ
2
3
Relativeꢀcrystallinityꢀ
%)ꢀ
Surfaceꢀareaꢀ(m /g)ꢀ
ꢀ
ꢀ
Poreꢀvolumeꢀ(cm /g)ꢀ
Sampleꢀ
Si/Alꢀ
(
BETꢀ
Microporeꢀ
414.6ꢀ
436.2ꢀ
402.0ꢀ
449.1ꢀ
378.3ꢀ
422.1ꢀ
407.1ꢀ
371.6ꢀ
404.7ꢀ
Externalꢀ
Totalꢀ
0.194ꢀ
0.220ꢀ
0.220ꢀ
0.209ꢀ
0.196ꢀ
0.246ꢀ
0.291ꢀ
0.276ꢀ
0.268ꢀ
Microporeꢀ
0.193ꢀ
0.203ꢀ
0.187ꢀ
0.209ꢀ
0.176ꢀ
0.197ꢀ
0.190ꢀ
0.177ꢀ
0.188ꢀ
Mesoporeꢀ
HM1ꢀ
HM2ꢀ
HM3ꢀ
HM4ꢀ
HM5ꢀ
HMꢀ
C1ꢀ
ꢀ 8.2ꢀ
10.2ꢀ
11.1ꢀ
11.8ꢀ
11.8ꢀ
ꢀ 8.2ꢀ
ꢀ 9.3ꢀ
10.8ꢀ
ꢀ 8.5ꢀ
104ꢀ
103ꢀ
103ꢀ
100ꢀ
ꢀ 93ꢀ
100ꢀ
ꢀ 93ꢀ
ꢀ 88ꢀ
ꢀ 98ꢀ
423.6ꢀ
464.8ꢀ
445.3ꢀ
459.0ꢀ
389.5ꢀ
447.5ꢀ
480.5ꢀ
437.5ꢀ
463.3ꢀ
ꢀ 9.0ꢀ
28.6ꢀ
43.3ꢀ
ꢀ 9.9ꢀ
11.2ꢀ
25.4ꢀ
73.4ꢀ
65.9ꢀ
58.6ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
0.001ꢀ
0.017ꢀ
0.033ꢀ
0ꢀ
0.020ꢀ
0.049ꢀ
0.101ꢀ
0.099ꢀ
0.080ꢀ
C2ꢀ
Pꢀ

ꢀ
MeixiaꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1530–1537ꢀ
1533ꢀ
phosphoricꢀ acid,ꢀ whichꢀ wasꢀ consistentꢀ withꢀ otherꢀ publishedꢀ
worksꢀ [21,22].ꢀ Furthermore,ꢀ whenꢀ aꢀ higherꢀ concentrationꢀ ofꢀ
citricꢀacidꢀsolutionꢀwasꢀused,ꢀaꢀmoreꢀsevereꢀdealuminationꢀwasꢀ
observed.ꢀ ꢀ
XRDꢀwasꢀappliedꢀtoꢀmonitorꢀtheꢀstructureꢀandꢀcrystallinityꢀ
ofꢀtheꢀMORꢀsamples.ꢀAsꢀdepictedꢀinꢀFig.ꢀ1,ꢀallꢀsamplesꢀshowedꢀ
theꢀcharacteristicꢀpeaksꢀofꢀzeoliteꢀMORꢀ(PDFꢀ43‐0171)ꢀwithoutꢀ
anyꢀotherꢀcrystalꢀphaseꢀ[23].ꢀTheꢀrelativeꢀcrystallinityꢀwasꢀcal‐
culatedꢀ byꢀ comparingꢀ theꢀ totalꢀ areasꢀ ofꢀ fiveꢀ peaksꢀ withꢀ theꢀ
commercialꢀsampleꢀHMꢀ(relativeꢀcrystallinity,ꢀ100%).ꢀTheꢀposi‐
tionꢀofꢀtheseꢀpeaksꢀwereꢀ2θꢀ=ꢀ9.8˚,ꢀ19.6˚,ꢀ22.3˚,ꢀ25.7˚,ꢀandꢀ26.3˚,ꢀ
whichꢀ correspondedꢀ toꢀ theꢀ crystalꢀ planesꢀ ofꢀ (200),ꢀ (330),ꢀ
HM1
HM2
HM3
HM4
HM5
HM
C1
C2
P
(150),ꢀ (202),ꢀ andꢀ (350).ꢀ Asꢀ summarizedꢀinꢀTableꢀ 1,ꢀ thisꢀindi‐
catedꢀthatꢀallꢀtheꢀsamplesꢀthatꢀuseꢀdifferentꢀsynthesisꢀmixtureꢀ
compositionsꢀ exhibitedꢀ similarꢀ crystallinity.ꢀ Theꢀ sampleꢀ di‐
rectedꢀbyꢀHMIꢀhadꢀaꢀlowerꢀcrystallinity.ꢀComparedꢀtoꢀTEAOH,ꢀ
HMIꢀ possessedꢀ weakerꢀ alkalinity.ꢀ Asꢀ aꢀ weakꢀ SDA,ꢀ HMIꢀ couldꢀ
notꢀ effectivelyꢀ induceꢀ nucleation,ꢀ whichꢀ resultedꢀ inꢀ aꢀ lowerꢀ
nucleationꢀrateꢀandꢀmoreꢀamorphousꢀsiliconꢀspecies.ꢀAꢀsimilarꢀ
phenomenonꢀwasꢀreportedꢀbyꢀWuꢀetꢀal.ꢀ[20]ꢀinꢀTS‐1ꢀsynthesis.ꢀ
Post‐treatmentꢀbyꢀcitricꢀacidꢀandꢀphosphoricꢀacidꢀledꢀtoꢀaꢀslightꢀ
lossꢀ ofꢀ theꢀ crystalꢀ architecture.ꢀ Inꢀ addition,ꢀ theꢀ crystallinityꢀ
decreasedꢀ withꢀ increasingꢀ acidꢀ concentration,ꢀ implyingꢀ theꢀ
removalꢀofꢀframeworkꢀT‐atoms.ꢀ
0.0
0.2
0.4
0.6
0.8
1.0
p/p0
Fig.ꢀ2.ꢀNitrogenꢀadsorptionꢀisothermsꢀofꢀtheꢀH‐MORꢀsamples.ꢀ
volumesꢀ wereꢀ alsoꢀ littleꢀ changed.ꢀ Thisꢀ indicatedꢀ thatꢀ theꢀ
changeꢀofꢀtheꢀSi/Alꢀratioꢀinꢀthisꢀrangeꢀhadꢀlittleꢀimpactꢀonꢀtheꢀ
poreꢀ structureꢀ ofꢀ MORꢀ underꢀ theꢀ sameꢀ synthesisꢀ conditions.ꢀ
HM5ꢀ synthesizedꢀ withꢀ HMIꢀ asꢀ theꢀ templateꢀ hadꢀ theꢀ smallestꢀ
BETꢀsurfaceꢀareaꢀandꢀmicroporeꢀvolumeꢀcomparedꢀtoꢀtheꢀotherꢀ
samples.ꢀThisꢀwasꢀrelatedꢀtoꢀtheꢀweakerꢀabilityꢀofꢀHMIꢀtoꢀdirectꢀ
theꢀMORꢀstructure,ꢀwhichꢀwasꢀalsoꢀsupportedꢀbyꢀtheꢀXRDꢀdataꢀ
Nitrogenꢀ adsorptionꢀ atꢀ liquidꢀ nitrogenꢀ temperatureꢀ wasꢀ
carriedꢀoutꢀtoꢀcharacterizeꢀtheꢀtexturalꢀpropertiesꢀofꢀtheꢀsam‐
ples.ꢀFigureꢀ2ꢀpresentsꢀtheꢀadsorptionꢀisotherms.ꢀAccordingꢀtoꢀ
theꢀ IUPACꢀ classification,ꢀ theꢀ samplesꢀ preparedꢀ byꢀ hydrother‐
malꢀ synthesisꢀ (HM1–HM5)ꢀexhibitedꢀTypeꢀIꢀisotherms,ꢀ whichꢀ
demonstratedꢀ theirꢀ microporousꢀ structure.ꢀ Theꢀ commercialꢀ
andꢀacid‐treatedꢀsamplesꢀshowedꢀaꢀcombinationꢀofꢀTypeꢀIꢀandꢀ
IVꢀisothermsꢀwithꢀhysteresisꢀloops,ꢀsuggestingꢀtheꢀexistenceꢀofꢀ
bothꢀ micro‐ꢀ andꢀ mesopores.ꢀ Theꢀ calculatedꢀ specificꢀ surfaceꢀ
areasꢀandꢀporeꢀvolumesꢀareꢀlistedꢀinꢀTableꢀ1.ꢀForꢀH‐MORꢀsam‐
plesꢀwithꢀTEAOHꢀasꢀtheꢀtemplateꢀ(HM1–HM4),ꢀtheꢀsurfaceꢀare‐
[
23].ꢀAllꢀtheꢀsamplesꢀafterꢀacidicꢀtreatmentꢀexhibitedꢀaꢀlargerꢀ
surfaceꢀareaꢀandꢀmesoporeꢀvolumeꢀthanꢀtheꢀparentꢀHMꢀsample.ꢀ
Meanwhile,ꢀtheꢀmicroporeꢀsurfaceꢀareaꢀandꢀvolumeꢀdecreasedꢀ
withꢀacidꢀleachingꢀbecauseꢀofꢀtheꢀslightꢀcollapseꢀofꢀtheꢀzeoliticꢀ
structureꢀcausedꢀbyꢀtheꢀremovalꢀofꢀframeworkꢀT‐atoms.ꢀTheseꢀ
resultsꢀwereꢀinꢀagreementꢀwithꢀtheꢀconclusionꢀobtainedꢀbyꢀtheꢀ
previousꢀworksꢀonꢀzeoliteꢀpost‐treatmentꢀ[24,25].ꢀ
2
asꢀwereꢀsimilarꢀinꢀtheꢀrangeꢀfromꢀ423ꢀtoꢀ459ꢀm /g.ꢀTheꢀporeꢀ
3.2.ꢀ ꢀ Acidityꢀcharacterizationꢀ
(202)
(
150)
(200)
(
330)
(350)
Forꢀreactionsꢀcatalyzedꢀbyꢀsolidꢀacidsꢀsuchꢀasꢀtheꢀcarbonyla‐
HM1
HM2
tionꢀofꢀDME,ꢀtheꢀquantity,ꢀstrengthꢀandꢀlocationꢀofꢀtheꢀacidꢀsitesꢀ
areꢀ theꢀ mostꢀ importantꢀ factorsꢀ thatꢀ influenceꢀ theꢀ catalyticꢀ
properties.ꢀTheseꢀareꢀdependentꢀonꢀtheꢀcontentꢀandꢀdistribu‐
tionꢀofꢀAlꢀinꢀtheꢀzeolite.ꢀInꢀpreviousꢀstudies,ꢀtheꢀstericꢀconfine‐
mentꢀeffectꢀofꢀMORꢀonꢀDMEꢀcarbonylationꢀhasꢀbeenꢀproposedꢀ
andꢀdiscussedꢀ[10].ꢀSoꢀitꢀisꢀparticularlyꢀimportantꢀtoꢀquantita‐
tivelyꢀdetectꢀtheꢀacidꢀsitesꢀlocatedꢀinꢀtheꢀdifferentꢀchannelsꢀofꢀ
MOR.ꢀTheꢀmicroporeꢀsystemꢀofꢀMORꢀpossessesꢀtwoꢀporeꢀchan‐
nels:ꢀ theꢀ largerꢀ poresꢀ consistꢀ ofꢀ 12‐MRꢀ channelsꢀ (0.67ꢀ nmꢀ ×ꢀ
HM3
HM4
HM5
HM
C1
0
.70ꢀnm)ꢀandꢀtheꢀsmallerꢀonesꢀconsistꢀofꢀ8‐MRꢀchannelsꢀ(0.26ꢀ
C2
nmꢀ×ꢀ0.57ꢀnm),ꢀparallelꢀtoꢀtheꢀdirectionꢀofꢀtheꢀ12‐MRꢀchannelsꢀ
[18].ꢀToꢀinvestigateꢀtheꢀnatureꢀofꢀtheꢀacidꢀsitesꢀinꢀzeolites,ꢀsev‐
eralꢀbasicꢀprobeꢀmoleculesꢀwithꢀdifferentꢀsizesꢀwereꢀemployed,ꢀ
P
NaM
suchꢀ asꢀ NH
3
,ꢀ d ‐acetonitrile,ꢀ trimethylamineꢀ andꢀ pyridineꢀ [2].ꢀ
3
1
0
20
30
40
50
NH ꢀwithꢀaꢀsmallꢀkineticꢀdiameterꢀ(0.26ꢀnm)ꢀisꢀextensivelyꢀap‐
pliedꢀtoꢀdetermineꢀtheꢀtotalꢀamountꢀofꢀacidꢀsites,ꢀespeciallyꢀinꢀ
microporousꢀzeolite,ꢀowingꢀtoꢀitsꢀstrongꢀalkalinityꢀandꢀaccessi‐
3
o
2 /(
)
Fig.ꢀ1.ꢀXRDꢀpatternsꢀofꢀtheꢀMORꢀsamples.ꢀ

1534ꢀ
MeixiaꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1530–1537ꢀ
bilityꢀ toꢀ theꢀ acidꢀ sitesꢀ inꢀ theꢀ smallꢀ channel.ꢀ Pyridineꢀ isꢀ alsoꢀ
widelyꢀusedꢀforꢀmonitoringꢀacidꢀsitesꢀbecauseꢀofꢀitsꢀsensitivityꢀ
inꢀtheꢀIRꢀspectrum.ꢀMoreꢀimportantly,ꢀitꢀisꢀeasyꢀtoꢀdiscriminateꢀ
BrönstedꢀandꢀLewisꢀacidꢀsitesꢀbyꢀtheirꢀcharacteristicꢀbands.ꢀInꢀ
considerationꢀofꢀtheꢀMORꢀporeꢀstructure,ꢀpyridineꢀ(kineticꢀdi‐
ameter,ꢀ aboutꢀ 0.5ꢀ nm)ꢀ canꢀ probeꢀ theꢀ acidꢀ sitesꢀ inꢀ theꢀ 12‐MRꢀ
channels,ꢀwhileꢀtheꢀacidꢀsitesꢀinꢀtheꢀ8‐MRꢀchannelsꢀareꢀnotꢀac‐
Tableꢀ2ꢀ
QuantityꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀdifferentꢀchannelsꢀofꢀMORꢀsam‐
plesꢀandꢀcatalyticꢀperformance.ꢀ
frameworkꢀaꢀ
12‐MRꢀbꢀ
B
B
B
8‐MRꢀ
B
8‐MRꢀ
STYMAꢀ
Sampleꢀ
–
1
–1
(μmol/g)ꢀ (μmol/g)ꢀ (μmol/g)ꢀ (%)ꢀ
(gꢀg ꢀh )ꢀ
0.31ꢀ
0.36ꢀ
0.35ꢀ
0.33ꢀ
0.47ꢀ
0.18ꢀ
0.19ꢀ
0.17ꢀ
0.16ꢀ
0.01ꢀ
HM1ꢀ
HM2ꢀ
HM3ꢀ
HM4ꢀ
HM5ꢀ
HMꢀ
C1ꢀ
C2ꢀ
Pꢀ
NaMꢀ
1372ꢀ
1520ꢀ
1451ꢀ
1425ꢀ
1662ꢀ
1025ꢀ
ꢀ 906ꢀ
ꢀ 862ꢀ
ꢀ 843ꢀ
n.d.ꢀ
530ꢀ
518ꢀ
491ꢀ
486ꢀ
454ꢀ
466ꢀ
328ꢀ
364ꢀ
375ꢀ
ꢀ 24ꢀ
ꢀ 842ꢀ
1002ꢀ
ꢀ 960ꢀ
ꢀ 939ꢀ
1208ꢀ
ꢀ 559ꢀ
ꢀ 578ꢀ
ꢀ 498ꢀ
ꢀ 468ꢀ
—ꢀ
61.4ꢀ
65.9ꢀ
66.2ꢀ
65.9ꢀ
72.7ꢀ
54.5ꢀ
63.8ꢀ
57.8ꢀ
55.5ꢀ
—ꢀ
cessibleꢀ toꢀ pyridine.ꢀ Here,ꢀ weꢀ usedꢀ bothꢀ NH ‐TPDꢀ andꢀ pyri‐
3
dine‐adsorptionꢀIRꢀtoꢀdetermineꢀtheꢀacidꢀpropertiesꢀofꢀtheꢀMORꢀ
samples.ꢀ
Figureꢀ3ꢀshowsꢀtheꢀNH ‐TPDꢀprofilesꢀofꢀtheꢀMORꢀsamplesꢀ
3
preparedꢀwithꢀtheꢀdifferentꢀmethods.ꢀOneꢀpeakꢀwasꢀatꢀ500–550ꢀ
Kꢀandꢀtheꢀotherꢀatꢀhighꢀtemperatureꢀwasꢀbroadꢀandꢀasymmet‐
ric.ꢀTheꢀcurvesꢀwereꢀsimilarꢀtoꢀthoseꢀinꢀtheꢀreportedꢀliteratureꢀ
a
ꢀ
CalculatedꢀbasedꢀonꢀtheꢀareaꢀofꢀpeakꢀP
3
ꢀinꢀFig.ꢀ3.ꢀ
b
[
26–29].ꢀ Untilꢀ now,ꢀ theꢀ interpretationꢀ ofꢀ NH ‐TPDꢀ ofꢀ zeolitesꢀ
3
ꢀCalculatedꢀbasedꢀonꢀFig.ꢀ5.ꢀ
wasꢀnotꢀcompletelyꢀconsistent.ꢀGenerallyꢀspeaking,ꢀtheꢀpeakꢀatꢀ
lowꢀ temperatureꢀ wasꢀ assignedꢀ toꢀ physicallyꢀ adsorbedꢀ orꢀ hy‐
aꢀ lowꢀ thermalꢀ stability,ꢀ andꢀ theꢀ oneꢀ centeredꢀ atꢀ theꢀ highestꢀ
temperatureꢀ correspondꢀ toꢀ theꢀ strongꢀ acidꢀ sites,ꢀ whichꢀ wereꢀ
referredꢀtoꢀasꢀframeworkꢀBrönstedꢀacidꢀsites.ꢀ ꢀ
drogen‐bondedꢀNH ,ꢀwhileꢀtheꢀacidꢀsitesꢀgaveꢀriseꢀtoꢀtheꢀpeakꢀatꢀ
3
theꢀ higherꢀ temperatureꢀ inꢀ zeolites.ꢀ Someꢀ researchersꢀ haveꢀ
proposedꢀ thatꢀ theꢀ higherꢀ asymmetricꢀ temperatureꢀ peakꢀ beꢀ
consideredꢀ asꢀ aꢀ typicalꢀ characteristicꢀ ofꢀ Brönstedꢀ acidꢀ sitesꢀ
bondedꢀ toꢀ theꢀ frameworkꢀ Alꢀ atomsꢀ [28,30,31].ꢀ Niwaꢀ andꢀ
coworkersꢀ [32]ꢀ foundꢀ goodꢀ agreementꢀ betweenꢀ IR‐TPDꢀ andꢀ
Inꢀourꢀwork,ꢀweꢀalsoꢀdeconvolutedꢀtheꢀNH
toꢀthreeꢀpeaksꢀ(P ,ꢀP ,ꢀandꢀP ).ꢀForꢀtheꢀNaMꢀsample,ꢀtheꢀpeakꢀatꢀ
00–850ꢀKꢀhadꢀcompletelyꢀdisappearedꢀandꢀaꢀlowꢀintensityꢀandꢀ
3
‐TPDꢀprofilesꢀin‐
1
2
3
8
broadꢀpeakꢀatꢀ650ꢀKꢀwasꢀobserved.ꢀFromꢀtheꢀresultsꢀofꢀtheꢀac‐
tivityꢀevaluationꢀ(Fig.ꢀ6ꢀandꢀTableꢀ2),ꢀNaMꢀwasꢀalmostꢀinactive.ꢀ
Itꢀ isꢀ acceptedꢀ thatꢀ extra‐frameworkꢀ Alꢀ speciesꢀ andꢀ cationsꢀ
compensatedꢀ byꢀ theꢀ negativeꢀ chargeꢀ ofꢀ theꢀ frameworkꢀ wereꢀ
theꢀLewisꢀacidꢀsitesꢀ[36].ꢀForꢀDMEꢀcarbonylation,ꢀBrönstedꢀacidꢀ
sitesꢀhadꢀbeenꢀconfirmedꢀasꢀtheꢀactiveꢀcentersꢀ[29].ꢀTherefore,ꢀ
MS‐TPDꢀ ofꢀ NH
suggestedꢀ thatꢀ theꢀ desorbedꢀ NH
mainlyꢀ cameꢀ fromꢀ NH
+ꢀ bondedꢀ onꢀ theꢀ Brönstedꢀ acidꢀ sites.ꢀ
3
ꢀ atꢀ theꢀ highꢀ temperatureꢀ desorption,ꢀ whichꢀ
3
ꢀ atꢀ theꢀ highꢀ temperatureꢀ
4
Gounder’sꢀ groupꢀ [33]ꢀ suggestedꢀ thatꢀ theꢀ centerꢀ ofꢀ theꢀ highꢀ
temperatureꢀ featureꢀ dependedꢀ onꢀ theꢀ typeꢀ ofꢀ zeolites,ꢀ whichꢀ
reflectꢀ theꢀ frameworkꢀ Brönstedꢀ acidity.ꢀ Inꢀ someꢀ otherꢀ work,ꢀ
2 3
weꢀ attributedꢀ P ꢀ andꢀ P ꢀ toꢀ Lewisꢀ acidꢀ sitesꢀ andꢀ frameworkꢀ
theꢀNH ‐TPDꢀcurveꢀwasꢀdeconvolutedꢀintoꢀthreeꢀpeaksꢀorꢀevenꢀ
3
Brönstedꢀacidꢀsites.ꢀLi’sꢀgroupꢀ[29]ꢀalsoꢀanalyzedꢀtheꢀNH
3
‐TPDꢀ
moreꢀpeaksꢀbecauseꢀofꢀtheꢀexistenceꢀofꢀaꢀshoulderꢀpeakꢀalongꢀ
withꢀtheꢀhighꢀtemperatureꢀdesorptionꢀpeakꢀ[29,34,35].ꢀAmongꢀ
profilesꢀ ofꢀ MORꢀ combinedꢀ withꢀ theꢀ catalyticꢀ performanceꢀ inꢀ
DMEꢀ carbonylationꢀ andꢀ cameꢀ toꢀ aꢀ similarꢀ conclusion.ꢀ Theyꢀ
foundꢀthatꢀtheꢀareaꢀofꢀtheꢀthirdꢀpeakꢀwasꢀcorrelatedꢀtoꢀtheꢀac‐
these,ꢀtheꢀfirstꢀpeakꢀorꢀgroupꢀwasꢀdueꢀtoꢀweaklyꢀadsorbedꢀNH ,ꢀ
3
theꢀmiddleꢀoneꢀwasꢀnormallyꢀattributedꢀtoꢀLewisꢀacidꢀsitesꢀwithꢀ
tivity,ꢀsoꢀtheyꢀbelievedꢀthatꢀP ꢀreflectꢀtheꢀamountꢀofꢀframeworkꢀ
3
27
Brönstedꢀacidꢀsites.ꢀBesides,ꢀ AlꢀMASꢀNMRꢀshowedꢀtheꢀexist‐
enceꢀofꢀextra‐frameworkꢀAlꢀspeciesꢀ(signalꢀnearꢀtoꢀ0ꢀppm,ꢀFig.ꢀ
HM1
HM2
HM3
4).ꢀItsꢀproportionꢀwasꢀfromꢀ11%–18%ꢀbasedꢀonꢀtheꢀintegratedꢀ
HM4
HM5
HM1
HM2
HM3
HM4
HM5
HM
C1
C2
HM
C1
P
C2
P
NaM
80
60
40
20
0
-20
4
00
500
600
Temperature (K)
‐TPDꢀprofilesꢀofꢀtheꢀMORꢀsamples.ꢀ
700
800
900
1000

27
Fig.ꢀ4.ꢀ AlꢀMASꢀNMRꢀspectraꢀofꢀH‐MORꢀpreparedꢀwithꢀdifferentꢀmeth‐
Fig.ꢀ3.ꢀNH
3
ods.ꢀ

ꢀ
MeixiaꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1530–1537ꢀ
1535ꢀ
area,ꢀwhichꢀwasꢀinꢀagreementꢀwithꢀtheꢀratioꢀofꢀtheꢀLewisꢀacidꢀ
sitesꢀ (12%–24%)ꢀ fromꢀ theꢀ NH ‐TPDꢀ peakꢀ fitting.ꢀ Fromꢀ theꢀ
analysisꢀabove,ꢀitꢀisꢀreasonableꢀtoꢀcalculateꢀtheꢀtotalꢀamountꢀofꢀ
theꢀ frameworkꢀ Brönstedꢀ acidꢀ sitesꢀ fromꢀ theꢀ areaꢀ ofꢀ P .ꢀ Com‐
Above,ꢀNH ‐TPDꢀwasꢀusedꢀtoꢀdetermineꢀtheꢀtotalꢀamountꢀofꢀ
frameworkꢀ Brönstedꢀ acidꢀ sitesꢀ byꢀ peakꢀ deconvolution,ꢀ whileꢀ
3
3
theꢀquantityꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀ12‐MRꢀchannelꢀwasꢀ
–1
3
calculatedꢀ fromꢀ theꢀ areaꢀ ofꢀ theꢀ bandꢀ atꢀ 1540ꢀ cm ꢀ inꢀ theꢀ IRꢀ
spectrum.ꢀ Therefore,ꢀ weꢀ calculatedꢀ theꢀ amountꢀ ofꢀ Brönstedꢀ
acidꢀsitesꢀinꢀtheꢀ8‐MRꢀ(B8‐MR)ꢀchannelsꢀbyꢀEq.ꢀ(3).ꢀTheꢀresultsꢀonꢀ
theꢀquantityꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀdifferentꢀchannelsꢀareꢀ
listedꢀinꢀTableꢀ2.ꢀ
paredꢀ toꢀ commercialꢀ HMꢀ andꢀ theꢀ post‐treatedꢀ samples,ꢀ theꢀ
as‐synthesizedꢀ samplesꢀ showedꢀ aꢀ moreꢀ intenseꢀ andꢀ broaderꢀ
peakꢀ atꢀ highꢀ temperature,ꢀ whichꢀ wasꢀ evidenceꢀ ofꢀ aꢀ largerꢀ
numberꢀofꢀBrönstedꢀacidꢀsites.ꢀTheꢀresultsꢀofꢀtheꢀquantitativeꢀ
analysisꢀ byꢀ peakꢀ fittingꢀ wereꢀ summarizedꢀ inꢀ Tableꢀ 2.ꢀ Itꢀ wasꢀ
noteworthyꢀ thatꢀ HM5ꢀ possessedꢀ theꢀ largestꢀ amountꢀ ofꢀ
Brönstedꢀacidꢀsites,ꢀalthoughꢀitꢀhadꢀtheꢀhighestꢀSi/Alꢀratio.ꢀThisꢀ
revealedꢀtheꢀeffectꢀofꢀHMIꢀasꢀtheꢀSDAꢀinꢀtheꢀsynthesisꢀofꢀMOR.ꢀ ꢀ
Figureꢀ5ꢀpresentsꢀtheꢀFTIRꢀspectraꢀofꢀadsorbedꢀpyridineꢀinꢀ
B8‐MRꢀ=ꢀBframeworkꢀꢀB12‐MRꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ (3)ꢀ
AsꢀshownꢀinꢀTableꢀ2,ꢀtheꢀvariationꢀofꢀB8‐MRꢀwasꢀsimilarꢀtoꢀtheꢀ
trendꢀofꢀBframework.ꢀItꢀwasꢀnotꢀeasyꢀtoꢀdistinguishꢀtheꢀdifferenceꢀ
inꢀtheꢀdistributionꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀMORꢀsamplesꢀ
obtainedꢀ byꢀ differentꢀ methods.ꢀ Thus,ꢀ inꢀ orderꢀ toꢀ provideꢀ aꢀ
moreꢀ intuitiveꢀ understandingꢀ ofꢀ theꢀ distributionꢀ ofꢀ Brönstedꢀ
acidꢀsitesꢀinꢀtheꢀdifferentꢀchannels,ꢀweꢀcalculatedꢀtheꢀpropor‐
tionꢀofꢀB8‐MRꢀ(%)ꢀusingꢀEq.ꢀ(4).ꢀ
–1
theꢀrangeꢀofꢀ1400–1700ꢀcm .ꢀAsꢀmentionedꢀabove,ꢀthisꢀillus‐
tratedꢀtheꢀacidicꢀpropertyꢀinꢀtheꢀ12‐MRꢀfromꢀknowingꢀtheꢀsizesꢀ
ofꢀtheꢀpyridineꢀmoleculeꢀandꢀtheꢀdifferentꢀporesꢀinꢀMOR.ꢀAllꢀtheꢀ
samplesꢀ exhibitedꢀ theꢀ characteristicꢀ bandsꢀ assignedꢀ toꢀ pyri‐
B8‐MRꢀ=ꢀB8‐MR/Bframeworkꢀꢀ100%ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ (4)ꢀ
–1
diniumꢀionsꢀonꢀBrönstedꢀacidꢀsitesꢀ(1540ꢀandꢀ1630ꢀcm )ꢀandꢀ
pyridineꢀmoleculesꢀcoordinatedꢀtoꢀLewisꢀacidꢀsitesꢀ(1450ꢀandꢀ
TheꢀresultsꢀrevealedꢀthatꢀtheꢀratioꢀofꢀB8‐MRꢀinꢀallꢀtheꢀsamplesꢀ
rangedꢀ fromꢀ 54.5%ꢀ toꢀ 72.7%.ꢀ Theꢀ commercialꢀ MORꢀ hadꢀ theꢀ
leastꢀamountꢀofꢀB8‐MR.ꢀComparedꢀtoꢀtheꢀcommercialꢀsampleꢀandꢀ
post‐treatedꢀones,ꢀ theꢀ as‐synthesizedꢀ MORꢀexhibitedꢀaꢀ higherꢀ
ratioꢀofꢀB8‐MR,ꢀindicatingꢀtheꢀsuccessfulꢀmodificationꢀofꢀAlꢀdis‐
tributionꢀbyꢀcontrollingꢀtheꢀsynthesisꢀconditions.ꢀInꢀparticular,ꢀ
HMIꢀasꢀtheꢀSDAꢀremarkablyꢀincreasedꢀtheꢀnumberꢀofꢀB8‐MRꢀinꢀ
termsꢀofꢀpreferentialꢀlocationꢀofꢀAlꢀatomsꢀinꢀtheꢀ8‐MRꢀchannelsꢀ
ofꢀMOR.ꢀJongkindꢀetꢀal.ꢀ[18]ꢀofferedꢀanꢀexplanationꢀforꢀthisꢀre‐
sult.ꢀBecauseꢀHMIꢀ(kineticꢀdiameter,ꢀ0.76ꢀnm)ꢀcanꢀonlyꢀbeꢀac‐
commodatedꢀinꢀtheꢀ12‐MRꢀpores,ꢀtheꢀincorporationꢀofꢀAlꢀinꢀtheꢀ
largerꢀporesꢀwouldꢀbeꢀblockedꢀbyꢀtheꢀpresenceꢀofꢀtheꢀtemplate.ꢀ
Hence,ꢀ Alꢀ atomsꢀ wereꢀ preferentiallyꢀ locatedꢀ inꢀ theꢀ smallerꢀ
poresꢀ(8‐MR).ꢀTreatmentꢀbyꢀcitricꢀacidꢀorꢀphosphoricꢀacidꢀwasꢀ
ableꢀtoꢀtuneꢀtheꢀdistributionꢀofꢀtheꢀBrönstedꢀacidꢀsites.ꢀHowev‐
er,ꢀtheꢀdissolutionꢀofꢀframeworkꢀT‐atomsꢀinevitablyꢀoccurredꢀatꢀ
theꢀsameꢀtime,ꢀresultingꢀinꢀtheꢀdecreaseꢀofꢀtheꢀtotalꢀnumberꢀofꢀ
–1
–1
1
610ꢀcm ),ꢀrespectivelyꢀ[37].ꢀMoreover,ꢀtheꢀbandꢀatꢀ1490ꢀcm ꢀ
wasꢀobservedꢀforꢀallꢀsamples,ꢀwhichꢀwasꢀattributedꢀtoꢀtheꢀcon‐
tributionꢀofꢀpyridineꢀinteractingꢀwithꢀbothꢀLewisꢀandꢀBrönstedꢀ
–1
acidꢀsitesꢀ[37].ꢀMoreꢀspecifically,ꢀtheꢀbandꢀatꢀ1454ꢀcm ꢀforꢀtheꢀ
H‐MORꢀsamplesꢀ(HM1–HM5,ꢀHM,ꢀC1,ꢀC2ꢀandꢀP)ꢀwasꢀdueꢀtoꢀtheꢀ
C–Cꢀstretchingꢀvibrationꢀofꢀtheꢀpyridineꢀcomplexꢀcoordinatedꢀtoꢀ
3+
unsaturatedꢀ Al ꢀ ionsꢀ [36].ꢀ Aꢀ redꢀ shiftꢀ occurredꢀ inꢀ theꢀ NaMꢀ
sampleꢀbecauseꢀofꢀtheꢀinteractionꢀbetweenꢀpyridineꢀmoleculesꢀ
+
andꢀNa ꢀionsꢀ[36].ꢀWhenꢀTEAOHꢀwasꢀusedꢀasꢀtheꢀSDA,ꢀtheꢀin‐
–1
tensityꢀ ofꢀ theꢀ bandsꢀ atꢀ bothꢀ 1540ꢀ andꢀ 1454ꢀ cm ꢀslightlyꢀde‐
creasedꢀ withꢀ theꢀ decreaseꢀ ofꢀ Alꢀ content.ꢀ Theseꢀ twoꢀ bandsꢀ ofꢀ
HM5ꢀshowedꢀaꢀweakerꢀintensity,ꢀdemonstratingꢀlessꢀBrönstedꢀ
3+
acidꢀ sitesꢀ andꢀ unsaturatedꢀ Al ꢀ ionsꢀ inꢀ theꢀ 12‐MR.ꢀ Theꢀ ac‐
id‐treatedꢀsamplesꢀ(C1,ꢀC2,ꢀandꢀP)ꢀdisplayedꢀlessꢀBrönstedꢀacidꢀ
sitesꢀ andꢀ moreꢀ Lewisꢀ acidꢀ sitesꢀ thanꢀ theꢀ parentꢀ HMꢀ sample,ꢀ
whichꢀcouldꢀbeꢀascribedꢀtoꢀtheꢀremovalꢀofꢀframeworkꢀAlꢀandꢀ
theꢀ formationꢀ ofꢀ unsaturatedꢀ coordinatedꢀ Alꢀ speciesꢀ throughꢀ
theꢀpost‐treatment.ꢀTheꢀnumbersꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀ
Brönstedꢀ acidꢀ sites.ꢀ Therefore,ꢀ increasingꢀ theꢀ ratioꢀ ofꢀ B8‐MR
ꢀ
couldꢀnotꢀneutralizeꢀtheꢀnegativeꢀeffectsꢀcausedꢀbyꢀtheꢀremovalꢀ
ofꢀframeworkꢀAlꢀspecies,ꢀwhichꢀcausedꢀanꢀultimateꢀreductionꢀofꢀ
12‐MRꢀwereꢀcalculatedꢀfromꢀFig.ꢀ4ꢀandꢀlistedꢀinꢀTableꢀ2.ꢀ
B8‐MR.ꢀ
3.3.ꢀ ꢀ CatalyticꢀperformanceꢀforꢀDMEꢀcarbonylationꢀ
HM1
HM2
HM3
HM4
TheꢀcarbonylationꢀofꢀDMEꢀtoꢀMAꢀwasꢀappliedꢀasꢀaꢀprobeꢀre‐
actionꢀtoꢀdetectꢀtheꢀvariationꢀofꢀBrönstedꢀacidꢀsites.ꢀTheꢀinitialꢀ
catalyticꢀperformanceꢀareꢀshownꢀinꢀTableꢀ2ꢀandꢀFig.ꢀ6.ꢀTheꢀse‐
lectivityꢀ forꢀ MAꢀ overꢀ theꢀ differentꢀ catalystsꢀ wasꢀ aboveꢀ 95%,ꢀ
reflectingꢀtheꢀspecificityꢀofꢀtheꢀ8‐MRꢀchannelsꢀofꢀMORꢀ[14].ꢀAcidꢀ
treatmentꢀ (sampleꢀ C1,ꢀ C2,ꢀ andꢀ P)ꢀ ledꢀ toꢀ aꢀ slightꢀ decreaseꢀ ofꢀ
selectivityꢀowingꢀtoꢀtheꢀdeteriorationꢀofꢀtheꢀframeworkꢀstruc‐
ture.ꢀThisꢀcanꢀbeꢀdeducedꢀbyꢀtheꢀincreaseꢀofꢀtheꢀsurfaceꢀareaꢀ
andꢀmesoporeꢀvolume,ꢀandꢀtheꢀdecreaseꢀofꢀrelativeꢀcrystallini‐
ty.ꢀTheꢀresultsꢀshowedꢀalmostꢀundetectableꢀMAꢀfromꢀtheꢀNaMꢀ
sampleꢀ andꢀ varyingꢀ amountsꢀ fromꢀ H‐MORꢀ fromꢀ 0.16ꢀ toꢀ 0.47ꢀ
HM5
HM
C1
C2
P
NaM
–1 –1
+
gꢀg ꢀh ,ꢀwhichꢀprovedꢀthatꢀtheꢀreplacementꢀofꢀNa ꢀcationsꢀbyꢀ
hydrogenꢀprotonsꢀgeneratedꢀactiveꢀsitesꢀforꢀMAꢀformation.ꢀForꢀ
theꢀH‐MORꢀsamplesꢀsynthesizedꢀwithꢀTEAOHꢀasꢀtheꢀtemplate,ꢀ
theꢀconversionꢀofꢀDMEꢀincreasedꢀfirstꢀandꢀthenꢀdecreasedꢀwithꢀ
increasingꢀ Si/Alꢀ ratio.ꢀ Whenꢀ HMIꢀ wasꢀ usedꢀ asꢀ aꢀ template,ꢀ aꢀ
1
700
1650
1600
Wavenumber (cm )
Fig.ꢀ5.ꢀFTIRꢀspectraꢀofꢀadsorbedꢀpyridineꢀonꢀtheꢀMORꢀsamples.ꢀ
1550
1500
1
1450
1400

1536ꢀ
MeixiaꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1530–1537ꢀ
theꢀ amountꢀ andꢀ distributionꢀ ofꢀ theꢀ Brönstedꢀ acidꢀ sites.ꢀ Com‐
1
20
00
DME conversion
MA selectivity
paredꢀwithꢀtheꢀpreviousꢀpost‐treatmentꢀapproaches,ꢀsyntheticꢀ
controlꢀ isꢀ aꢀ moreꢀ effectiveꢀ strategyꢀ toꢀ promoteꢀ theꢀ carbon‐
lyationꢀofꢀDME.ꢀUpꢀtoꢀnow,ꢀsomeꢀsynthesisꢀmethodsꢀwereꢀap‐
pliedꢀ toꢀ improveꢀ theꢀ catalyticꢀ activityꢀ ofꢀ MORꢀ forꢀ DMEꢀ car‐
bonylation.ꢀShen’sꢀgroupꢀ[39]ꢀfoundꢀanꢀexcellentꢀactivityꢀoverꢀ
nanosizedꢀH‐MOR,ꢀwhichꢀwasꢀsynthesizedꢀusingꢀN,N,N,N’,N’,N’‐ꢀ
hexaethylpentanediammoniumꢀ cationꢀ asꢀ theꢀ template.ꢀ Theyꢀ
ascribedꢀtheꢀsignificantꢀimprovementꢀtoꢀaꢀfacilitatedꢀdiffusionꢀ
process.ꢀ Liu’sꢀ groupꢀ [40]ꢀ alsoꢀ reportedꢀ enhancedꢀ activityꢀ onꢀ
nanocrystal‐assembledꢀ hierarchicalꢀ MORꢀ zeolitesꢀ becauseꢀ ofꢀ
theꢀ shortenedꢀ diffusionꢀ path.ꢀ Li’sꢀ groupꢀ [29]ꢀ fabricatedꢀ
nanosheet‐assembledꢀH‐MORꢀwithoutꢀanꢀorganicꢀtemplate.ꢀTheꢀ
uniqueꢀ structureꢀ gaveꢀ aꢀ largerꢀ amountꢀ ofꢀ theꢀ frameworkꢀ
Brönstedꢀacidicꢀsites,ꢀwhichꢀresultedꢀinꢀhigherꢀactivityꢀandꢀalsoꢀ
betterꢀstability.ꢀHere,ꢀweꢀfoundꢀthatꢀtheꢀBrönstedꢀacidꢀsitesꢀinꢀ
MORꢀ canꢀ beꢀ tailoredꢀ byꢀ controllingꢀ theꢀ compositionꢀ ofꢀ theꢀ
sol‐gelꢀorꢀusingꢀanꢀappropriateꢀSDA.ꢀInꢀparticular,ꢀaꢀmuchꢀhigh‐
erꢀproportionꢀofꢀB8‐MRꢀwasꢀobtainedꢀwhenꢀHMIꢀwasꢀusedꢀasꢀtheꢀ
SDA.ꢀTheꢀhigherꢀratesꢀofꢀDMEꢀcarbonylationꢀverifiedꢀtheꢀsuc‐
cessfulꢀmodificationꢀofꢀtheꢀacidꢀsitesꢀdistributionꢀinꢀMOR.ꢀ
1
8
6
4
2
0
0
0
0
0
HM1 HM2 HM3HM4 HM5 HM C1 C2
Sample
P
NaM
Fig.ꢀ6.ꢀConversionꢀofꢀDMEꢀandꢀselectivityꢀforꢀMAꢀoverꢀMORꢀprepared
withꢀdifferentꢀmethods.ꢀReactionꢀcondition:ꢀDME/COꢀ=ꢀ1/49,ꢀ473ꢀK,ꢀ1.5
MPa,ꢀ6000ꢀh .ꢀ
–1
maximumꢀ conversionꢀ withꢀ similarꢀ selectivityꢀ wasꢀ obtainedꢀ
evenꢀatꢀlowꢀAlꢀcontent,ꢀpoorerꢀcrystallinityꢀandꢀsmallerꢀsurfaceꢀ
–1
–1
area.ꢀTheꢀyieldꢀwasꢀupꢀtoꢀ0.47ꢀgꢀg ꢀh .ꢀByꢀconsideringꢀtheꢀre‐
sultsꢀofꢀacidityꢀcharacterization,ꢀtheꢀgoodꢀcatalyticꢀperformanceꢀ
wasꢀattributedꢀtoꢀtheꢀconcentrationꢀofꢀframeworkꢀAlꢀatomsꢀinꢀ
theꢀ8‐MRꢀpores.ꢀEvenꢀunderꢀmildꢀconditionsꢀbyꢀusingꢀaꢀweakꢀ
acidꢀ solutionꢀ withꢀ aꢀ lowꢀ concentration,ꢀ acidꢀ treatmentꢀ de‐
creasedꢀtheꢀactivityꢀofꢀtheꢀcatalystꢀdueꢀtoꢀAlꢀleachingꢀofꢀtheꢀzeo‐
liteꢀframework.ꢀ ꢀ
4.ꢀ ꢀ Conclusionsꢀ
Weꢀ successfullyꢀ regulatedꢀ theꢀ acidꢀ propertiesꢀ ofꢀ MORꢀ byꢀ
differentꢀmethods.ꢀTheꢀquantityꢀofꢀBrönstedꢀacidꢀsitesꢀandꢀalsoꢀ
theirꢀ distributionꢀ wereꢀ modifiedꢀ throughꢀ bothꢀ synthesisꢀ andꢀ
post‐treatmentꢀmethods.ꢀControllableꢀsynthesisꢀisꢀaꢀpromisingꢀ
approachꢀtoꢀsynthesizeꢀH‐MORꢀzeoliteꢀwithꢀaꢀhighꢀconcentra‐
tionꢀofꢀBrönstedꢀacidꢀsites.ꢀTheꢀcompositionꢀofꢀSiꢀandꢀAlꢀinꢀtheꢀ
sol‐gelꢀinfluencedꢀtheꢀdistributionꢀofꢀBrönstedꢀacidꢀsites.ꢀMoreꢀ
importantly,ꢀHMIꢀasꢀtheꢀSDAꢀgaveꢀanꢀenrichmentꢀofꢀBrönstedꢀ
acidꢀsitesꢀinꢀtheꢀ8‐MRꢀchannelsꢀevenꢀatꢀaꢀlowꢀAlꢀcontentꢀinꢀzeo‐
liteꢀframework.ꢀTheꢀrateꢀofꢀMAꢀformationꢀfromꢀDMEꢀcarbonyla‐
tion,ꢀwhichꢀisꢀaꢀtypicalꢀspatiallyꢀconfinedꢀreactionꢀinꢀMOR,ꢀex‐
hibitedꢀ aꢀ linearꢀ dependenceꢀ onꢀ theꢀ amountꢀ ofꢀ Brönstedꢀ acidꢀ
sitesꢀlocatedꢀinꢀtheꢀ8‐MR.ꢀThisꢀconfirmedꢀthatꢀtheꢀregulationꢀofꢀ
theꢀ Brönstedꢀ acidꢀ siteꢀ distributionꢀ andꢀ locationꢀ inꢀ MORꢀ wasꢀ
achieved.ꢀ Ourꢀ resultsꢀ provideꢀ aꢀ betterꢀ understandingꢀ ofꢀ theꢀ
catalyticꢀ siteꢀ requirementꢀ inꢀ zeolites.ꢀ Rationalꢀ designꢀ ofꢀ theꢀ
spatialꢀconstraintsꢀaroundꢀactiveꢀsitesꢀinꢀinorganicꢀstructuresꢀisꢀ
aꢀpromisingꢀstrategyꢀtoꢀdevelopꢀanꢀefficientꢀcatalystꢀwithꢀexcel‐
lentꢀactivityꢀandꢀselectivity.ꢀ
Figureꢀ7ꢀshowsꢀtheꢀSTYꢀofꢀMAꢀasꢀaꢀfunctionꢀofꢀtheꢀnumberꢀofꢀ
8‐MRꢀforꢀtheꢀdifferentꢀsamples.ꢀMAꢀformationꢀincreasedꢀinꢀpar‐
B
allelꢀwithꢀtheꢀamountꢀofꢀBrönstedꢀacidꢀsitesꢀinꢀtheꢀ8‐MRꢀchan‐
nels.ꢀLiu’sꢀgroupꢀ[38]ꢀconfirmedꢀthatꢀtheꢀcarbonylationꢀreactionꢀ
onlyꢀoccurredꢀonꢀtheꢀacidꢀsitesꢀinꢀtheꢀ8‐MRꢀsideꢀpocketsꢀbyꢀinꢀ
situꢀdiffuseꢀreflectanceꢀinfraredꢀFourierꢀtransformꢀspectrosco‐
pyꢀ(DRIFTS).ꢀIglesia’sꢀgroupꢀ[14]ꢀhaveꢀreportedꢀaꢀsimilarꢀresultꢀ
inꢀ theirꢀ workꢀ previously;ꢀ Na ꢀ andꢀ Co ꢀ cationꢀ exchangeꢀ wereꢀ
usedꢀtoꢀreduceꢀtheꢀacidꢀsitesꢀinꢀtheꢀdifferentꢀchannels.ꢀInꢀaꢀfur‐
therꢀstudy,ꢀanꢀaqueousꢀsolutionꢀofꢀoxalicꢀacidꢀwasꢀusedꢀtoꢀdis‐
cernꢀtheꢀeffectꢀofꢀAlꢀcontentꢀonꢀtheꢀcarbonylationꢀofꢀDMEꢀ[15].ꢀ
However,ꢀ allꢀ theseꢀ conclusionsꢀ wereꢀ obtainedꢀ fromꢀ theꢀ sameꢀ
parentꢀH‐MORꢀandꢀpost‐treatedꢀsamples.ꢀInꢀthisꢀstudy,ꢀsynthe‐
sisꢀasꢀwellꢀasꢀchemicalꢀpost‐treatmentꢀwasꢀusedꢀforꢀmodifyingꢀ
+
2+
0.5
0.4
0.3
0.2
0.1
0.0
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ꢀ
MeixiaꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1530–1537ꢀ
GraphicalꢀAbstractꢀ
1537ꢀ
Chin.ꢀJ.ꢀCatal.,ꢀ2016,ꢀ37:ꢀ1530–1537ꢀ ꢀ ꢀ doi:ꢀ10.1016/S1872‐2067(16)62484‐1
ModifyingꢀtheꢀacidityꢀofꢀH‐MORꢀandꢀitsꢀcatalyticꢀcarbonylationꢀ
ofꢀdimethylꢀetherꢀ ꢀ
Different
Structure-
direct agents
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ ꢀ
MeixiaꢀWang, ShouyingꢀHuang*,ꢀJingLü,ꢀZaizheꢀCheng,ꢀYingLi,
ꢀ
ShengpingꢀWang,ꢀXinbinꢀMa*ꢀ
TianjinꢀUniversity;ꢀCollaborativeꢀInnovationꢀCenterꢀofꢀChemicalꢀ
ScienceꢀandꢀEngineeringꢀ(Tianjin)ꢀ
8-MR
of MOR
Various Si/Al
composition
ꢀ
Usingꢀhydrothermalꢀsynthesisꢀthatꢀfavoredꢀaꢀhigherꢀproportionꢀofꢀ
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