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Chenhui Wang, [Nobuyuki Sakai](https://orcid.org/0000-0002-9395-6751), [Yasuo Ebina](https://orcid.org/0000-0003-3471-9825), [Takayuki Kikuchi](https://orcid.org/0000-0003-0588-2172), Justyna Grzybek, Wieslaw J. Roth, Barbara Gil, [Renzhi Ma](https://orcid.org/0000-0001-7126-2006), [Takayoshi Sasaki](https://orcid.org/0000-0002-2872-0427)

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[Construction of Hierarchical Films via Layer‐by‐Layer Assembly of Exfoliated Unilamellar Zeolite Nanosheets](https://mdr.nims.go.jp/datasets/7202758a-8c78-4ccf-9dfb-d31b9c940ce6)

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Construction of Hierarchical Films via Layer‐by‐Layer Assembly of Exfoliated Unilamellar Zeolite NanosheetsRESEARCH ARTICLEwww.small-journal.comConstruction of Hierarchical Films via Layer-by-LayerAssembly of Exfoliated Unilamellar Zeolite NanosheetsChenhui Wang, Nobuyuki Sakai, Yasuo Ebina, Takayuki Kikuchi, Justyna Grzybek,Wieslaw J. Roth, Barbara Gil, Renzhi Ma, and Takayoshi Sasaki*Zeolites have been widely applied as versatile catalysts, sorbents, and ionexchangers with unique porous structures showing molecular sievingcapability. In these years, it is reported that some layered zeolites can bedelaminated into molecularly thin 2-dimensional (2D) nanosheetscharacterized by inherent porous structures and highly exposed active sites.In the present study, two types of zeolite nanosheets with distinct porousstructures with MWW topology (denoted mww) and ferrierite-related structure(denoted bifer) are deposited on a substrate through the solution process viaelectrostatic self-assembly. Alternate deposition of zeolite nanosheets withpolycation under optimized conditions allows the layer-by-layer growth oftheir multilayer films with a stacking distance of 2–3 nm. Furthermore,various hierarchical structures defined at the unit-cell dimensions can beconstructed simply by conducting the deposition of mww and bifernanosheets in a designed sequence. Adsorption of a dye, Rhodamine B, inthese films, is examined to show that adsorption is dependent on constituentzeolite nanosheets and their assembled nanostructures. This work hasprovided fundamental advancements in the fabrication of artificialzeolite-related hierarchical structures, which may be extended to other zeolitenanosheets, broadening their functionalities, applications, and benefits.1. IntroductionSoft-chemical process of delaminating/exfoliating layered ma-terials into unilamellar nanosheets dispersed in solution andreassembling them as building blocks is one of the mostC. Wang, N. Sakai, Y. Ebina, T. Kikuchi, R. Ma, T. SasakiResearch Center for Materials Nanoarchitectonics (MANA)National Institute for Materials Science (NIMS)1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanE-mail: sasaki.takayoshi@nims.go.jpJ. Grzybek, W. J. Roth, B. GilFaculty of ChemistryJagiellonian UniversityGronostajowa 2, Kraków 30–387, PolandThe ORCID identification number(s) for the author(s) of this articlecan be found under https://doi.org/10.1002/smll.202308293© 2024 The Authors. Small published by Wiley-VCH GmbH. This is anopen access article under the terms of the Creative Commons AttributionLicense, which permits use, distribution and reproduction in anymedium, provided the original work is properly cited.DOI: 10.1002/smll.202308293effective approaches for designing andfabricating advanced nanostructured ma-terials with desired functionality.[1–6] Thetailored structures and specific propertiesassociated with them can be constructed byprecisely controlling the arrangements ofselected nanosheets or other components ata molecular scale. It has been reported thata range of homo- or hetero-multilayer filmsconsisting of various 2D nanosheets canbe constructed layer-by-layer on a supportthrough mechanical transfer,[7] sequentialadsorption,[8–10] spin-coating,[11–13] onedrop assembly,[14] and Langmuir–Blodgettdeposition.[15–17] The latter four are basedon the solution processes, which aresuitable for facile fabrication of centimeter-wide films. The supports for layer-by-layerassembly can be flat substrates withsmooth or rough surfaces or even poly-mer beads in various sizes,[17–19] and thefilm thickness can be controlled stepwiseat the nanoscale range by the numberof deposition cycles. The superlattice-like structures of alternately restackeddifferent nanosheets can be successfullyconstructed by this simple procedure, providing new and en-hanced functionalities, useful for ferroelectric/dielectrics,[20,21]photocatalysis,[22–25] electrocatalysis,[26–28] photo- and electro-chemical energy storage,[29–33] and photoluminescence.[34,35]Thus, layer-by-layer assembly has been proven to be a ver-satile and powerful method to develop functional materialswith precisely controllable designed structures. A wide range ofcolloidal 2D nanosheets such as graphene, chalcogenides, ox-ides, and hydroxides are available as building blocks for theseprocesses,[3,4,36,37] demonstrating high potential for achieving ad-vanced functionalities and applications. Thus, it is of significantimportance to extend the application of the layer-by-layer assem-bly technique to novel nanosheets as building blocks, which maycreate unique materials and achieve sophisticated applications.Zeolites possess diverse structures with well-defined porousframeworks, which have been widely used as industrial cata-lysts and adsorbents.[38–42] Intensive efforts have been devotedto the synthesis of new zeolite frameworks with improvedperformance.[43,44] However, there are still limitations in achiev-ing tailored pore size, accessibility of active sites, and structurediversity.[45,46] The traditional zeolites have extended 3D struc-tures, but ≈10% of them have been shown to have a secondSmall 2024, 20, 2308293 © 2024 The Authors. Small published by Wiley-VCH GmbH2308293 (1 of 10)http://www.small-journal.commailto:sasaki.takayoshi@nims.go.jphttps://doi.org/10.1002/smll.202308293http://creativecommons.org/licenses/by/4.0/http://crossmark.crossref.org/dialog/?doi=10.1002%2Fsmll.202308293&domain=pdf&date_stamp=2024-01-28www.advancedsciencenews.com www.small-journal.comFigure 1. Top and side views of the structures for a,b) mww nanosheets and c,d) bifer nanosheets represented by the FER structure.form, consisting of layers that can condense into the extended3D framework.[47] These unique classes of layered zeolites areexpected to break through the limitations of the traditional 3Dforms.[47–50] In particular, if they are exfoliated into single lay-ers, the resulting products, or unilamellar zeolite nanosheets, aremolecularly thin with a very high aspect ratio and ultimate ex-posure of active sites.[51,52] In contrast to the other known 2Dnanosheets, the zeolite ones can have internal open channels,which provide unique properties and opportunities. For example,such open channels facilitate the transport of ions and moleculesespecially across the nanosheets, which has been a big obstaclefor other 2D materials due to absence of channels/pores. On thebasis of these advantages, 2D zeolite nanosheets can be envi-sioned for promising applications, such as sensing, adsorption,storage, catalysis, separation, and others, wherein abundant ac-tive sites and fast diffusion of ions/molecules can play importantroles in enhancing their performance.Recently, we have reported the preparation of two kinds ofhigh-quality zeolite nanosheets with MWW topology (denotedmww)[53] and a ferrierite-related structure (denoted bifer)[54] byexfoliating the corresponding layered zeolites into colloidal so-lutions of single layers. Zeolite MWW is commercially used forcatalytic alkylation of aromatics and its framework structure iswell-known.[47,55,56] The structure of bifer is unknown but itsunit cell is similar to the zeolite ferrierite and it is preparedwith the template, choline, that is also known to produce fer-rierite layers.[54,57] Recently reported zeolite ECNU-28 shows X-ray diffraction (XRD) data and other features similar to bifer buthas been assigned the framework topology SZR with a cross-section similar to ferrierite.[58] The relationship between biferand ECNU-28 and their exact structure remain to be elucidated.Figure 1 depicts the 2D porous structures of MWW and FER as apossible model for bifer. It is possible to tailor various hierarchi-cal zeolite-based materials using zeolite nanosheets as buildingblocks, which is exemplified by ≈15 different architectures ob-tained with zeolite MWW layers.[50,52] Exfoliated nanosheets al-low combining different frameworks together at the unit cell leveland further expand the zeolite library and its applications. Its con-crete benefits are demonstrated by the reported mixture of biferand mww layers[54] and mixed zeolite hybrids of mww layers andzeolite MFI.[59] The hybrid zeolites exhibit an enhanced catalyticactivity in a model reaction by showing conversions greater thanthe sum of each component alone. A particularly notable capa-bility enabled by exfoliated zeolite nanosheets in comparison tothe standard crystals is a top-down assembly into films and self-standing discs.[53,60] This has a wide range of possibilities but hasbeen rarely reported so far, mainly due to the relative novelty ofsuch liquid zeolite systems.In this work, multilayer films of zeolite nanosheets of mww,bifer, and their composites of different stacking order are fab-ricated by the layer-by-layer assembly process, which involvesalternate adsorption/deposition of cationic polymers and zeo-lite nanosheets. The optimized parameters for the assembly canachieve regular deposition of zeolite nanosheets. The layer-by-layer film growth is demonstrated by monitoring FT-IR spec-troscopy and X-ray diffraction (XRD) measurement/simulation.Various hierarchical nanostructures can be designed by this so-lution process. The adsorption behavior of the fabricated filmsto dye molecules of Rhodamine B is examined, as an examplefor their applications. This work has provided a solid foundationfor the design of new zeolites based onmolecularly thin zeolitenanosheets as 2D building blocks, which will greatly enrich theSmall 2024, 20, 2308293 © 2024 The Authors. Small published by Wiley-VCH GmbH2308293 (2 of 10) 16136829, 2024, 27, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202308293 by National Institute For, Wiley Online Library on [04/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.small-journal.comwww.advancedsciencenews.com www.small-journal.commaterial library and exhibit huge potential for promising appli-cations.2. Results and Discussion2.1. Preparation of mww and bifer NanosheetsLayered zeolites designated as MCM-56 and Al-ZSM-55, whichcontain the mww and bifer layers, respectively, are prepared ac-cording to the previous reports.[53,54] The obtained MCM-56 iscomposed of grains of several micrometers in size (Figure S1a,Supporting Information). Al-ZSM-55 is a mixture of 2 phases,unexfoliable zeolite precursor (formally ZSM-55 producing ze-olite CDO upon calcination) composed of fer layers, 0.9 nmthick, and exfoliating bifer layers which are 1.8 nm thick.[57]The Al-ZSM-55 sample is obtained as platy microcrystals (FigureS1b, Supporting Information). The XRD pattern of MCM-56can be indexed to the hexagonal structure of the mww topologi-cal framework (Figure S2a, Supporting Information).[61] The or-thorhombic unit cell of bifer is similar to that of ferrierite, FER,as well as CDO and SZR zeolite frameworks (XRD shown inFigure S2b, Supporting Information),[57] but its exact structureis unknown.The zeolite nanosheets of mww and bifer are prepared via de-lamination of the layered zeolites MCM-56 and Al-ZSM-55, re-spectively, through a soft-chemical route via osmotic swellingwith tetrabutylammonium hydroxide solution (see Experimen-tal Section for details). Unilamellar nanosheets are separatedfrom the unexfoliated material via centrifugation of crude sus-pensions at an appropriate rotation speed. To optimize condi-tions for collecting unilamellar nanosheets, the samples recov-ered at different rotation speeds are characterized by atomic forcemicroscopy (AFM) observation (Figure S3, Supporting Informa-tion). The solutions obtained from layered zeolites of MCM-56 and Al-ZSM-55 are centrifuged at 20 and 10 krpm, respec-tively, producing turbid suspensions at the top and sedimentsat the bottom. The top suspensions are separated and cen-trifuged at higher rotation speeds of 30 and 20 k rpm, bring-ing about total sedimentation of the dispersed nanosheets. Therecovered glue-like sediments are redispersed in water to pro-duce the suspensions of mww and bifer nanosheets (Figure 2).These suspensions are appropriately diluted and deposited ona Si wafer chip. As observed by AFM in Figure 2, many sheet-like objects with a lateral size of ≈0.2 and 0.4 μm are observed,respectively. Their thickness is ≈2.5 and 2.1 nm, being con-sistent with that for unilamellar mww and bifer nanosheetsreported.[53,54]In-plane XRD data are collected for monolayer films for eachsample on Si supports. Sharp diffraction peaks indicate thehighly crystalline nature of the nanosheets (Figure S4, Support-ing Information). The peaks can be indexed in terms of 2D hexag-onal and rectangular lattices for mww and bifer, respectively. Theunit cell dimensions are refined as a = 1.4284(8) nm for theformer and b = 1.4642(6) nm × c = 0.7450(1) nm for the lat-ter. The a parameter for mww is very close to the in-plane lat-tice parameters of the precursory MCM-56,[47] indicating thatthe host layer architecture is preserved after exfoliation into theunilamellar nanosheets. The 3D structure, i.e., framework topol-ogy, of bifer is not known, but presumably, its internal layerFigure 2. Photographs of colloidal suspensions of a) mww and b) bifernanosheets and corresponding AFM images. The height profiles are ob-tained along the red lines indicated in the AFM images.architecture is preserved upon exfoliation. The obtained mwwnanosheets with the unilamellar thickness possess horizontal in-tralayer 10-member-ring (MR) channels and vertical open bowl-like cavities, with a diameter of 12-MR aperture and a depthof 0.7 nm, on the surface (Figure 1a,b).[55] On the other hand,the bifer unilamellar sheets are initially analyzed based on theFER or CDO structure. Our previous study suggests the FERstructure as more likely, i.e., containing alternating 10- and 6-MR channels parallel to the lateral direction and 8-MR channelsperpendicular to these two channels (Figure 1c,d).[54] As shownin Figure 2, the mww and bifer nanosheets are well dispersedas colloidal suspensions with an opalescent appearance. Theirzeta potentials are measured to be −30 and −32 mV (Figure S5,Supporting Information), indicating their negatively charged na-ture.2.2. Deposition of Zeolite Nanosheets on a SubstrateDeposition of these zeolite nanosheets on a substrate is exam-ined. Since the nanosheets are negatively charged, polycationssuch as poly(diallyldimethylammonium) chloride (PDDA) areemployed to facilitate adsorption by electrostatic attraction. Inthe first step, a cleaned Si wafer substrate is primed with PDDAto turn the surface positively charged and, in the subsequentprocess, it is immersed in a colloidal suspension of the zeoliteSmall 2024, 20, 2308293 © 2024 The Authors. Small published by Wiley-VCH GmbH2308293 (3 of 10) 16136829, 2024, 27, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202308293 by National Institute For, Wiley Online Library on [04/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 3. AFM images a,c) and corresponding height histograms b,d) ofthe Si substrate surface after deposition of mww and bifer nanosheets, re-spectively. The deposition time is 15 min and the nanosheet concentrationis 0.08 and 0.12 g dm−3, respectively.nanosheets. The nanosheet concentration and deposition timeare studied as key deposition parameters. The resulting filmsamples are observed by AFM, to gain information on how thezeolite nanosheets are deposited. Figure 3a,c depicts AFM im-ages of the samples after adsorbing the nanosheets under typicalconditions. It is obvious that the substrate surface is densely cov-ered with nanosheets. As shown in Figure 3b,d, the histogramis composed of multiple peaks at 1.1, 3.4, 5.7, 8.1, 10.5 nm formww and 1.3, 3.5, 5.6, 7.7, 9.8, and 12.0 nm for bifer. Notethat the peak intervals roughly correspond to each nanosheetthickness. This indicates that the first peak with the smallestheight, the second peak, and the following peaks should repre-sent the regions uncovered by the zeolite, i.e., bare Si surface,covered by monolayer nanosheets, and by multiple overlappednanosheets, respectively. The relative abundance of each areais estimated to assess how the nanosheets are adsorbed on thesubstrate. Through such analysis of films fabricated with vari-ous deposition parameters (Figures S6–S9, Supporting Informa-tion), the optimum deposition time and concentration are de-termined under the criteria to achieve a larger monolayer areaas well as a smaller uncovered region (Figure S10, Support-ing Information). The optimum deposition parameters chosenare 15 min and 0.08 g cm−3 for the mww film fabrication, and15 min and 0.12 g cm−3 for the bifer film (Figure 3). The differ-ence between these optimum conditions may reflect the differ-ent lateral sizes, thicknesses, and charge densities of the mwwand bifer nanosheets. Under these optimum parameters, theratio of the uncovered gap and the covered region in a mono-layer, bilayer, and tri-layer are ≈12%, ≈38%, ≈34%, and ≈15%with mww nanosheets, respectively, while ≈8%, ≈36%, ≈33%,and ≈14% with bifer nanosheets. This film architecture maylook rather disorganized, but actually, similar film quality hasbeen reported for films of other 2D materials such as metaloxide nanosheets.[9,10] The formation of uncovered regions andoverlapped areas is inevitable for such self-assembly processeswith 2D materials possessing submicrometer-scale lateral di-mensions.2.3. Multilayer Build-Up of Zeolite NanosheetsHaving the optimized parameters, multilayer films of zeolitenanosheets are constructed by alternately depositing zeolitenanosheets and PDDA layers, which is similar to the mul-tilayer build-up of metal oxide nanosheets.[8–10] The layer-by-layer deposition is monitored by Fourier transform infrared (FT-IR) spectroscopy. The mww and bifer nanosheets exhibit ab-sorption bands in the wavenumber range of 1000–1100 cm−1(Figure 4a,b), which are ascribed to the antisymmetric stretch-ing vibration Si-O─Si between tetrahedra.[62,63] This band is tripledegenerated, due to the presence of three oscillators (3N-6). Allthree vibrations are active in IR. The maximum at 1058 cm−1is very symmetric, suggesting the absence of the maxima de-rived from Si─O─Al bridges, due to low Al content for bifer.[64]The absorbance increases linearly with the number of depo-sition cycles for both cases (Figure 4c). This indicates that anearly equal amount of nanosheets was deposited in each cycle,demonstrating the successful growth of multilayer films of ze-olite nanosheets. The absorbance increment per layer is 0.0060at 1072 cm−1 and 0.0114 at 1058 cm−1 for mww and bifer films,respectively.The fabricated multilayer films are further characterized byXRD analysis (Figure 5). The ten-layer mww film exhibits twopeaks at 2.6° and 5.7°, which are indexed to the 001 and 002 re-flections from the restacked structure with the intersheet spacingof 3.4 nm (Figure 5a). This value can be reasonably explained interms of the stacked mww nanosheets (2.5 nm in thickness) ac-commodating PDDA between them. On the other hand, the ten-layer bifer film shows two basal peaks at 3.5° and 7.3°, indicatingthe intersheet spacing of 2.5 nm (Figure 5b), which is again con-sistent with the multilayer structure of bifer nanosheets (2.1 nmin thickness) with intercalated PDDA.Furthermore, a simulation of basal diffraction series has beenconducted based on the ten-layer multilayer structures. The sim-ulated profiles (red line) are generally in accord with the ex-perimental XRD pattern (blue) in terms of the peak position(Figure 5; Figure S11, Supporting Information), confirming theordered layered structures based on the building blocks of mono-layer mww and bifer nanosheets. The sharp basal peaks fromthe ideal structures appear together with the Laue ripple peaks(Figure S11a,e, Supporting Information). The broad nature ofthe observed patterns should be ascribed to some structural dis-order as can be deduced from the deposition behavior of thenanosheets giving uncovered gaps and overlapped patches be-sides the ideal monolayer region. Such a broadening effect istaken into account by applying the lattice distortion parameter, 𝛼,in Equation (1) (see Experimental section). Then a better fit is ob-tained with 𝛼 = 0.39 nm and 0.24 nm, for the films of mww andbifer nanosheet, respectively (Figure 5 and Figure S11c,g, Sup-porting Information).2.4. Heating of Multilayer Films of Zeolite NanosheetsFigure 6 depicts XRD data of the multilayer films of mww andbifer nanosheets before and after the heat treatment at 400 °C.Simulations confirm (Figures S12 and S13, Supporting Infor-mation) that the stacked multilayer structures remain substan-Small 2024, 20, 2308293 © 2024 The Authors. Small published by Wiley-VCH GmbH2308293 (4 of 10) 16136829, 2024, 27, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202308293 by National Institute For, Wiley Online Library on [04/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 4. FT-IR spectra showing the build-up process of multilayer films ofa) mww and b) bifer nanosheets on a Si wafer. c) Absorbance at 1072 cm−1(mww, red) and 1058 cm−1 (bifer, blue) plotted against the number ofrepeating cycles.tially unchanged except for the intersheet shrinkage; from 3.4 to2.3 nm for the mww film and from 2.5 to 1.8 nm for the bifer.The removal of interlayer inclusions through the combustion ofPDDA should be responsible for this contraction. Similar mag-nitudes of shrinkage are observed for multilayer films composedof oxide nanosheets and polycations.[65]Figure 5. The measured (blue line) and simulated (red line) XRD patternsof a) mww and b) bifer nanosheets. The numbers indicate the reflectionorders. Simulation parameters are N = 10, 𝛼 = 0.39 nm, and N = 10,𝛼 = 0.24 nm, respectively.It is important to point out that the resulting repeating dis-tances, 2.3 nm for mww and 1.8 nm for bifer, are somewhatshorter than the apparent layer thickness values based on 3D zeo-lite structures, MWW and FER zeolites, with c-axis lengths equalto 2.520 and 1.8708 nm, respectively.[47,66] This shorter repeatingdistance can be explained by failure in perfect topotactic conden-sation of neighboring nanosheets. The surface silanols and oxy-gen atoms of the neighboring nanosheets can be interdigitated.Layered zeolite materials with an interlayer distance shorter thanthe theoretical layer thickness have been reported earlier and de-noted “sub-zeolites”.[57] Considering the layer-by-layer assemblyprocess from colloidal suspension, it is reasonable to expect thatthe nanosheets will be preferentially restacked without making aregular sheet-to-sheet registry, making the perfect 3D condensa-tion difficult.2.5. Heteroassembled FilmsLayer-by-layer deposition of multiple zeolite nanosheets in var-ious sequences may produce artificial or superlattice zeolites,bringing about a new diversity of structures, properties, and func-tions of zeolites with emergent applications and performance. AsSmall 2024, 20, 2308293 © 2024 The Authors. Small published by Wiley-VCH GmbH2308293 (5 of 10) 16136829, 2024, 27, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202308293 by National Institute For, Wiley Online Library on [04/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 6. XRD patterns of as-fabricated (blue line) and heated to 400 °C(red line) multilayer films of a) mww and b) bifer nanosheets.a demonstration, three kinds of heteroassembled films with theunit of (mww/bifer)6, (mww2/bifer2)3, and (mww3/bifer3)2 arefabricated by repeating the immersion processes in the designedsequences. The growth of these films was monitored by FT-IRspectra (Figure 7). The absorbance increases with the numberof layers for all samples. Importantly, the absorbance gain is de-pendent on which nanosheet is deposited in the cycle. Its mag-nitude is equal to the values observed in multilayer film growthfor mww and bifer nanosheets; 0.0060 at 1072 cm−1 and 0.0114 at1058 cm−1, respectively. The deposition sequences of mww/bifer,mww2/bifer2, and mww3/bifer3 result in distinct modes of ab-sorbance change, clearly confirming the successful formation ofthe heteroassembled films in the designed structures.These are taken as new zeolites or mixed-layer zeolites, whichcannot be obtained by conventional synthetic methods. The “hi-erarchical zeolites” have been reported recently.[67–69] These hier-archical zeolites/MOFs are directly synthesized in different mor-phological forms for different purposes, for example, nanopar-ticles, sheets/plates, and membranes for applications in catal-ysis, sensing, and gas separation, respectively. In contrast, thehierarchical structures reported in this study are defined at theunit-cell level, typically superlattice assemblies of mww andbifer nanosheets alternately stacked, which cannot be realizedthrough any direct synthetic approach. The obtained ultrathinfilms/coatings are regarded as more favorable for ultrathin cat-alyst layers, high-precision and high-sensitivity sensors, etc.Figure 8 depicts the XRD data for the superlattice filmsof (mww/bifer)6 nanosheets. The experimental profile is ex-tracted by subtracting a baseline based on the Sonneveld–Vissermethod[70] (Figure 8a). XRD simulation is then carried out basedon the superlattice structure of alternate mww/bifer sequence incomparison with the random stacking model (Figures S12 andS13, Supporting Information). The experimental profile lookslike an intermediate pattern between these two models, whichmay be reasonable considering the rather disordered adsorptionof the nanosheets at each deposition step (Figure 8b). Figure S14shows the cross-sectional TEM image of the alternately depositedfilm of (mww/bifer)5. The lamellar fringes are observed and thetotal thickness of 28.9 nm is roughly consistent with an estimatedvalue based on the thickness of the nanosheets and the film archi-tecture. On the other hand, a regular alternate structure of mwwand bifer nanosheets was not clearly resolved, which may be con-sistent with the XRD analysis above.2.6. Dye AdsorptionDye-adsorption capacities of multilayer films of mww and bifernanosheets and their superlattice film of mww/bifer are exam-ined. The films, heated at 400 °C, are immersed in an aqueoussolution of a typical dye, Rhodamine B. After 1 day, the filmsare taken out, rinsed with copious amounts of water, and sub-ject to measurements of UV–visible (UV–vis) absorption spec-tra. A clear absorption band at 567 nm, which is attributable toRhodamine B, is detected in multilayer films of mww nanosheetsand superlattice films of mww/bifer, while it is negligible for thefilms of bifer nanosheets (Figure S15, Supporting Information).Figure 9 shows that the absorbance at 567 nm is almost linearlyenhanced as a function of the mww layer number. The adsorp-tion capacity is clearly dependent on the zeolite nanosheets andthe film architecture.The adsorption capacity of the multilayer films of mwwnanosheets is estimated. Absorbance gain at the peak top(567 nm) is 0.006 per layer of mww nanosheets (Figure 9), con-sidering two films on both sides of the glass substrate. Becausethe molar extinction coefficient of Rhodamine B at 553.5 nm is1.05 × 105 mol−1 dm3 cm−1 (Figure S16, Supporting Informa-tion), the amount of Rhodamine B adsorbed is calculated to be5.83 × 10−11 mol cm−2, which corresponds to 0.46 molecule per2D unit cell area of the mww nanosheet. The mww nanosheet isfeatured with a vertical open bowl-like cavity of 0.7 nm in diam-eter and 0.7 nm in depth on its surface. This cavity space mayaccommodate one dye molecule per unit cell (Figure S17, Sup-porting Information). Note that the mww nanosheet does nothave open channels across it, which means that vertical penetra-tion of the Rhodamine B molecules in the restacked multilayerfilm is not allowed. Furthermore, horizontal 10 MR intrasheetchannels are too small to take up the dye molecules. Thus, thedye molecules may migrate in the intersheet gallery to the cavity,where they are trapped mainly via electrostatic interaction.The XRD data after the dye adsorption (Figure S18, SupportingInformation) shows basal diffraction peaks with a stacking dis-tance of 2.3 nm, which is the same as that before the treatment.Small 2024, 20, 2308293 © 2024 The Authors. Small published by Wiley-VCH GmbH2308293 (6 of 10) 16136829, 2024, 27, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202308293 by National Institute For, Wiley Online Library on [04/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 7. FT-IR absorption spectra in the construction process of heteroassembled multilayer films with a different repeating unit of a,b) mww/bifer,c,d) mww2/bifer2, and e,f) mww3/bifer3; the absorbance at ≈1072 cm−1 of the films. The red and blue traces and circles represent the deposition ofmww and bifer nanosheets, respectively.This suggests that the dye molecule is taken up into the cav-ity without altering the restacked structure. The uptake of Rho-damine B into the bulk 3D zeolite composed of ordered stackingof fused mww layers, MWW-22, has been reported,[71,72] and theadsorbed amount is estimated as 1.1 × 10−4 mol g−1. The abovevalue of 5.83 × 10−11 mol cm−2 calculated for the multilayer filmproduces 1.44 × 10−4 mol g−1, upon conversion to unit mass,showing remarkable similarity between the bulk zeolite and film.This result clearly indicates that the dye adsorption takes placeeven in ultrathin films in a similar way to that in the bulk zeolite.This feature is important, expecting some advantageous applica-tions of zeolite nanofilms.The bifer multilayer film, on the other hand, does not adsorbRhodamine B, apparently because of the absence of such voidspaces on the nanosheet. The 6 and 10 MR channels are too smallfor the dye molecules. The heteroassembled superlattice film ofmww/bifer, can provide the open cavities from mww nanosheets,although their population is half of that in the multilayer film.This may be responsible for the somewhat smaller adsorptioncapacity of Rhodamine B. These results are encouraging, sug-gesting that specific structural materials can be controllably fab-ricated to achieve specific functions through the layer-by-layer as-sembly, which greatly expands the scope beyond the capabilitiesof the conventional direct synthesis process.3. ConclusionWe have successfully demonstrated the construction of artifi-cial zeolite films with unique structures by employing molec-ularly thin zeolite nanosheets as building blocks. A substrateSmall 2024, 20, 2308293 © 2024 The Authors. Small published by Wiley-VCH GmbH2308293 (7 of 10) 16136829, 2024, 27, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202308293 by National Institute For, Wiley Online Library on [04/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 8. XRD patterns of a) experimental profile and b) simulated profileof superlattice films of mww/bifer nanosheets.Figure 9. Absorbance at 567 nm for films of (mww)n, (bifer)n, and(mww/bifer)n/2.primed with polycation is immersed in colloidal suspensions ofmww and bifer nanosheets under optimized conditions, achiev-ing dense coverage of the substrate surface with the nanosheets.Subsequent repetition of this process in a desired sequence en-ables the design of various hierarchical films such as multilay-ers and superlattice films, which cannot be realized throughany direct synthetic approach. Furthermore, this methodologycan be extended to different types of zeolites or various othernanosheets, which expands the potential for zeolite-based mate-rials with designed functionality for various applications. Suchtailored structures with ultrathin thickness are regarded as morefavorable for advanced applications, e g., high-precision and high-sensitivity sensors, ultrathin catalysts layers, adsorbents, and ionexchangers. This potential is expected to grow when other zeo-lite frameworks become available as exfoliated nanosheets,[73,74]especially like MFI with pores perpendicular to its layers enabling3D transport.[60]4. Experimental SectionReagents: Tetrabutylammonium hydroxide solution (TBAOH,10 wt.%, Wako special grade, FUJIFILM Wako Pure Chemical),poly(diallyldimethylammonium) chloride (PDDA, 20 wt.% in water,Sigma Aldrich), Rhodamine B (for fluorescence, Sigma Aldrich). Thesematerials were used as purchased. Milli-Q filtered water was usedthroughout the experiments.Preparation of the Suspensions of mww and bifer Zeolite Nanosheet: Lay-ered zeolites MCM-56 and Al-ZSM-55 were prepared according to theprevious reports.[53,54] The obtained MCM-56 (0.5 g) was dispersed ina TBAOH aqueous solution (10 wt.%, 30 cm3). Then, deionized water(4.5 cm3) was added to the mixture. After shaking for 48 h at 180 rpm,the mixture was first centrifuged at 20 krpm for 30 min to separate theswollen zeolite from the mixture. Then, the sediment was redispersed indeionized water (13 cm3). After shaking for another 48 h, the mixture wascentrifuged to separate the well-exfoliated zeolite nanosheet from the un-exfoliated residue wherein the centrifuge speed was adjusted to accom-plish this target. After washing the obtained nanosheets with deionizedwater two times, the mww nanosheets were dispersed in water to pro-duce a suspension. The bifer nanosheet suspension was prepared fromAl-ZSM-55 by a similar procedure.Layer-by-layer Assembly of mww, bifer, and Their Hetero-Film: The typi-cal layer-by-layer assembly procedure for depositing one zeolite layer con-sisted of four steps. Step I, a cleaned substrate was immersed in a solutionof PDDA (20 g dm−3, pH 9) for 15 min; step II, the substrate was takenout from the PDDA solution and carefully washed with deionized water,followed by flushing with N2 gas stream; step III, the dried substrate wasimmersed in a suspension of the nanosheets at the desired concentrationfor appropriate time. Step IV was the same rinsing procedure as step II.Films with designed structures were fabricated layer-by-layer by repeatingthe procedures with desired nanosheets.Materials Characterization: XRD patterns were recorded with a pow-der X-ray diffractometer (Rigaku, Ultima IV) using Cu K𝛼 radiation(𝜆 = 1.5405 Å). A zeta-potential and particle size analyzer (Otsuka Elec-tronics, ELSZ-2) was employed to measure the zeta potential of the aque-ous suspension. AFM (Hitachi High-Tech Science, AFM5000II) was usedto characterize the topography of the nanosheets. In-plane XRD measure-ments were performed with synchrotron X-ray radiation (𝜆 = 1.1991 Å) atline BL-6C of the Photon Factory, High Energy Accelerator Research Or-ganization. FT-IR and UV–vis absorption spectra are recorded by Fouriertransform infrared spectrometer (Perkin Elmer Instruments, SpectrumOne) and UV–vis spectrometer (Shimadzu, SolidSpec-3700 DUV), respec-tively.Adsorption Tests of Rhodamine B: Zeolite films such as multilayers andsuperlattice films based on mww and bifer nanosheets were fabricated onSmall 2024, 20, 2308293 © 2024 The Authors. Small published by Wiley-VCH GmbH2308293 (8 of 10) 16136829, 2024, 27, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202308293 by National Institute For, Wiley Online Library on [04/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.small-journal.comwww.advancedsciencenews.com www.small-journal.coma quartz glass substrate by layer-by-layer assembly process. Then, the fabri-cated samples were heated at 400 °C for 1 h and soaked in the RhodamineB solution (0.1 mol dm−3) for 24 h. After removal from the solution, thesample was carefully washed with copious amounts of deionized waterto remove the dye from the surface, and UV–vis absorption spectra wererecorded to estimate the amount of adsorbed dye.Simulation of XRD Profile: XRD patterns of zeolite nanosheet films, inwhich the intersheet distance, d, is assumed to show Gaussian distribu-tion, were simulated according to the following equations,I (𝜃) = Lp (𝜃) |F (𝜃)|2 [N + 2N−1∑n = 1(N − n) e−8𝜋2 n𝛼2 sin2𝜃𝜆2 cos(4𝜋nd sin 𝜃𝜆)](1)F (𝜃) =∑njfjexp2𝜋i(2zj sin (𝜃)𝜆)(2)where Lp and F(𝜃) were Lorenz polarization factor and structure factor.The number of the stacked nanosheets, N, is 10 in this case and 𝜃 rep-resents the scattering angle. The parameters of nj, fj, and zj were multi-plicity, atomic scattering factors, and the positions for Si(Al) and O atomsused on the mww and ferrierite structure representing bifer, respectively.The parameter, 𝛼, was the standard deviation of Gaussian distribution asa measure of structural disorder. Detailed calculation procedures for thestructure factors have been described in the previous report.[10]Supporting InformationSupporting Information is available from the Wiley Online Library or fromthe author.AcknowledgementsThe authors greatly acknowledge the support of the World Premier In-ternational Research Center Initiative (WPI), Ministry of Education, Cul-ture, Sports, Science and Technology (MEXT), Japan, and CREST of theJapan Science and Technology Agency (JST) (Grant No. JPMJCR17N1 &JPMJCR22B1). C.W. acknowledges the Japan Society for the Promotion ofScience (JSPS) fellowship (Grant No. P21036). The in-plane XRD measure-ments were performed with the approval of the Photon Factory ProgramAdvisory Committee (Proposal No. 2022G501). The XRD simulations wereconducted with the supercomputer at the Numerical Materials SimulatorStation in NIMS. TEM images were recorded with the assistance of Dr.Daiming Tang in NIMS. Financing was provided with funds from the Na-tional Science Centre Poland, Grant no 2020/37/B/ST5/01258 (for W.J.R.and B.G.) and 2019/32/T/ST5/00188 (for J.G.).Conflict of InterestThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are available from the cor-responding author upon reasonable request.Keywords2D materials, dye adsorption, hierarchical structures, layer-by-layer assem-bly, open channels, unilamellar zeolite nanosheetsReceived: September 20, 2023Revised: December 19, 2023Published online: January 28, 2024[1] A. K. Geim, I. V. Grigorieva, Nature 2013, 499, 419.[2] S. Z. Butler, S. M. 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See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.small-journal.com Construction of Hierarchical Films via Layer-by-Layer Assembly of Exfoliated Unilamellar Zeolite Nanosheets 1. Introduction 2. Results and Discussion 2.1. Preparation of mww and bifer Nanosheets 2.2. Deposition of Zeolite Nanosheets on a Substrate 2.3. Multilayer Build-Up of Zeolite Nanosheets 2.4. Heating of Multilayer Films of Zeolite Nanosheets 2.5. Heteroassembled Films 2.6. Dye Adsorption 3. Conclusion 4. Experimental Section Supporting Information Acknowledgements Conflict of Interest Data Availability Statement Keywords