Structure of zeolites and their acid sites a multinuclear NMR investigation
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1 Research Collection Doctoral Thesis Structure of zeolites and their acid sites a multinuclear NMR investigation Author(s): Anuji, Abraham Publication Date: 2006 Permanent Link: Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library
2 Doctoral Thesis ETH No Struetureof Zeolites and their Aeid Sites: A Multinuclear NMRInvestigation A dissertation submitted to the SWISS FEDERAL INSTITUTEOF TECHNOLOGY (ETH)ZÜRICH SWITZERLAND for the degree of Doctor of Sciences Presented by ANUJIABRAHAM Master of Science, University of Madras, Chennai, India Born on October7,1977 Citizen of India Accepted on the recommendationof Prof. Dr. Roel Prins, examiner Prof. Dr. Arno P. M. Kentgens, co-examiner Prof. Dr. Jeroen A. van Bokhoven, co-examiner Zürich,2006
3 Summary Studying the strueture of zeolites and their aeid sites is important for understandingthe strueture-performance relationships of zeolites. Zeolites are crystalline aluminosilicates having an open framework strueture built from corner-sharing SiCM and AIO4" tetrahedra to form three-dimensional Channel Systems. The aeid sites in a zeolite are Brensted and Lewis aeid sites and silanol groups. The aim of the thesis was to determine the local strueture of zeolites, in particular the characterization of the aeid sites. State-of-the-art multinuclear and double-resonance solid-state nuclear magnetic resonance techniques were applied to determine the zeolite local structures, those of the aeid sites, and the interaction of probe molecules with the aeid sites. the zeolite strueturewas also determined. The infiuence of synthesis and of post-synthesis treatments on AI MAS and 27A1 triple-quantum magic-angle spinning (3Q-MAS)NMR techniques were used to study the aluminum coordination and distribution over the crystallographically inequivalent T-sites in the frameworkof zeolite Beta framework. The Si/Al ratio affected the aluminum oecupationof T-sites and a non-randomdistribution, which is more restricted than prescribed by Loewenstein's rule, was observed. When exchanged to H-Beta, octahedral aluminum was observed and its amount decreased with increasing Si/Al ratios and was absent for high-silica H-Beta (Si/Al = 110 and 215). Only specific tetrahedral T-sites in the frameworkconvertedto octahedral sites during calcination and two such T-sites, adjacent or in close proximity, may be necessary for the hydrolysis of the Si-O-Al bond and, thus affect the zeolite stability. Structural changes in zeolite MCM-22 after various post-synthesis treatments were determined using 27A1 MAS/3Q-MAS and 29Si MAS NMR. The local strueture of aluminum in the frameworkof zeolite MCM-22 was highly sensitive to temperatureand gas treatments, in particularmoisture. The frameworkof calcined MCM-22 was found to be different from that of as-synthesized MCM-22. Like in zeolite Beta, partial resolution of the T-sites was observed. Unlike Beta, preferential positioning of aluminum on specific T-sites of the MCM-
4 8 22 framework was not detected. The stability of aluminum in the zeolitic frameworkof H- MCM-22 depended on the Si/Al ratio. Zeolites with a higher Si/Al ratio contained a lower percentageof octahedral aluminum, which confirmed that aluminum atoms in close proximity affect each other. The coordination of the octahedral aluminum species changed to tetrahedrally coordinated framework species upon ammonia treatment, which is a general phenomenon in zeolites. The reversibility of the coordination shows that such octahedral species formed during the calcination are framework-associatedaluminum species. An enhanced disorder of the framework was observed after the conversion of aluminum coordination from octahedral to tetrahedral. A model study on aluminum alkoxides was done to optimize the TRAnsfer of Population in DOuble-Resonance (TRAPDOR) NMR before applying this technique to zeolitic Systems. 13C-{27A1} TRAPDOR experiments were employed successfully and the aluminum-carbon dipolar couplings for aluminum alkoxide Compounds with Al-O-C Connectivities were determined. Such Connectivities are also relevant in zeolitic Systems, because they also occur in zeolite-reaetantinteractions. Moreover, aluminum alkoxides have equally large quadrupolar couplings constants as non-hydrated zeolites. nc-{27al} TRAPDORexperiments were very efficient in distinguishing terminal and bridging carbons in aluminum alkoxide structures and unambiguousdetermination of the aluminum alkoxide solid state structureswere made. A combination of 27A1 MAS/3Q-MAS and 27A1-{14N} TRAPDOR NMR was used to resolve various structural anomalies in the strueture of zeolite ZSM-5. The two resonances observed in the 27A1 MAS/3Q-MAS spectra of as-synthesized ZSM-5 and H-ZSM-5 were unambiguously assigned to two groups of aluminums occupying crystallographically inequivalent T-sites. The methyl peak at 10.3 ppm was more dephased than the methyl peak at 11.4 ppm in a 13C-{27A1} TRAPDOR double-resonancenmr experiment indicating a closer proximityofthe 10.3 ppm methyl to the aluminum atoms in the framework. This agreed with the earlier suggestions that the methyl peak at 10.3 ppm is projeeted into the zig-zag Channel and the peak at 11.4 ppm into the straight Channels ofthe three dimensionalzsm-5 zeolite. A detailed structural characterizationof the Bronsted aeid sites, the silanols, and the Al(OH) acidic species was done using 'H and 27A1 MAS NMR under dehydratedconditions. The results were compared to those obtained with infra red, which provided data with higher spectral resolution. The 27A1 MAS NMR spectra showed only tetrahedrally coordinated aluminum in zeolites under fully dehydrated states, although a multiple of coordinations was observed in the hydrated State. In the 27A1 MAS NMR spectra, these species were very broad,
5 because of the large quadrupolar couplings constant, which limits the spectral resolution. Despite this much worse spectral resolution in 27A1 MAS NMR, such conditions are preferred as they reflect the dehydrated states of many catalytic reactions and the zeolites did not undergo hydrolysis of frameworkaluminum. The response of the Bronsted adsorption of probe molecules like acetonitrile and methylamine on zeolites Y and Ultrastable Y (USY) was determined using *H high-speedmas and ]H-{27A1} REDORNMR at high magnetic fields. Acetonitrile molecules formed hydrogen-bonded species and methylamine formed protonated species (CH3NH3+) with the Bronsted hydroxyl groups. Aeid aeid sites after sites in super and sodalite cages interact to methylamine due to its strong basicity. Higher Si/Al ratios of the frameworkincreased the hydrogen-bonded interaction and no effect of extra-frameworkaluminumwas observed. In high aluminum zeolite Y (Si/Al = 2.6), the strain in the aeid site was relaxed after hydrogen-bonding with acetonitrile. Although zeolites Y with a higher framework Si/Al ratio showed hydrogen-bonded acetonitrile, no relaxation in the strained aluminum tetrahedron was observed. The post-synthesis activation apparently affected the flexibility ofthe zeolite framework, which could infiuence catalytic reactions by differentlyaecommodatingreaetantsand intermediates on the catalytically activesites. Clearly, the application of state-of-the-art NMR provides detailed insights into the structures of zeolites and that of the catalytically active sites, which is essential in the determination of strueture-performance relationships. This thesis has provided new insights into zeolite structures, those of the active sites, and into the interactionof probe molecules with the active sites. A basis for further structural characterization of the strueture of the Bronsted aeid sites and the infiuence of post-synthesis activation was laid and, moreover, hints of how to prepare zeolites with novel properties and that with more stability were provided.
6 Zusammenfassung Die Untersuchung von Zeolithstrukturen und ihren sauren Zentren ist für das Verständnisihrer katalytischen Aktivität wichtig. Zeolithe sind kristalline Alumosilikate die aus eckenverknüpften Si04 und AIO4" Tetraedern aufgebaut sind und eine offene Gerüststruktur sowie dreidimensionale Porensysteme aufweisen. Bei den sauren Zentren von Zeolithen kann es sich sowohl um Brensted und Lewis-Zentren,als auch um Silanolgruppen handeln. Das Ziel dieser Arbeit liegt darin, die lokale Struktur der Zeolithe zu bestimmen, wobei besonderesaugenmerk aufdie Charakterisierung der sauren Zentren gelegt wurde. Um die lokalen Zeolithstrukturen, die Säurezentren und die Wechselwirkungenvon bestimmten Molekülenmit den sauren Zentrenzu bestimmen, wurde Kernresonanzspektroskopie(NMR) von verschiedenenatomen, sowie Doppelresonanz-FestkÖrper-NMR verwendet.der Einfluss von verschiedenen Syntheseparametern, sowie von auf die Synthese folgenden Nachbehandlungen auf die Zeolithstrukturen,wurde ebenfallsuntersucht. 27A1 MAS und 27A1 triple-quantum magic-angle spinning (3Q-MAS) NMR Techniken wurden eingesetzt um die Aluminiumkoordination und Verteilung über die verschiedenentsites in Zeolith Beta zu analysieren. Es konnte gezeigt werden, dass die Verteilung der Aluminiumatome über die verschiedenen T-sites in Zeolith Beta eine Funktion des Si/AI- Verhältnisses ist. Dies zeigt, dass die Verteilung nicht zufällig ist, sondern strikteren Regeln folgt als durch die Loewenstein-Regel beschrieben. Je höher das Si/Al-Verhältnis ist, desto besser können die verschiedenent-sites unterschieden werden. Nach einem Ionenaustausch hin zu H-Beta kann oktaedrisches Aluminium nachgewiesen werden, wobei umso weniger oktaedrisches Aluminium entsteht, je höher das Si/Al- Verhältnis ist. In H-Beta mit hohem Siliziumanteil (Si/Al =110, bzw. 215) entsteht kein oktaedrisches Aluminium.Nur spezielle tetraedrische T-sites im Zeolithgerüst können beim Kalzinieren in oktaedrische T-sites umgewandelt werden. Für die Hydrolyse von Si-O-Al Bindungen und die damit einhergehendebildung von oktaedrischen Spezies sind anscheinend zwei T-sites notwendig, die gegenüber oder zumindest eng benachbartliegen müssen.
7 12 Änderungen der Struktur von Zeolith MCM-22 durch verschiedene Nachbehandlungenwurden mit 27A1 MAS/3Q-MAS und 29Si MAS NMR untersucht. Die lokale Struktur von Aluminium im Zeolithgerüst von MCM-22 ist sehr empfindlichbezüglich Temperatur und der Behandlung mit Gas. Das Zeolithgerüst von kalziniertem MCM-22 unterscheidet sich von frisch synthetisiertem MCM-22. Wie bereits bei Zeolith Beta konnten verschiedene T-sites unterschieden werden. Im Gegensatz zu Zeolith Beta konnten jedoch keine bevorzugten T-sites identifiziert werden an denen sich die Aluminiumatome befinden. Die Stabilität von Aluminium im Zeolithgitter von H-MCM-22 hängt vom Si/AI-Verhältnis ab, wobei ein höheres Si/Al-Verhältnis weniger oktaedrisches Aluminium bedeutet. Oktaedrische Aluminiumspezies wandeln sich bei der Behandlung mit Ammoniak in tetraedrisch koordinierte Spezies um, was bei Zeolithen öfters beobachtetwerden kann. Die Umkehrbarkeit der Koordination zeigt, dass die bei der Kalzinierung entstandenen oktaedrischen Spezies am Zeolithgitter assoziiert sind. Die Umwandlungvon oktaedrischen Spezies in tetraedrische verringert die Ordnung des Gitters. Bevor die TRAPDOR Doppelresonanz-NMR Technik (TRansfer of Population in DOuble-Resonance)auf Zeolithe angewendet wurde, wurde sie am Modellsystem gestestet (Aluminium Alkoxide). 13C-27A1 TRAPDOR Experimente wurden erfolgreich durchgeführt um die dipolaren Kopplungen zwischen Aluminium und Kohlenstoff in Al-O-C Bindungen abzuschätzen. Es zeigt sich, dass 13C-27A1 TRAPDOR Experimente auch gut dafür geeignet sind, zwischen endständigenund verbrückenden Kohlenstoffatomen in Aluminium Alkoxiden zu unterscheiden. Eine Kombinationaus 27A1 MAS/3Q-MAS und 27A1-{14N} TRAPDOR NMR wurde verwendet um die Umgebung der Aluminiumatomein Zeolith ZSM-5 zu charakterisieren.die zwei Banden im 27A1 MAS/3Q-MAS Spektrum von frisch synthetisiertem ZSM-5 und H- ZSM-5 kommen von zwei kristallographisch unterschiedlichen Gruppen von T-sites. 27A1- { TM} TRAPDOR Doppelresonanz-NMR zeigte den Zusammenhang der beiden Aluminiumbandenmit den 14N-Banden von TPA+ und NIL"1" in frisch synthetisiertem ZSM-5. Das Methyl-Signalbei 10.3 ppm war stärker ausser Phase als das bei 10.4 ppm im,3c-{27a1} TRAPDORDoppelresonanz-NMRExperiment.Daraus kann auf eine grössere Nähe der 10.3 ppm Methylgruppe mit dem Aluminium im Kristallgitter geschlossen werden. Dies ist in Übereinstimmungmit früheren Vermutungen, dass die 10.3 ppm Methylbande mit den Zickzack-Kanälen korrespondiert, während die 10.4 ppm Bande mit den geraden Poren des dreidimensionalenporennetzwerks des Zeolithen ZSM-5 korreliert.
8 13 Unter dehydratisiertenbedingungenwurden verschiedenesaure Zentren, wie Bronsted Zentren, Silanolgruppenund Al(OH)-Spezies durch eine Kombinationvon 'H, 27A1 MAS NMR und IR-Spektroskopie charakterisiert. 27A1 MAS NMR zeigte für Zeolithe im vollständig dehydratisierten Zustand nur tetraedrischkoordiniertes Aluminium,währendunter hydratisierten Bedingungeneine Vielzahl von Spezies nachgewiesen werden kann. Obwohl die Auflösung der Spektren im dehydratisierten Zustand deutlich schlechter ist, so sind diese Experimente doch wichtig, da sie dem dehydratisierten Zustand der katalysiertenreaktionen entsprechen. Die Adsorption von Testmolekülen wie Acetonitrilund Methylaminauf Zeolith Y oder USY und ihre Auswirkungauf die Bronsted-Zentrenwurde mit ]H high-speed MAS REDORNMR Messungen bei hoher Magnetfeldstärkegemessen. Acetonitril wird an Bronsted- OH-Zentren über Wasserstoffbrücken gebunden, während Methylamin protonierte Spezies bildet (CH3NH3+). In nicht gesteamtem Zeolith Y zeigen nur die Bronsted- OH-Zentren in den Supercages eine Wechselwirkungmit Acetonitril. In USY zeigte ein Teil der Bransted- OH-Zentrenin den Sodalith-Käfigen eine Wechselwirkungmit Acetonitril. Aufgrund seiner hohen Basizität ist Methylamin in der Lage mit den sauren und ]H-{27A1} Zentren in den Super- und Sodalith Käfigen in Wechselwirkung zu treten. Das Verhalten der basischen Moleküle gegenüber den sauren Zentren wird durch post-synthesis Behandlungen des Zeolithen beeinflusst. "State-of-the-art" NMR Experimente lieferten detailierte Informationen über die Zeolithe und deren aktiven Zentren. Diese Erkenntnisse sind essentiel für die Bestimmung von Struktur-Aktivitäts-Beziehungen. Zusammenfassend kann gesagt werden dass vorliegende Arbeit neue Einblicke in die Strukuren der Zeolithe und der aktiven Zentren, sowie in die Wechselwirkung von Testmolekülen mit den aktiven Zentren ermöglichte. Es wurde eine Basis für weitere sturkturelle Charakterisierung der Bronsted-saurenZentren und dem Einfluss von postsynthetischer Aktivierunggeschaffen. Darüberhinaus wurden Hinweise zur Synthese von Zeolithen mit neuartigen Eigenschaftenund erhöter Stabilität gegeben.
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