Microporous Zeolites and Related Nanoporous Materials Synthesis, Characterization and Applications in Catalysis Edited by Narendra Kumar Printed Edition of the Special Issue Published in Catalysts www.mdpi.com/journal/catalysts Microporous Zeolites and Related Nanoporous Materials: Synthesis, Characterization and Applications in Catalysis Microporous Zeolites and Related Nanoporous Materials: Synthesis, Characterization and Applications in Catalysis Editor NarendraKumar MDPI•Basel•Beijing•Wuhan•Barcelona•Belgrade•Manchester•Tokyo•Cluj•Tianjin Editor NarendraKumar A˚boAkademiUniversity Finland EditorialOffice MDPI St.Alban-Anlage66 4052Basel,Switzerland ThisisareprintofarticlesfromtheSpecialIssuepublishedonlineintheopenaccessjournalCatalysts (ISSN2073-4344)(availableat: https://www.mdpi.com/journal/catalysts/specialissues/Zeolites NanoporousMaterials). 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Contents AbouttheEditor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii NarendraKumar Microporous Zeolites and Related Nanoporous Materials: Synthesis, Characterization and ApplicationinCatalysis Reprintedfrom:Catalysts2021,11,382,doi:10.3390/catal11030382 . . . . . . . . . . . . . . . . . 1 EvaVrbkova´,ElisˇkaVyskocˇilova´,MiloslavLhotkaandLiborCˇerveny´ Solvent Influence on Selectivity in α-Pinene Oxide Isomerization Using MoO3-Modified ZeoliteBETA Reprintedfrom:Catalysts2020,10,1244,doi:10.3390/catal10111244 . . . . . . . . . . . . . . . . . 5 Toshiki Nishitoba, Takuya Nozaki, Sungsik Park, Yong Wang, Junko N. Kondo, Hermann Gies and Toshiyuki Yokoi CHA-Type Zeolite Prepared by Interzeolite Conversion Method Using FAU and LTL-Type Zeolite: Effect of the Raw Materials on the Crystallization Mechanism, and Physicochemical and Catalytic Properties Reprintedfrom:Catalysts2020,10,1204,doi:10.3390/catal10101204 . . . . . . . . . . . . . . . . . 23 SoudabehSaeid,MatildaKra˚kstro¨m,PasiTolvanen,NarendraKumar,KariEra¨nen,Markus Peurla,Jyri-PekkaMikkola,LaurentMae¨l,LeifKronberg,PatrikEklundandTapioSalmi Synthesis andCharacterization ofMetal ModifiedCatalysts forDecomposition of Ibuprofen fromAqueousSolutions Reprintedfrom:Catalysts2020,10,786,doi:10.3390/catal10070786 . . . . . . . . . . . . . . . . . 39 XianjunNiu,KaiWang,YangBai,Yi-enDu,YongqiangChen,MeiDongandWeibinFan SelectiveFormation ofPara-Xylene byMethanolAromatization overPhosphorous Modified ZSM-5Zeolites Reprintedfrom:Catalysts2020,10,484,doi:10.3390/catal10050484 . . . . . . . . . . . . . . . . . 63 Soudabeh Saeid, Matilda Kra˚kstro¨m, Pasi Tolvanen, Narendra Kumar, Kari Era¨nen, Jyri-Pekka Mikkola, Leif Kronberg, Patrik Eklund, Atte Aho, Heikki Palonen, Markus Perula, Andrey Shchukarev and Tapio Salmi Pt Modified Heterogeneous Catalysts Combined with Ozonation for the Removal of Diclofenac from Aqueous Solutions and the Fate of by-Products Reprintedfrom:Catalysts2020,10,322,doi:10.3390/catal10030322 . . . . . . . . . . . . . . . . . 75 SangminJeong,Ki-JoonJeon,Young-KwonPark,Byung-JooKim,Kyong-HwanChungand Sang-ChulJung CatalyticPropertiesofMicroporousZeoliteCatalystsinSynthesisofIsosorbidefromSorbitol byDehydration Reprintedfrom:Catalysts2020,10,148,doi:10.3390/catal10020148 . . . . . . . . . . . . . . . . . 101 Soudabeh Saeid, Matilda Kra˚kstro¨m, Pasi Tolvanen, Narendra Kumar, Kari Era¨nen, Jyri-Pekka Mikkola, Leif Kronberg, Patrik Eklund, Markus Peurla, Atte Aho, Andrey Shchukarev and Tapio Salmi Advanced Oxidation Process for Degradation of Carbamazepine from Aqueous Solution: Influence of Metal Modified Microporous, Mesoporous Catalysts on the Ozonation Process Reprintedfrom:Catalysts2020,10,90,doi:10.3390/catal10010090 . . . . . . . . . . . . . . . . . . 115 v YajunLuo,ChangxiMiao,YinghongYue,WeiminYang,WeimingHuaandZiGao Chromium Oxide Supported on Silicalite-1 Zeolite as a Novel Efficient Catalyst for DehydrogenationofIsobutaneAssistedbyCO2 Reprintedfrom:Catalysts2019,9,1040,doi:10.3390/catal9121040 . . . . . . . . . . . . . . . . . . 135 Huda Sharbini Kamaluddin, Sulaiman Nassir Basahel, Katabathini Narasimharao and MohamedMokhtar H-ZSM-5MaterialsEmbeddedinanAmorphousSilicaMatrix: HighlySelectiveCatalystsfor PropyleneinMethanol-to-OlefinProcess Reprintedfrom:Catalysts2019,9,364,doi:10.3390/catal9040364 . . . . . . . . . . . . . . . . . . . 149 Yichen Wang, Hongjuan Wang, Yuanchao Shao, Tianduo Li, Takashi Tatsumi and Jin-Gui Wang Direct Synthesis of Ti-Containing CFI-Type Extra-Large-Pore Zeolites in the Presence of Fluorides Reprintedfrom:Catalysts2019,9,257,doi:10.3390/catal9030257 . . . . . . . . . . . . . . . . . . . 167 Ya-Nan Miao, Yuan Wang, Dong-Hui Pan, Xiang-Hai Song, Si-Quan Xu, Li-Jing Gao and Guo-MinXiao Zn-Co@N-Doped Carbon Derived from ZIFs for High-Efficiency Synthesis of Ethyl Methyl Carbonate:TheFormationofZnOandtheInteractionbetweenCoandZn Reprintedfrom:Catalysts2019,9,94,doi:10.3390/catal9010094 . . . . . . . . . . . . . . . . . . . 177 I.Santamar´ıa-Holek,S.I.Herna´ndez,C.Garc´ıa-Alca´ntaraandA.Ledesma-Dura´n ReviewontheMacro-TransportProcessesTheoryforIrregularPoresabletoPerformCatalytic Reactions Reprintedfrom:Catalysts2019,9,281,doi:10.3390/catal9030281 . . . . . . . . . . . . . . . . . . . 193 vi About the Editor NarendraKumarobtainedhisDoctorofTechnology(ChemicalEngineering)degreefromA˚bo AkademiUniversity,LaboratoryofIndustrialChemistryandReactionEngineering,Turku,Finland in1996. HehasbeenworkingattheLaboratoryofIndustrialChemistryandReactionEngineering since February 1990. His duties are research, education, teaching, and supervision of PhD, M.Sc. and B.Sc. students. His scientific output numbers over 550, including peer-reviewed articles in internationaljournals,conferenceproceedingsandbookchapters. Hish-Indexis40. Dr. Narendra Kumar has more than 40 years of experience in research, education and process development in Chemical Engineering and Chemical Sciences. He acts as an expert for the project evaluation of severalnationalandinternationalorganizations.Hisexpertiseisinthefieldofchemicalengineering, heterogeneous catalysis, catalyst synthesis, material characterization, industrial catalysis, catalytic processes, biomass valorization, green fuel components, refinery processes and petro-chemicals. DocentDr. NarendraKumarhasbeenawardedanA˚boAkademiUniversitymedalforhisresearch, education,scientificknowledgecontributionsandcontinuousservicesattheuniversityforover25 years. Heistherecipientofseveralnationalandinternationalawards,medalsandprizes,including the prestigious International Eurand Award for research in Drug Delivery Systems. Prof. Dr. NarendraKumarisanAcademicEditorofthejournalCatalysts,andGuestEditoroftheSpecialIssue Catalysts and Editor Frontiers in Chemical Engineering. He is an editorial Board Member of the journalsCatalysts,FrontiersinChemicalEngineering,Journal,AmericanJournalofChemicalEngineering, Journal of Waste Engineering and Biomass Valorization and Current Catalysis. He is a reviewer for severalinternationaljournalsinthefieldofchemicalengineering,heterogeneouscatalysis,catalytic materials,biomassconversionandcatalyticchemicalprocesses. Hehasgivenmorethan60plenary, keynoteandinvitedlecturesininternationalconferences. vii catalysts Editorial Microporous Zeolites and Related Nanoporous Materials: Synthesis, Characterization and Application in Catalysis NarendraKumar LaboratoryofIndustrialChemistryandReactionEngineering,JohanGadolinProcessChemistryCentre, FacultyofScienceandEngineering,ÅboAkademiUniversity,Biskopsgatan8,FI-20500Turku/Åbo,Finland; narendra.kumar@abo.fi Microporouszeolitesandrelatednanoporousmaterialshavebeenstudiedintensively inacademicandindustriallaboratoriesaroundtheworld. Thereasonsforinterestin thesematerialsaretheuniquepropertiesofmicroporouszeolitessuchasuniformchannel systems,poredimensions,shapeselectivity,tunableBrønstedandLewisacidicsites,coke resistance,ion-exchangeandthermalstabilityproperties.Theprimaryfocusofresearch inthisfieldhasbeensynthesis,characterizationandapplicationsofacidic,nobleand transitionmetal-modifiedmicroporouszeolitesandrelatednanoporousmaterials.Itshould bementionedthatsincethe1960s,thesecatalyticmaterialshavebeenutilizedinseveral industrialprocessesforsynthesisofhigh-qualitygasoline,aromatics,isomersandethyl benzenes.Furthermore,developmentofnovelcatalystsynthesistechnologyandinvention ofnewtypesofmicroporouszeoliteswithvaryingstructureshasledtotheapplicationof thesecatalyticmaterialsinpetro-chemicalproductions,oilrefineryprocesses,andspeciality andfinechemicalsyntheses. Inrecentyears,microporous,mediumporousandlarge porouszeolitesandrelatednanoporousmaterialshavebeenstudiedforapplicationsin greenchemicalprocesses,environmentallyfriendlytechnologies,purificationofindustrial Citation: Kumar,N.Microporous wastewater, exhaust-emissioncontrol, synthesisofpharmaceuticals, drugs, medicinal ZeolitesandRelatedNanoporous productsandcarriersforproteinsanddrugmolecules. Materials:Synthesis,Characterization TheSpecialIssueofCatalystscontains12publishedpapers.Oneofthesepublished andApplicationinCatalysis. papersisareviewarticle[1]regardingtheprocessestheoryforirregularpores;theremain- Catalysts2021,11,382. ing11areresearchpapers[2–12].TheresearchpaperonZn-Co@N-Dopedcarbonderived https://doi.org/10.3390/catal 11030382 fromZIFsforhigh-efficiencysynthesisofethylmethylcarbonateandtheformationofZnO andtheinteractionbetweenCoandZn[2]elaboratesonthesynthesisandcharacterization Received:5March2021 oftheZn-Co-modifiedzeoliticimidazolateframework(ZIF)forthesynthesisofethyl Accepted:9March2021 methylcarbonate. Thesignificantresearchresultswerethesynthesisofanewtypeof Published:16March2021 zeolitematerialzeoliticimidazolateframework(ZIF).Furthermore,itwasreportedthat theloadingofcobaltandcalcinationtemperatureinfluencedtheparticlesize,oxidation Publisher’sNote:MDPIstaysneutral statesandcatalyticproperties. withregardtojurisdictionalclaimsin Synthesisoflargeporezeolitesisimportantfromthepointofviewofprocessingof publishedmapsandinstitutionalaffil- largesizeorganiccompounds.ThedirectsynthesisofTi-containingCFI-typeextra-large iations. porezeolitesinthepresenceoffluorideswasachievedin[3]. TheTi-CFicatalystwas synthesizedwithadditionofseedstoenhancethecrystallizationprocessanddecreasethe crystallitesize. Themethanoltoolefinprocessisaveryimportantindustrialprocessforthepro- Copyright: © 2021 by the author. ductionofolefins. Thereisasignificantissuewiththestabilityofcatalystsduetocoke Licensee MDPI, Basel, Switzerland. formation.Hence,thereiscontinuousresearchregardingthedevelopmentofnewcatalytic Thisarticleisanopenaccessarticle materials.ZSM-5zeoliteembeddedinanamorphoussilicamatrixwerehighlyselective distributed under the terms and catalystsforpropyleneinthemethanol-to-olefinprocess[4].Sincetheamount,strengthand conditionsoftheCreativeCommons distributionsofBrønstedacidsitesareimportantfortheproductionofolefins,embedding Attribution(CCBY)license(https:// ofmicroporouszeolitesinamorphoussilicagivesnewdirectionforsynthesisoftailored creativecommons.org/licenses/by/ acidsites. 4.0/). 1 Catalysts2021,11,382.https://doi.org/10.3390/catal11030382 https://www.mdpi.com/journal/catalysts Catalysts2021,11,382 Silicalite-1zeolitemodifiedwithchromiumoxidehasbeenusedfordehydrogenation ofisobutanetoisobuteneinpresenceofCO2. Isobuteneisusedfortheproductionof butylrubber,fuelcomponentssuchasethyl-butyletherandantioxidantssuchasbutylated hydroxyanisole.Chromiumoxideissupportedonsilicalite-1zeoliteasanovelefficientcat- alystfordehydrogenationofisobuteneassistedbyCO2in[5].Oxidativedehydrogenation oflightalkanessuchaspropane,butaneandisobuteneusingCO2isverycost-effective waytoobtainisobutene. Contaminationofriver,seaandoceanwaterwithpharmaceuticalcomponentsisa growingenvironmentalproblemwhichneedsimmediatesolutionsthroughdevelopmentof advancedtechnologies.Takingintoconsiderationthelimitedwaterresources,development ofgreenprocessesforpurificationsofpharmaceuticalcontaminatedwaterisofimmense importance. An advanced oxidation process for degradation of carbamazepine from aqueoussolutionsusingmetalmodifiedmicroporous,mesoporouscatalystsiscoveredin [6,8,9].Theresearchpaperreportsthemetal-modifiedcatalyticmaterialsforremovalof pharmaceuticalsfromthewastewater. Diclofenac,anonsteroidalanti-inflammatorydrugusedfortreatmentofosteoarthritis, rheumatoidarthritis,migraineheadacheandmenstrualcramps,hasbeenfoundinfresh watersources.Theremovalofdiclofenacfromthewatersourcesisimportantfortheenvi- ronmental,ecological,wastewaterpurificationandsustainabledevelopmentofbiodiversity. DifferenttypesofcatalyticmaterialssuchasacidicandPt-modifiedMCM-22microporous zeolitesandPt-Al2O3catalystshavebeenstudiedfortheremovalofdiclofenacfromaque- oussolutionsources.ItwasobservedthatPt-modifiedMCM-22zeolitecatalystsenhanced thedegradationofdiclofenac.AmethodusingPt-modifiedheterogeneouscatalystscom- binedwithozonationfortheremovalofdiclofenacfromaqueoussolutionsandfateof by-productscanbeseenin[8]. Isosorbideisusedasanimportantbiomaterialinthepharmaceuticalindustry.Green processtechnologydevelopmentforsynthesisofpureisosorbidefromsorbitolhasbeen proposedusingdifferenttypesofcatalyticmaterials.Theresearchpublishedinthisspecial issueutilizesMordenite,ZSM-5,MCM-22,USYandBetazeoliteswithvaryingstructures andacidicpropertiesforsynthesisofisosorbidefromsorbital. Catalyticpropertiesof microporouszeolitecatalystsinsynthesisofisosorbidefromsorbitolbydehydrationis coveredin[7]. Productionofpara-xyleneusingtheH-ZSM-5zeolitecatalystisanimportantindus- trialchemicaltechnologyintheoilrefineryprocess.Therehasbeencontinuousresearchin developmentofnewselectivecatalystsforsynthesisofpara-xylene.Selectivesynthesis ofpara-xyleneoverP-ZSM-5zeolitecatalystsbymethanolaromatizationandamethod of phosphorus modification of physico-chemical and catalytic properties is described in[10].Theresearchpapersalsoelaborateontheinfluenceofphosphorusmodificationson BrønstedandLewisacidsites,crystallinityandsurfaceareaofP-ZSM-5zeolitecatalysts. Synthesis,characterizationandapplicationsofCHA-typezeoliteinseveralreactions haveattractedtheattentionofacademicandindustrialresearchlaboratories. In-depth researchregardingthepreparationofCHA-typezeolitesusingFAU-andLTL-typezeolites asrawmaterialsandtheinfluenceofvariationsofsynthesisparameters,reactionmecha- nismandcatalyticpropertieshasbeenreported[11].ThesynthesizedCHAzeolitecatalyst showedhighcatalyticactivityandselectivityinconversionofmethanoltoolefins. Campholenicaldehydeandtrans-carveolareimportantchemicalsusedinthesyn- thesisofpharmaceuticals,medicinalproducts,specialitychemicals,drugmoleculesand fragrancesproductions.Thesechemicalcompoundsareobtainedbycatalyticisomeriza- tionofα-pineneoxideusingdifferenttypesofmetal-modifiedheterogeneouscatalytic materials.Theeffectofsolvents,metalnanoparticlesizedistributions,dispersionofMoO3 inBetazeolite,surfaceareaandstructuralpropertieshavebeenstudiedinα-pineneoxide isomerizationreactions[12]. TheresearchpaperspublishedintheSpecialIssue“Microporouszeolitesandrelated nanoporousmaterials: synthesis, characterizationandapplicationincatalysis”reflect 2 Catalysts2021,11,382 thenoveltrendsinthesynthesisofpetro-chemicals,fuelcomponents,fineandspeciality chemicals,pharmaceuticals,drugmoleculesandfragrancesusingprinciplesofsustainable developmentofourplanet,greenprocesstechnology,environmentallyfriendlytechnology andmitigationofclimatechange.Furthermore,researchresultsinthesepublishedpapers willenhanceanddeepenthescientificknowledgeofyoungergenerationsofacademicians, researchers,scientistsandengineersworkinginthefieldofheterogeneouscatalysis,cat- alystsynthesisandcharacterization,reactionmechanisms,zeolitesynthesis,oilrefinery processes,environmentalcatalysisandporousmaterialsproductions. InstitutionalReviewBoardStatement:Notapplicable. InformedConsentStatement:Notapplicable. ConflictsofInterest:Theauthordeclaresnoconflictofinterest. References 1. Santamaria-Holek,I.;Hernandez,S.I.;Gracia-Alcantara,C.;Ledesma-Duran,A.Reviewonmacro-transportprocesstheoryfor irregularporesabletoperformcatalyticreactions.Catalysts2019,9,281.[CrossRef] 2. Miao,Y.;Wang,Y.;Pan,D.-H.;Song,X.-H.;Xu,S.-Q.;Gao,L.-J.;Xiao,G.Zn-Co@N-DopedcarbonderivedfromZIFsforhigh efficiencysynthesisofethylmethylcarbonate:TheformationofZnOandtheInteractionbetweenCoandZn.Catalysts2019,9,94. [CrossRef] 3. Wang,Y.;Wang,H.;Shao,Y.;Li,T.;Tatsumi,T.;Wang,J.G.DirectsynthesisofTi-containingCFI-typeextra-large-porezeolitesin thepresenceoffluorides.Catalysts2019,9,257.[CrossRef] 4. Kamaluddin,H.S.;Basahel,S.N.;Narasimharao,K.;Mukhtar,M.H-ZSM-5materialsembeddedinanamorphoussilicamatrix: Highlyselectivecatalystsforpropyleneinmethanol-to-olefinprocess.Catalysts2019,9,364.[CrossRef] 5. Luo,Y.;Miao,C.;Yue,Y.;Yang,W.;Hua,W.;Gao,Z.Chromiumoxidesupportedonsilialite-1zeoliteasanovelefficientcatalyst fordehydrogenationofisobuteneassistedbyCO2.Catalysts2019,9,1040.[CrossRef] 6. Saeid,S.;Kråkström,M.;Tolvanen,P.;Kumar,N.;Eränen,K.;Mikkola,J.;Kronberg,L.;Eklund,P.;Peurla,M.;Aho,A.;etal. Advancedoxidationprocessfordegradationofcarbamazepinefromaqueoussolution:Influenceofmetalmodifiedmicroporous, mesoporouscatalystsontheozonationprocess.Catalysts2020,10,90.[CrossRef] 7. Jeong,S.;Jeon,K.;Park,Y.;Kim,B.;Chung,K.;Jung,S.Catalyticpropertiesofmicroporouszeolitecatalystsinsynthesisof isosorbidefromsorbitolbydehydration.Catalysts2020,10,148.[CrossRef] 8. Saeid,S.;Kråkström,M.;Tolvanen,P.;Kumar,N.;Eränen,K.;Mikkola,J.-P.;Kronberg,L.;Eklund,P.;Aho,A.;Palonen,H.;etal. Ptmodifiedheterogeneouscatalystscombinedwithozonationfortheremovalofdiclofenacfromaqueoussolutionsandthefate ofby-products.Catalysts2020,10,322.[CrossRef] 9. Saeid,S.;Kråkström,M.;Tolvanen,P.;Kumar,N.;Eränen,K.;Peurla,M.;Mikkola,J.-P.;Mael,L.;Kronberg,L.;Eklund,P.;etal. Synthesisandcharacterizationofmetalmodifiedcatalystsfordecompositionofibuprofenfromaqueoussolutions.Catalysts2020, 10,786.[CrossRef] 10. Niu,X.;Wang,K.;Bai,Y.;Du,Y.E.;Dong,M.;Fan,W.Selectiveformationofpara-xylenebymethanolaromatizationover phosphrousmodifiedZSM-5zeolites.Catalysts2020,10,484.[CrossRef] 11. Nishitoba,T.;Nozaki,T.;Park,S.;Wang,Y.;Kondo,J.N.;Gies,H.;Yokoi,T.CHA-typezeolitepreparedbyinterzeoliteconversion methodusingFAUandLTL-typezeolite:Effectoftherawmaterialsoncrystallizationmechanismandphysicochemicaland catalyticproperties.Catalysts2020,10,1204.[CrossRef] 12. Vrbkova,E.;Vyskocilova,E.;Lhotka,M.LiborCerveny,Solventinfluenceonselectivityinpineneoxideisomerizationusing MoO3-modifiedzeoliteBeta.Catalysts2020,10,1244.[CrossRef] 3