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[Ondřej Veselý](https://orcid.org/0000-0002-8350-7725), [Nobuyuki Sakai](https://orcid.org/0000-0002-9395-6751), [Yasuo Ebina](https://orcid.org/0000-0003-3471-9825), [Takayoshi Sasaki](https://orcid.org/0000-0002-2872-0427)

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[High-Precision Assembly of Molecularly Thin Zeolite Nanosheets into Tiled Mono- and Multilayer Films for Robust Corrosion Protection](https://mdr.nims.go.jp/datasets/c0866b97-b51d-43db-b8b6-649a34a6fba3)

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High-Precision Assembly of Molecularly Thin Zeolite Nanosheets into Tiled Mono- and Multilayer Films for Robust Corrosion ProtectionHigh-Precision Assembly of Molecularly Thin Zeolite Nanosheetsinto Tiled Mono- and Multilayer Films for Robust CorrosionProtectionOndrěj Vesely,́ Nobuyuki Sakai,* Yasuo Ebina, and Takayoshi SasakiCite This: ACS Appl. Nano Mater. 2026, 9, 6618−6630 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: The fabrication of zeolite films by conventionalhydrothermal methods limits their practical use because itproduces irregular, nonuniform thick coatings under harshsynthesis conditions. In this study, to address these limitations,MCM-56 and bifer nanosheets exfoliated from their precursorlayered zeolites were employed, and solution-based depositionmethods were examined to prepare compact nanoscale-thickmonolayer films of neatly tiled nanosheets under mild conditions.Atomic force microscopy revealed that spin coating, the pick-upmethod, and the Langmuir−Blodgett technique yielded high-quality monolayer films with predominantly monolayer coverage of>80% and low surface roughness (<1 nm), in contrast to thepreviously reported electrostatic adsorption method, whichproduced rough and uneven films. By repeating the deposition of monolayer films using the pick-up method, multilayer zeolitefilms were also successfully constructed. Their well-ordered stacked structure was confirmed by the progressive enhancement of theFT-IR band corresponding to Si−O−Si of the zeolite upon repeated deposition of monolayer films, as well as by the sharp X-raydiffraction peaks derived from the multilayer structure. The multilayer films were further deposited on a copper substrate, and theircorrosion resistance was examined. As a result, the corrosion current density decreased by nearly an order of magnitude, and thecorrosion potential shifted toward more positive values. These results indicate that highly ordered zeolite films exhibit pronouncedanticorrosion effects while being deposited to a thickness of only tens of nanometers under mild conditions. These findings provide ageneral strategy for constructing highly ordered ultrathin zeolite films and expand the potential of zeolite nanosheets for functionalsurface coatings.KEYWORDS: zeolite nanosheets, layered materials, exfoliation, layer-by-layer deposition, spin-coating, Langmuir−Blodgett deposition,nanofilm deposition, anticorrosion■ INTRODUCTIONTwo-dimensional (2D) nanosheets derived from layeredinorganic materials have become valuable building blocks forconstructing functional films and novel materials withcontrolled architectures.1−5 Among these materials, zeolitenanosheets�exfoliated from layered precursors such as MCM-56 (MWW) and bifer (FER)6−9�remain relatively overlookeddespite offering an interesting combination of the uniqueporosity, chemical and thermal stability and catalytic activity ofzeolites while being processable as ultrathin 2D layers. Zeolitesare crystalline microporous silicates and aluminosilicates(generally, with pores less than 1 nm in size) whose robustframeworks, adsorption, ion-exchange and catalytic properties,and stability under wide range of conditions have enabledwidespread applications in catalysis and separation technolo-gies.10−13Although most known zeolite structures are three-dimen-sional,14 a small subset of 2D zeolite precursors consists ofdiscrete layers that can be delaminated into nanosheets withthicknesses of only a few nanometers or even just one or twounit cells.15,16 Their layered nature offers a unique flexibilityand variability in their applications; it not only enhances accessto their active sites but also enables various texturalmodifications such as swelling or pillaring,16−20 or trans-formation of the crystalline structure into a different zeoliteframework using the layers as building blocks.21−24 Notably,exfoliation of 2D zeolites into suspension of isolatednanosheets has also been a subject of extensive research.Received: January 13, 2026Revised: March 22, 2026Accepted: March 27, 2026Published: April 7, 2026Articlewww.acsanm.org© 2026 The Authors. Published byAmerican Chemical Society6618https://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−6630This article is licensed under CC-BY 4.0Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on April 17, 2026 at 08:25:38 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Ondr%CC%8Cej+Vesely%CC%81"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Nobuyuki+Sakai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yasuo+Ebina"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Takayoshi+Sasaki"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acsanm.6c00178&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/aanmf6/9/15?ref=pdfhttps://pubs.acs.org/toc/aanmf6/9/15?ref=pdfhttps://pubs.acs.org/toc/aanmf6/9/15?ref=pdfhttps://pubs.acs.org/toc/aanmf6/9/15?ref=pdfwww.acsanm.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://www.acsanm.org?ref=pdfhttps://www.acsanm.org?ref=pdfhttps://creativecommons.org/licenses/by/4.0/Early attempts at zeolite exfoliation utilized swelling bysurfactants or shearing in melt; however, these methods werenotably difficult and provided only limited yields.7,25Conversely, the soft chemical exfoliation emerged as a morepromising method for the exfoliation of 2D zeolites into thesuspension, allowing complete separation of layers under mildconditions and in high yields.7,9,26 These suspensions cansubsequently be utilized in the construction of compositematerials and other structured forms, such as oriented disksand membranes, opening new possibilities for advancedmaterial design.8,9,26Aside from 2D zeolites, various exfoliated 2D materials, suchas graphene, clays, metals, metal oxides, and MXenes, havedemonstrated significant potential for advanced materialdesign, especially in film fabrication or construction ofnanoscale devices including capacitors, electrodes, andsensors.27−31 These materials, when suspended in solution,enable layer-by-layer assembly using methods such as electro-static adsorption,32 the Langmuir−Blodgett (LB) method,33spin-coating,34,35 drop casting,36 and the pick-up method.37Among these, electrostatic adsorption is relatively facile andscalable but typically results in rough, irregular films withoverlapping nanosheets.32,38−40 Spin-coating under optimizedconditions, by contrast, enables improved control over filmthickness and uniformity by adjusting the concentration of thenanosheet suspension and rotation speed.34,35,41 The pick-upmethod uses Marangoni convection to neatly assemblenanosheets into a monolayer film at the water−air interface.In principle, the method is similar to the LB technique;however, the nanosheet assembly is driven by forces at thephase interface instead of moving barriers, making it feasible tocarry out without specialized equipment.37,42,43 Similarly, theLB technique creates closely packed nanosheet layers trans-ferable to solid substrates.33 The method provides highercontrol over the deposition conditions, enabling more precisenanosheet arrangement on flat substrates as demonstrated onlarge variety of 2D materials.5,31,34,37As one of various applications of nanosheet arrangement, aprevious study has successfully demonstrated the use of titaniananosheet film as corrosion protection coating.44 Zeolite-basedfilms could offer several potential advantages. Their insulatingnature, in contrast to the semiconducting character of titaniumoxide, can further suppress electrochemical current flowbetween the metal substrate and the surrounding electrolyte.Moreover, the intrinsic pore system of zeolites can provide thecapacity to host corrosion inhibitors or other active agents forself-healing.45−47 Zeolite coatings have already been reportedto effectively reduce corrosion of various metals, such as steeland aluminum alloys.48,49 However, the reported zeolite filmsare typically around 10 μm thick, rough, and grown directly onsubstrates under harsh hydrothermal conditions, which maydamage the coated materials. Consequently, although theprotective capability of zeolite coatings has been demonstrated,relationship with the film thickness, control over its uniformityand structural ordering, and deposition under mild conditionsremain unresolved. Previous work explored fabrication ofzeolite nanosheet films via electrostatic adsorption.38 However,films produced by this method generally exhibited roughsurfaces and lacked higher-order structural regularity innanosheet stacking. Therefore, it is possible that the intrinsicproperties of zeolites have not been fully exploited. To take fulladvantage of the unique characteristics of zeolites, techniquescapable of producing dense and well-organized packing ofzeolite nanosheets are required.In this study, to address the issue mentioned above, weemploy zeolite nanosheets obtained via soft chemicalexfoliation to demonstrate their applicability in fabricatinguniform films only several nanometers thick. We make acomprehensive comparison of several key methods for thedeposition of exfoliated zeolite nanosheets, including spin-coating, pick-up deposition, and LB method, all of which yieldmore compact and uniform films than the electrostaticadsorption. We further demonstrate that the pick-up methodcan rapidly produce highly ordered multilayer films under mildconditions, resulting in thin coatings (∼20 nm) that provideadequate corrosion protection of metal substrates despite theirminimal thickness.■ EXPERIMENTAL SECTIONSynthesis of MCM-56The MCM-56 was prepared following an established procedure.19First, 2.0 g of 50% NaOH (Merck) was diluted with 52.8 mL ofultrapure water (Milli-Q, >18 MΩ cm) and subsequently 1.3 g ofNaAlO2 (≥53% Al2O3, Carl Roth) was dissolved in the mixture. Uponcomplete dissolution, 10.28 g of SiO2 (Ultrasil VN3) was added,followed by 6.18 mL of hexamethylenimine (>98.0%, TCI). Themixture was transferred to a Teflon-lined steel autoclave and heated at143 °C under rotation at 30 rpm for 32 h. The solid product wasrecovered by filtration, washed with ultrapure water, and dried at 60°C.Synthesis of BiferThe bifer was synthesized following a previously publishedprocedure.9 The synthesis gel was prepared by mixing 30 mL ofultrapure water with 2.5 mL of 50% NaOH (Merck), 0.25 g ofNaAlO2 (≥53% Al2O3, Carl Roth), 10 g of choline chloride (>98.0%,Merck), and 16.2 g of 30% colloidal silica (prepared by diluting 12.15g of LUDOX HS-40 (40%, Sigma-Aldrich) to the requiredconcentration). The synthesis gel was stirred overnight at roomtemperature and subsequently transferred into a Teflon-lined steelautoclave. The crystallization was carried out at 150 °C with rotationat 30 rpm for 11 days. The solid product was recovered bycentrifugation at 5000 rpm for 5 min, washed with water, and dried at60 °C.Exfoliation of MCM-56 and BiferThe zeolite (MCM-56 or bifer) was dispersed in 10% aqueoussolution of tetrabutylammonium (TBA) hydroxide (TBAOH, FujifilmWako) with the ratio of 60 mL g−1. The mixture was shaken for 48 hat 180 rpm and subsequently centrifuged at 10,000 rpm for 30 min toseparate the solid. The sediment was redispersed in the same volumeof ultrapure water and shaken for another 48 h at 180 rpm. Theobtained mixture was centrifuged to separate the suspension ofexfoliated zeolite nanosheets from the unexfoliated solid for 30 min at10,000 and 5000 rpm for the MCM-56 and bifer, respectively. Theunexfoliated solid was redispersed in an equal volume of ultrapurewater and the procedure was repeated one more time to obtain asecond batch of the suspension.38 The concentration of nanosheets inthe suspension was estimated thermogravimetrically by heating anexact volume of the suspension in a platinum crucible at 85 °C toevaporate most of the solvent, followed by calcination at 450 °C for 6h, and then measuring the weight of the remaining solid.Substrate PreparationIndium tin oxide (ITO) glass plates and Si wafers were used assubstrates for the deposition. Prior to the deposition, the ITO glassplates were cut into the desired size (see each method separately)using a diamond-tip cutter and cleaned by oxygen plasma (PIB-20,Vacuum Device). The Si wafers were cleaned by immersion in a 1:1methanol/HCl solution for 30 min and washed with copious amountACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306619www.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asof ultrapure water. Subsequently, they were immersed in aconcentrated H2SO4 for 30 min followed by thorough washing withultrapure water.Electrostatic DepositionThe cleaned substrate (5.0 cm × 1.0 cm) was immersed into a 20 gL−1 solution of polydiallyldimethylammonium chloride (PDDA, 20%in H2O, Sigma-Aldrich, adjusted to pH 9 by addition of 2.5% TBAOHsolution) for 15 min. The excess PDDA was washed away withcopious amount of ultrapure water and subsequently the substrate wasimmersed for 15 min into a 0.08 g L−1 suspension of respective zeolitenanosheets adjusted to pH 9.1 with 0.01 M HCl, according to theconditions optimized in our previous work.38 The coated substratewas washed with copious amount of ultrapure water and dried in air.32Spin-CoatingPrior to the spin-coating, 1 mL of the aqueous suspension of zeolitenanosheets was centrifuged at 15,000 rpm for 30 min to sediment thenanosheets and decanted, and the sediment was redispersed in 0.5 mLdimethyl sulfoxide (DMSO, 99%, Fujifilm Wako) to obtain the zeolitenanosheets dispersed in DMSO.ITO glass plates or Si wafers (1.5 cm × 1.5 cm) were used assubstrates for the deposition. The cleaned substrate was anchoredonto the sample holder of a Mikasa MS-B100 spin coater, coveredwith 60 μL of the DMSO-based suspension and rotated at therespective rotation speed for 800 s. The temperature was maintainedat 26.5 ± 0.1 °C during the spin-coating.35Pick-Up DepositionThe aqueous zeolite suspension was mixed with 99.5% ethanol in a1:1 v/v ratio. A Petri-dish with an inner diameter of 93 mm was half-filled with ultrapure water and subsequently 8.62 μL of the preparedsuspension was carefully dispensed onto the water−air phaseboundary using a pipet to form a zeolite film on the liquid phase.The film was let to settle for 3 min (unless stated otherwise) beforethe deposition. The film was transferred onto the cleaned ITO glassplates or Si wafers (1.5 cm × 1.5 cm) by scooping it up from thephase boundary using tweezers with the substrate wafer itself. Thecoated substrate was placed onto a heater at 100 °C to evaporate thewater.37Langmuir−Blodgett (LB) DepositionIn a typical procedure, the zeolite nanosheet suspension was dilutedwith ultrapure water to a concentration of 8 mg L−1, and was placed inthe LB trough (USI FSD-3−777 double barrier Langmuir trough withTeflon coating, trough volume 250 mL, Wilhelmy-type balance forsurface pressure measurement) at a regulated temperature of 25.0 ±0.5 °C. After 30 min of equilibration, the barrier began compressingthe suspension surface at a rate of 0.5 mm s−1 until the surfacepressure reached 10 mN m−1. The constant pressure was maintainedfor 30 min, and then the film at the interface was transferred onto thecleaned substrate (5.0 cm × 1.0 cm) by lifting up the preimmersedsubstrate at a rate of 1.0 mm min−1.33Anticorrosion TestsPotentiodynamic polarization/Tafel curves and electrochemicalimpedance spectroscopy (EIS) data were obtained using a SolartronSI 1280B electrochemical measurement unit. The measurement wascarried out in an aqueous 3.5 wt % NaCl solution with standard three-electrode system, where a zeolite-coated copper plate, a coiled Pt wire,and an Ag/AgCl (3 M NaCl) electrode served as the workingelectrode, the counter electrode, and the reference electrode,respectively. Polished copper plates were separately coated with 3,5, or 10 subsequent layers of bifer nanosheets using the pick-upmethod, and with 10 layers using the electrostatic adsorption. Thecoated copper plates were covered with a Kapton tape with circular5.5 mm hole, topped with an O-ring and placed into a Teflon-madeevaluating cell (Plate Material Evaluating Cell, BAS Inc.). Themeasurements were performed on the sample polarized at ± 150 mVwith respect to its open circuit potential (OCP) at a scan rate of 0.167mV s−1 after the systems reached their steady-state condition (stableOCP) for at least 60 min. Values of corrosion potential and corrosioncurrent density were determined from the intersection of linear fits tothe measured anodic and cathodic current. The EIS data wereacquired at OCP with an amplitude of 5 mV and a frequency rangefrom 10 kHz to 100 mHz.CharacterizationX-ray diffraction (XRD) data were collected using a Rigaku Ultima IVpowder diffractometer with monochromatized Cu Kα radiation (λ =0.15406 nm). Scanning electron microscopy (SEM) images wereobtained using a JEOL JSM-6010LA SEM at an acceleration voltageof 1 and 3 kV for deposited nanosheets and bulk samples, respectively.In-plane XRD measurements were performed using synchrotron X-rayradiation (λ = 0.11988(4) nm) at BL-6C, Photon Factory, HighEnergy Accelerator Research Organization (KEK). AFM imaging wascarried out using a Hitachi AFM5200S scanning probe microscopeequipped with a SI-DF20 cantilever in tapping mode. Zeta potentialof the nanosheet suspensions was analyzed using an OtsukaElectronics ζ-potential and particle size analyzer ELSZ-2. Brewsterangle microscopy (BAM) images were collected using the Kibron G-BAM equipped with a 660 nm excitation laser, set at an incident angleof 53° (the Brewster angle for the air/water interface) relative to thesurface normal. Fourier-transform infrared (FT-IR) spectra wererecorded using the Thermo Scientific Nicolet Summit X FT-IRspectrometer equipped with iD1 Transmission module. The peakareas were obtained by integration of the area under the peak between980 and 1150 cm−1. Cross-sectional transmission electron microscopy(TEM) images of the 10-layer bifer nanosheet films deposited on Siwafers were obtained using a JEOL JEM-2100F1 field-emissiontransmission electron microscope (FE-TEM) operated at anacceleration voltage of 200 kV. The TEM specimen was preparedby a focused ion beam (FIB) process after depositing carbon on thefilm. The adhesion test was performed by applying and removing anadhesive tape in accordance with the ISO 2409 standard on the 10-layer bifer film.Simulation of XRD ProfilesSimulation of basal diffraction patterns has been conducted based onthe bifer structure according to the previously reported procedure.The layer structure factor F was calculated according to the eq 1:9,32,33=ikjjjjikjjj y{zzzy{zzzzF n f i zexp 2 2sinjj j j(1)where nj, f j, θ, and λ are the number of atoms, atomic scatteringfactors, diffraction angles, and X-ray wavelength, respectively. Theintensity I was estimated as the product of Laue interference functionand the square of the structure factor as described in the eq 2:Scheme 1. Schematic of the Synthesis, Exfoliation, and Deposition of Zeolite NanosheetsACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306620https://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=sch1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=sch1&ref=pdfwww.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-as= · *·I F FNhhsin ( )sin ( )22 (2)where the second term is the Laue interference function and N = 10in this case.■ RESULTS AND DISCUSSIONExfoliated Nanosheets and Their Assembly viaElectrostatic AdsorptionLayered zeolites MCM-56 and bifer were synthesized andexfoliated by following previously established procedures(Scheme 1),8,38 yielding colloidal suspensions of single-layernanosheets with lateral dimensions ranging from 0.2 to 0.5 μmand thickness ca. 2.5 nm for MCM-56 and 2.1 nm for bifer(Figures S1 and S2), which are in good agreement withpreviously reported dimensions of single-layer nanosheets,supporting successful exfoliation to single-layer sheets. Thepreservation of their intrinsic crystalline structure wasconfirmed by in-plane XRD measurements (Figure S3). Theobserved diffraction peaks matched the intralayer reflectionsreported for MCM-56 and bifer, consistent with boththeoretical patterns and prior literature, verifying thepreservation of their internal structure after exfoliation.The previous work investigated the electrostatic adsorptionand optimized the deposition conditions. Coating with 0.08 gL−1 for 15 min provided coverage between 80% and 90% bothfor MCM-56 and bifer nanosheets. We repeated the experi-ments, verifying the previous results and using the data forTable 1. Characteristics of the Deposited Zeolite Films Depending on the Deposition Methods Derived from AFMMeasurementsamethod zeolite Ra (nm) uncovered (%) monolayer (%) overlaps (%)electrostatic adsorption MCM-56 3.04 ± 0.48 19.8 38.3 41.9bbifer 2.25 ± 0.12 19.3 33.3 47.4bspin-coating MCM-56 1.02 ± 0.10 13.1 67.5 19.4bifer 0.48 ± 0.08 4.5 90.8 4.7pick-up MCM-56 1.04 ± 0.19 4.9 79.3 15.8bifer 0.66 ± 0.07 3.3 85.1 11.6Langmuir−Blodgett MCM-56 0.74 ± 0.03 <1 89.6 10.4bifer 0.75 ± 0.04 8.0 74.9 17.1aThree 5 μm × 5 μm images each. bIt includes not only double layers but also overlaps of three or more layers.Figure 1. AFM images and corresponding height histograms of MCM-56 nanosheets deposited on the Si wafer by spin-coating their suspension(0.4 wt % in DMSO) at (a, d) 1000 rpm, (b, e) 1200 rpm followed by 1000 rpm, and (c, f) 1400 rpm followed by 1000 rpm.ACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306621https://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig1&ref=pdfwww.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ascomparison purposes.32,38,39 While this method is facile andstraightforward, it consistently produced films with significantnanosheet overlap and high roughness due to the ratherirregular adsorption of nanosheets to the substrate surface(Figure S4). The average surface roughness (Ra) and ratios ofarea which is uncovered, covered by monolayer, and coveredby overlapping nanosheets of the prepared films aresummarized in Table 1. These are consistent with previouslyreported data.38Spin-Coating of Zeolite NanosheetsPrevious studies have successfully used spin-coating to achievedense packing of titania nanosheets.5,35 Therefore, weexamined the possibility of using this method to producecompact films of zeolite nanosheets. Spin-coating was appliedto a 0.4 wt % suspension of MCM-56 nanosheets in DMSO todemonstrate the applicability of the method to the zeolitenanosheets in forming a highly uniform film. At 1200 rpm,uncovered dark areas at the substrate center were evident inthe SEM images (Figure S5a−c), but these diminished withdecreasing speed to 1100 rpm (Figure S5d−f), anddisappeared entirely at 1000 rpm (Figure S5g−i), whichresulted in a complete substrate coverage. However, AFMimages revealed significant nanosheet overlaps (Figure 1a, d),showing that 62% of the area at the center and 35% at theperipheral regions were covered by more than one layer(Scheme S1 illustrates how single-layer nanosheets, gaps, andoverlaps appear in AFM images, as well as the definition of thecenter and peripheral regions of the substrate), suggesting theneed for optimization of the spin-coating conditions. A two-step rotation process was devised and employed to minimizeoverlaps; with an initial high-speed step (1200−1400 rpm for10 s) to expel the excess suspension from the substrate,followed by a prolonged low-speed rotation (1000 rpm for 800s) to slow down solvent evaporation and providing sufficienttime for the nanosheets to self-assemble on the solvent surfaceand to deposit a uniform monolayer film. At an initial speed of1200 rpm followed by 1000 rpm, nearly perfect monolayerfilms were obtained, with 67% of the area at both the centerand peripheral regions covered by a single layer, while minoroverlaps accounted for up to 26% at the center and 12% at theperipheral regions (Figures 1b, e and Figure S6a−c). Thesurface roughness was estimated to be 1.03 nm, which is muchsmoother than that of the film obtained by the electrostaticadsorption process (Table 1). In contrast, initial speedsexceeding 1400 rpm caused film breakage, leaving large,uncovered areas and reducing surface coverage. While an AFMimage obtained at the substrate center showed total coverageonly 2%, an image obtained at the peripheral regions showed64% of its area covered by overlapping nanosheets (Figure 1c, fand Figure S6d−f).The same workflow applied to a 0.4 wt % suspension of bifernanosheets in DMSO proved less complex. A single-steprotation at 1000 rpm resulted in complete substrate coverage(Figure S7a−c), though AFM images revealed significantnanosheet overlaps, with 40% of the area covered by a singlelayer and 48% by overlapping nanosheets (Figure 2a).Increasing the rotation speed to 1200 rpm produced a near-perfect monolayer with 96% surface coverage, showing onlyminor ruptures in the center and 5% overlapping nanosheets,while 91% of the area was covered by a single-layer (Figure 2band Figure S7d−f). This eliminates the need for the two-steprotation used for MCM-56. The surface roughness wasestimated to be 0.50 nm, which is even smaller than that ofthe MCM-56 film (Table 1). We successfully achieved a well-ordered monolayer tiling of zeolite nanosheets via the spin-coating method.Assembly of Zeolite Nanosheets via Pick-Up MethodSubsequently, we applied the pick-up method to a 0.3 wt %suspension of MCM-56 nanosheets in a water/ethanolmixture, and the film forming at the water−air interface wasscooped and transferred onto a Si substrate. Strikingly, theresults varied depending on the timing of the transfer. Whenthe film was picked up immediately after applying thesuspension onto the water surface, it exhibited significantoverlaps, and only 57% of the substrate was covered by amonolayer, as observed in the AFM image (Figure 3a).However, delaying transfer by 3 min resulted in a neatly tiledmonolayer, covering 92% of the surface with only occasionaloverlaps up to 15% of the area (Figure 3b). The surfaceFigure 2. AFM images and corresponding height histograms of bifernanosheets deposited on the Si wafer by spin-coating their suspension(0.4 wt % in DMSO) at (a) 1000 rpm and (b) 1200 rpm.ACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306622https://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig2&ref=pdfwww.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asroughness was estimated to be 0.91 nm, which is comparableto that of the film prepared by spin-coating (Table 1). BAMobservations revealed that the film formed almost instantly atthe water−air interface upon introducing the suspension, withno significant macroscopic changes occurring during the delayperiod (Figure S8). We speculated that the improved filmuniformity after a delay is likely a result of larger multilayeraggregates submerging and sinking to the bottom. Never-theless, extending the delay to 30 min yielded no furtherimprovement with a certain small degree of overlappingnanosheets persisting (Figure 3c). It implies that themonolayer forms relatively quickly; however, a certain delaybefore deposition is required. Although 3 min cannot beregarded as a key parameter, a reproducible monolayer filmwas consistently obtained as long as a sufficient waiting time(3−30 min) was allowed.Comparable results were observed for bifer nanosheets, withoverlaps diminishing further at a reduced concentration of 0.25wt %, yielding a neatly tiled film (Figure 4). This concentrationadjustment, however, did not yield similar improvements forMCM-56 nanosheets. Overall, the method produced well-ordered monolayer films in a rapid and straightforwardmanner, and with high quality comparable to those obtainedby spin-coating.Deposition of Zeolite Nanosheet Films viaLangmuir−Blodgett (LB) MethodNext, we focused on the deposition of zeolite nanosheets viathe LB method which has demonstrated high precision inassembling various oxide nanosheets including Ti0.87O2.33 LBdeposition of MCM-56 nanosheets at a surface pressure of 10mN m−1 with an MCM-56 suspension concentration of 8 mgL−1 (Figure S9a) resulted in a densely packed film, with 89% ofthe substrate covered by a single layer, as confirmed by AFM(Figure 5b), suggesting that the behavior of the MCM-56nanosheets closely resembles that of the Ti0.87O2 nanosheets.The surface roughness was estimated to be 0.75 nm, which iscomparable to that of the films prepared by spin-coating andpick-up methods (Table 1). However, occasional nanosheetoverlaps accounting for up to 10% of the area were observed.Reducing the concentration to 4 mg L−1 in order to diminishthe overlaps created significant gaps between nanosheets (26%of the area), compromising film integrity (Figure 5a).Conversely, increasing the concentration to 16 mg L−1 causedexcessive overlaps (21% of the area), with some nanosheetsaggregating into larger multilayer domains (Figure 5c).Figure 3. AFM images and corresponding height histograms of MCM-56 nanosheets deposited on the Si wafer from their suspension (0.3 wt % in1:1 (w/w) water/ethanol mixture) by the pick-up method (a) without delay, (b) after 3 min delay, and (c) after 30 min delay.Figure 4. AFM images and corresponding height histograms of bifernanosheets deposited on the Si wafer via the pick-up method from (a)0.3 wt % and (b) 0.25 wt % suspensions.ACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306623https://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig4&ref=pdfwww.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asThe LB deposition of MCM-56 nanosheets as well as bifernanosheets was also performed under various surface pressures(Figure S9b, c). Decreasing the surface pressure from 10 mNm−1 (Figure 6b, e) to 4 mN m−1 led to less dense nanosheetpacking and the formation of gaps in the films for both MCM-56 and bifer (16% and 63% of the area, respectively), whilesome nanosheet overlaps persisted accounting for 11% of thearea in both cases (Figure 6a, d). Remarkably, increasing thesurface pressure to 16 mN m−1 led to a decrease in the numberof overlaps to 10% and 1%, respectively, and to generation ofnew gaps between the nanosheets (7% and 3% of the area,respectively; Figure 6c, f), showing a deviation from thebehavior previously observed for the Ti0.87O2 nanosheetswhere increasing the surface pressure only produces moreoverlaps.33 This phenomenon was particularly apparent in thebifer film (Figure 6e, f); upon increasing the surface pressurefrom 10 to 16 mN m−1 virtually all overlaps between thenanosheets disappeared, accompanied by a decrease of typicalFigure 5. AFM images and corresponding height histograms of MCM-56 nanosheets deposited on the Si wafer by the LB method at a surfacepressure of 10 mN m−1 with nanosheet concentrations of (a) 4 mg L−1, (b) 8 mg L−1, and (c) 16 mg L−1.Figure 6. AFM images and corresponding height histograms of (a−c) MCM-56 and (d−f) bifer nanosheets deposited on the Si wafer by the LBmethod at a concentration of 8 mg L−1 and surface pressures indicated at the top.ACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306624https://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig6&ref=pdfwww.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asnanosheet lateral size. This observation suggests that theincreased pressure forces more nanosheets to overlap. Theprevious studies reported the tendency of oversized Ti0.87O2nanosheets to submerge over time. The lateral dimensions ofMCM-56 and bifer zeolite nanosheets, ranging from 0.2 to 0.5μm, eliminate such concerns for single-layer nanosheets.However, the overlapping nanosheets may form largermultilayer particles with reduced buoyancy, which subse-quently sink to the bottom of the trough. This producestemporary gaps in the film which are eventually filled bysmaller nanosheets. The LB method also successfully yieldedthe well-ordered monolayer films of zeolite nanosheets.Comparison of the Deposition MethodsThe examined deposition methods each demonstrate uniqueadvantages and limitations, that need to be taken into anaccount before their applications. The electrostatic adsorptionis relatively straightforward, allows for automation, and can bescaled up efficiently, but owing to the nature of the principle,the resulting films are inherently disordered and rough (FigureS4), which does not meet the objective of achieving compact,uniform films. The films produced by the latter three methods(spin-coating, pick-up, and LB) are comparable in quality;compact and uniform, featuring occasional overlaps (Table 1)which appear to stem from nanosheet suspension properties,particularly the nanosheet aggregation dependent on ζ-potential and pH, rather than the deposition methodsthemselves (Figures S10, S11).The spin-coating process offers high precision and versatilitywhen optimized, producing compact and uniform films asconfirmed by AFM imaging (Figures 1b, 2b, and Figure S12).However, it is highly sensitive to experimental conditions, suchas temperature and humidity, and requires solvent exchangewith DMSO, making it less favorable compared to water-basedtechniques.35 Maintaining uniform coverage becomes increas-ingly challenging with larger substrates due to the need fortightly controlled deposition parameters, which limits itspractical scalability and makes it most suitable for relativelysmall substrates (typically ∼1.5 cm × 1.5 cm).In contrast, the pick-up method stands out for its simplicity,time-efficiency, and minimal equipment requirements, produc-ing high-quality uniform films (Figures 3b, 4b). Film formationoccurs through self-assembly at the water−air interface,enabling deposition without specialized instrumentationwhile allowing transfer onto substrates of diverse size, shape,and composition, including Si and ITO glass. Previous studiesby Osada et al. demonstrated that the process can be extendedto printing or continuous roll-transfer approaches, indicatingstrong potential for large-area and industrial-scale fabrication.Although control over nanosheet packing during deposition isinherently less direct than in the other methods, the pick-upmethod produces films of comparable quality to spin-coatingor LB method.Finally, the LB method achieves uniform films with excellentnanosheet packing, as the internanosheet spacing can be tunedby adjusting the compression barriers (Figures 5b, 6e). Thisfeature can yield high film uniformity, but the method requiresspecialized instrumentation, large volumes of nanosheetsuspension, and significantly longer processing times. More-over, the attainable coating area is constrained by the size ofthe LB trough. Among the studied techniques, the pick-upmethod emerges as the most practical choice, combiningexcellent film quality with operational simplicity, cost-effectiveness, and scalability�properties previously demon-strated for other materials,37 but shown here for the first timeto extend to zeolite nanosheets, opening a straightforward andscalable route to fabricate high-quality zeolite nanofilms.Construction of Multilayer FilmsTo assess their suitability of these fabrication methods forpractical applications, where multiple stacked layers may berequired, we further explored repeated deposition into amultilayer film. The layer-by-layer buildup of the multilayerfilms by repeating the monolayer deposition of bifer nano-Figure 7. FT-IR spectra and the area of the peak at 1058 cm−1 plotted against the number of consecutive deposition cycles showing the build-upprocess of multilayer films of bifer nanosheets on the Si wafer using (a, b) the pick-up method and (c, d) the electrostatic adsorption.ACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306625https://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig7&ref=pdfwww.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-assheets using the pick-up method was followed by FT-IRspectroscopy, which revealed a systematic increase in theintensity of the Si−O−Si asymmetric stretching vibration bandat 1058 cm−1.38 The total peak area increased byapproximately 0.209 ± 0.003 units per each deposition cycle(Figure 7a, b), reflecting the consistent growth of themultilayer film. In comparison, the multilayer build-upachieved via electrostatic adsorption exhibited a consistentincrease of the 1058 cm−1 peak area by 0.590 ± 0.015 units percycle (Figure 7c, d). The value was expected to beapproximately two-times higher, as electrostatic adsorptioninherently deposits nanosheets on both sides of the substrate,while the pick-up method coats only one. The net nanosheetuptake normalized per film was thus approximately 1.41 timeshigher for the electrostatic adsorption method, likely due to itsdisorderly deposition, where frequent overlaps result in adenser but less regular film. Deconvolution of the heighthistograms presented in Figure S4b and 4b reveals that thesubstrate is covered by 1.63 and 1.08 layers of nanosheets onaverage when coated using the electrostatic adsorption andpick-up method, respectively. Comparison of these valuesyields a ratio of 1.51, which is in close agreement with the stepvalue ratio of 1.41 obtained from FT-IR spectroscopy. Thisagreement suggests that the densely packed film achieved inthe first layer is successfully reproduced and accumulatedthrough ten repeated depositions using the pick-up method.To examine the stacking order of bifer nanosheets, XRDanalysis was conducted on the multilayer films. For filmsdeposited by electrostatic adsorption, the as-prepared sampleexhibited a broad diffraction peak corresponding to aninterlayer spacing of 2.49 nm (Figure 8a). Upon calcination,the peak became narrower and shifted to 1.79 nm, as a result ofcombustion of TBA ions and dehydration. The obtained valueis slightly lower than the reported bifer nanosheet thickness of1.87 nm, consistent with previously published data.38 Incontrast, films prepared by the pick-up method showed sharp,intense diffraction peaks already in the as-deposited state,indicating a high degree of nanosheet ordering (Figure 8b).The observed spacing of 2.23 nm is in excellent agreementwith the predicted 2.22 nm, derived from the sum of the bifernanosheet thickness (1.87 nm) and the intercalated TBA+ layer(0.35 nm).50,51 After calcination, the diffraction peak shifted to1.83 nm, matching closely with the bifer nanosheet thickness.The experimental XRD patterns are in a good agreement withthe simulated patterns, matching the peak positions as well asattenuation of the intensity of the first order reflection aftercalcination (Figure 8b, Figure S13). The superior ability of thepick-up method to produce well-ordered bifer nanosheet filmsis clearly demonstrated by the good agreement with thesimulated data and sharper, higher intensity of the observedpeaks compared to those from the films prepared by theelectrostatic adsorption.The improvement in the film organization is furthersupported by cross-sectional TEM imaging. Films preparedby electrostatic adsorption exhibit less ordered stacking ofnanosheets, resulting in incomplete condensation and theformation of gaps between adjacent layers (Figure 9a).Consequently, the films display an average thickness of 31.2± 2.5 nm, corresponding to more than ten nominal layers. Thedisorderly stacking causes broadening of the XRD reflectionsindicative of reduced structural ordering. In contrast, filmsfabricated by the pick-up method show an assembly of denselypacked nanosheets with a film thickness of 22.0 ± 2.3 nm,which is noticeably thinner than the film prepared by theelectrostatic adsorption due to the absence of observable voids(Figure 9b). The high-resolution image (Figure 9c) shows aclear lamellar pattern suggesting a parallel alignment of thenanosheets with an elementary thickness of 2.1 ± 0.1 nm,consistent with the interlayer distance indicated by XRD. Thetotal film thickness of 22.0 ± 2.3 nm corresponds to 10−12stacked layers, consistent with AFM height analysis and FT-IRspectroscopic data.Furthermore, in-plane XRD patterns were collected for the10-layer bifer film prepared by the pick-up method (FigureS14). The patterns show sharp high-intensity diffraction peakscharacteristic for the bifer material proving the film integrityboth directly after deposition and after calcination.38 Thenotable absence of h00 reflections further proves the parallelorientation of the nanosheets and highly ordered nature of thedeposited film. The 10-layer film also exhibited sufficientadhesion to the substrate as demonstrated by a peeling testwith adhesive tape. The AFM images and FT-IR spectra(Figure S15) collected prior to and after the test show onlynegligible difference, confirming the durability of the films.Corrosion Protection PropertiesTo explore a practical application of the densely packed zeolitenanofilms, we evaluated their corrosion-protection perform-ance. Mirror-polished copper plates with a surface roughness of1.37 nm were coated with the as-prepared film of bifernanosheets using the pick-up method under conditionsdescribed above. The resulting ten-layer film exhibited asignificant reduction in corrosion current density, decreasingFigure 8. Simulated (orange) and experimental XRD patterns of bifernanosheets deposited in 10 consecutive layers (a) by the electrostaticadsorption and (b) by the pick-up method.ACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306626https://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig8&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig8&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig8&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig8&ref=pdfwww.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asfrom 2.32 × 10−7 to 3.79 × 10−8 A cm−2, accompanied by apositive shift in corrosion potential from −0.179 to −0.110 V(Figure 10a). These changes indicate a marked enhancementin corrosion resistance provided by the nanosheet coating.Systematic variation of the film thickness (3, 5, and 10 layers)revealed a gradual decrease in corrosion current density and acorresponding positive shift in corrosion potential (Figure10b), confirming that the protective effect strengthens withincreasing film thickness.In comparison, as-prepared coating by 10 layers via theelectrostatic adsorption also reduced the corrosion current butonly to 2.21 × 10−7 A cm−2 and shifted the corrosion potentialto −0.158 V (Figure S16), highlighting the superior corrosioninhibition properties of the compact, uniform film produced bythe pick-up method. Compared with earlier studies that havedemonstrated reductions of 2−7 orders of magnitude incorrosion current using 10 μm thick zeolite coatings grownunder harsh hydrothermal or ionothermal conditions, which,while effective, can damage sensitive substrates,48,49 our resultsshow that a zeolite film only tens of nanometers thick canalready suppress the corrosion current of copper by 1 order ofmagnitude while being deposited under mild and sensitiveconditions.Comparable corrosion protection has also been reported forother 2D nanosheet systems. Spray-coated Ca2Nb3O10 filmsreduced the corrosion current by 3 orders of magnitude,although the coatings were substantially thicker (∼1 μm) andless structurally controlled requiring larger amounts of thematerial.52 Similarly, Ti0.87O2 nanosheets assembled byelectrostatic adsorption achieved significant protection, partlyattributed to their larger lateral dimensions, which obstructaccess to the coated surface more effectively.44 Vapor-deposited boron nitride nanocoatings provided improvementscomparable to those observed here but required morespecialized processing.53 These comparisons suggest that thelateral nanosheet size plays a decisive role, and that compact,well-organized assemblies can deliver adequate corrosionprotection even at reduced thickness.To gain a deeper understanding of the corrosion protectioneffect provided by the zeolite nanosheet coating, EISmeasurements were conducted. Compared with the barecopper electrode, an increase in the charge transfer resistancewas observed for the copper electrode coated with nanosheets(Figure S17). Furthermore, the charge transfer resistanceincreased monotonically with increasing number of nanosheetlayers. These results suggest that the compact zeolitenanosheet coating physically inhibits contact between thecopper surface and the electrolyte, thereby providing corrosionprotection for the copper.■ CONCLUSIONSIn the present work, we have examined the arrangement ofexfoliated zeolite (MCM-56 and bifer) nanosheets into neatlyFigure 9. Cross-sectional TEM images of bifer nanosheets depositedusing (a) the electrostatic adsorption and (b, c) pick-up method in 10consecutive layers onto a Si substrate. TEM images reproduced withpermission from Y. Nakayama and Y. Nemoto.Figure 10. (a) Potentiodynamic polarization curves of the copperplates coated with 0, 3, 5, and 10 bifer layers and (b) corrosioncurrent density and corrosion potential plotted as a function ofnumber of bifer layers. The error bars were determined based on threemeasurements.ACS Applied Nano Materials www.acsanm.org Articlehttps://doi.org/10.1021/acsanm.6c00178ACS Appl. Nano Mater. 2026, 9, 6618−66306627https://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsanm.6c00178/suppl_file/an6c00178_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig9&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig9&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig9&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig9&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig10&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig10&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig10&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsanm.6c00178?fig=fig10&ref=pdfwww.acsanm.org?ref=pdfhttps://doi.org/10.1021/acsanm.6c00178?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-astiled monolayer films by employing various depositiontechniques. The deposition by electrostatic adsorption, whilefacile and experimentally undemanding, resulted in inherentlyless ordered and rough films. In contrast, the other depositionmethods, such as spin-coating, pick-up, and LB method,produced uniform films of laterally aligned unilamellarnanosheets with only occasional overlaps. While yieldinghigh-quality films, the spin-coating and LB methods werecomparatively slower and equipment demanding. In contrast,the pick-up approach stood out for its simplicity, speed, andlow equipment demands while yielding comparable filmquality, making it a particularly effective and practical choicefor fabricating high-quality zeolite thin films with low surfaceroughness. The method is also versatile with respect to thesubstrate, as nanosheet films can be assembled on variousmaterials including Si, ITO, and copper, with previous studiesdemonstrating similar assembly on quartz glass and stainlesssteel. Furthermore, repeating deposition by the pick-upmethod produced well-ordered multilayer films of nanosheets.The zeolite nanofilms can effectively improve the corrosionresistance of copper by reducing the corrosion current andshifting the potential toward more positive values. The effectenhances more significant with increasing film thickness up to10 consecutive layers, demonstrating significant corrosionsuppression despite thickness of only several tens of nanome-ters, while being deposited under mild conditions in contrastto previous reports relying on micrometer-scale coatings grownunder harsh conditions. These findings highlight the potentialof zeolite nanosheet films as ultrathin, transparent, andchemically robust coatings for protective corrosion-resistantcoatings which can be easily applied under mild conditionssuitable even for sensitive materials.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acsanm.6c00178.Supplementary experimental details; Characterization ofprecursor layered materials and nanosheets; AFMimages of zeolite nanosheet films prepared by electro-static adsorption; SEM images of nanosheet films; BAMimages of nanosheets assembled at the water−airinterface; Pressure−area (π−A) isotherms during LBdeposition; AFM images and height histograms of filmsprepared from nanosheet suspensions with various ζ-potentials; Structure factor calculated based on the biferarchitecture; In-plane XRD patterns of 10-layer bifernanosheet films; AFM images and FT-IR spectra beforeand after adhesion test; Potentiodynamic polarizationcurves of 10-layer bifer nanosheet film prepared byelectrostatic adsorption; EIS data of bifer nanosheet filmprepared by the pick-up method (PDF)■ AUTHOR INFORMATIONCorresponding AuthorNobuyuki Sakai − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; orcid.org/0000-0002-9395-6751;Email: SAKAI.Nobuyuki@nims.go.jpAuthorsOndrěj Vesely ́ − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; orcid.org/0000-0002-8350-7725Yasuo Ebina − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; orcid.org/0000-0003-3471-9825Takayoshi Sasaki − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; orcid.org/0000-0002-2872-0427Complete contact information is available at:https://pubs.acs.org/10.1021/acsanm.6c00178NotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSThis work was supported by World Premier InternationalResearch Center Initiative (WPI), Ministry of Education,Culture, Sports, Science and Technology (MEXT), Japan, andCREST of the Japan Science and Technology Agency (JST)(grant no. JPMJCR22B1), Japan. The in-plane XRD measure-ments were performed under the approval of the PhotonFactory Program Advisory Committee (Proposal No.2024G501). A part of this work was supported by “AdvancedResearch Infrastructure for Materials and Nanotechnology inJ ap an (ARIM)” o f MEXT . P ropo s a l Numbe rJPMXP1225NM5077. We would like to thank YoshikoNakayama and Yoshihiro Nemoto (Electron MicroscopyUnit, NIMS) for performing TEM observation and YukiHemmi (Materials Forming Unit, NIMS) for preparing ofmirror-polished copper plates.■ REFERENCES(1) Schaak, R. E.; Mallouk, T. E. Perovskites by Design: A Toolboxof Solid-State Reactions. Chem. Mater. 2002, 14, 1455−1471.(2) Lotsch, B. V. Vertical 2D Heterostructures. Annu. Rev. Mater.Res. 2015, 45, 85−109.(3) Timmerman, M. A.; Xia, R.; Le, P. T. P.; Wang, Y.; ten Elshof, J.E. Metal Oxide Nanosheets as 2D Building Blocks for the Design ofNovel Materials. Chem.�Eur. J. 2020, 26, 9084−9098.(4) Jin, X.; Gu, T.-H.; Kwon, N. H.; Hwang, S.-J. 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