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Catalysts 2015, 5 2163 between the zeolite layer and the alumina support [56,57]. Moreover, considerable effort has been directed towards controlled crystal orientation of MFI by in situ applied. Thereby, the surface of the untreated either tubular or disc support is brought in a direct contact crystallization [58–61]. with an aluminosilicate precursor solution and the membrane crystallization is performed under On the other hand, two-step syntheses referred to as secondary growth are hydrothermal conditions as shown exemplarily in the following references [49–55]. Alternatively, applied for zeolite membrane preparation. Therefore, a seeding layer is deposited Caro et al. proposed a seeding-free synthesis strategy for the preparation of dense and phase-pure zeolite on the membrane support at first and the membrane layer is grown in a second LTA and FAU membranes using 3-aminopropyltriethoxysilane (APTES) as covalent linker between the step via hydrothermal synthesis [62–67]. Seeds can be prepared either by bottom-up zeolite layer and the alumina support [56,57]. Moreover, considerable effort has been directed towards approaches [15] or by top-down techniques ex situ. The latter include template controlled crystal orientation of MFI by in situ crystallization [58–61]. assisted nanoscale zeolite syntheses [68,69], exfoliation of zeolite sheets [34,70,71] On the other hand, two-step syntheses referred to as secondary growth are applied for zeolite or simply crushing. The nature of the obtained zeolite membrane depends membrane preparation. Therefore, a seeding layer is deposited on the membrane support at first and the msetmrobnragnleyloaynerthies sgereowdinnginaandsetchoendsustbespeqvuiaenhytdsreocthoenrmdalrysygnrthoewsisth[6te2–c6h7n].iqSueedaspcpalniedbe. pFreipgaurerdee1ithderisbpylabyotstomtw-uop aepxparmoapchles[1o5f]MorFbIymtope-mdobwrnantecshnoiqbuteasinexedsitub.yThtheelattweroin-sctluedpe tehmypdlartoetahsesirsmtedalnapnroespcalreazteiolnitepsryonctheedseusr[e6.8F,6i9g]u, erexf1olaiaitlilounsotfrazeteoslittehseheoeutstc[3o4m,70e,7o1f]aoresicmepnlty crushing. The nature of the obtained zeolite membrane depends strongly on the seeding and the development resulting in the most probable thinnest membrane ever reported [34]. subsequent secondary growth technique applied. Figure 1 displays two examples of MFI membranes In detail, MFI-nanosheets were prepared by exfoliation of multilamellar MFI. After obtained by the two-step hydrothermal preparation procedure. Figure 1a illustrates the outcome of a purification, these sheets were supported onto either Stöber silica supports or novel recent development resulting in the most probable thinnest membrane ever reported [34]. In detail, highflux, high-strength porous silica fibre supports. Secondary intergrowth of the MFI-nanosheets were prepared by exfoliation of multilamellar MFI. After purification, these sheets were film was performed using the so called gel-less growth technique first described supported onto either Stöber silica supports or novel highflux, high-strength porous silica fibre supports. by Pham et al. [35]. This approach could be a more powerful strategy for the Secondary intergrowth of the film was performed using the so called gel-less growth technique first preparation of sub-μm membranes compared to the alternative Langmuir through described by Pham et al. [35]. This approach could be a more powerful strategy for the preparation of assembly [36,72]. sub-μm membranes compared to the alternative Langmuir through assembly [36,72]. FFigiguurere11..SSccaannninigngelelcetcrtornonmmicircorgorgarpahpshosfo(fa()aM)MFIFIfifilmlmpprerpeapraerdedbybygegle-le-lsessgsrgorwotwhtohf MoFfIM-nFanI-onsahneeotshoenetasSotnöbaerStsöilbicear suilpicpaorstu(pRpeporitn(teRdepwriitnhtpedermwiistshiopnefrrmomiss[i3o4n].fCrompy[r3ig4h].t (2C0o1p5)yrJioghnt W(20il1e5y)aJnodhnSoWnsil.e);yaanndd(bS)onMsF.)I; amnedm(br)anMeFfIromembabllramniellefrdoMmFbIaslleemdsillaendd subsequent secondary growth (I) MFI membrane; (II) MFI seed layer; and (III) alumina MFI seeds and subsequent secondary growth (I) MFI membrane; (II) MFI seed microfiltration layer on a macroporous alumina support. (Reprinted from [67]. Copyright layer; and (III) alumina microfiltration layer on a macroporous alumina support. (2011) Elsevier). (Reprinted from [67]. Copyright (2011) Elsevier). Figure 1b shows a MFI membrane obtained by seeding of ball milled silicalite used for the functionalization of an inert alumina microfiltration layer (denoted as III in Figure 1b) located on a 6PDF Image | Zeolite Catalysis
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