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Ordered Mesoporous Zeolite Thin Films with Perpendicular Reticular Nanochannels of Wafer Size Area Hsueh-Jen Chang, Tzu-Ying Chen, Zi-Ping Zhao, ZihJyun Dai, Yu-Lin Chen, Chung-Yuan Mou, and Yi-Hsin Liu Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.8b03789 • Publication Date (Web): 05 Nov 2018 Downloaded from http://pubs.acs.org on November 5, 2018

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Chemistry of Materials

Ordered Mesoporous Zeolite Thin Films with Perpendicular Reticular Nanochannels of Wafer Size Area Hsueh-Jen Chang,‡,∥ Tzu-Ying Chen,‡,† Zi-Ping Zhao,‡,∥ Zih-Jyun Dai,∥ Yu-Lin Chen,∥ ChungYuan Mou,*,† and Yi-Hsin Liu,*,∥ ∥Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan † Department of Chemistry, and Center for Condensed Matter Sciences, National Taiwan University, Taipei 10617, Taiwan ABSTRACT: Highly-ordered mesoporous zeolite thin films (MZTFs) are grown at rigid substrates via molecular interaction from ternary structure-directing-agents (SDAs) in a Stöber-like condition. The ultrathin films (10-20 nm) were deposited layer-by-layer via self-assembly of beta-zeolite seeds and SDAs at 40-50 ℃, resulting reticular cellular pores and perpendicular nanochannels with average pore sizes (6.7 ± 1.1 nm). The walls of the nanochannels consists of zeolitic structures in microcrystallines. Compared to cylindrical mesochannels of amorphous silica thin films, the MZTFs with reticular mesochannels demonstrate 5R/6R stretching modes (550-650 cm-1) and significantly enhanced hydrothermal stability. The MZTFs were characterized in top-view and cross-sectional electron microscopies (SEM/HRSEM/HRTEM) as well as X-ray scattering techniques (GIXRD/GISAXS), which confirm a body-centered tetragonal (𝐼𝑚3𝑚) unit cell with unique Moiré patterns. Upon calcination, the film thickness is reduced to 10.6 nm with a structure transformation to a hexagonal phase. The hydrothermally stable MZTFs can serve as excellent hard-templates for growing dense nanoparticle arrays and confining their diameters to well-defined sizes (4.8 ± 1.3 nm).

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INTRODUCTION

Silica-,1-10 alumina-,11-14 titania,15-19 COF-,20-21 and MOFbased22-23 thin films with vertical mesochannels have been processed via evaporation-induced self-assembly (EISA),1-3 molecular interaction,4-6 external fields,7 external perturbation force15 and electrochemically assisted selfassembly (EASA).8-10, 22 Recently, Mou and co-workers have demonstrated a general chemical approach of growing large-area mesoporous silica thin films (MSTFs) with perpendicularly oriented mesochannels24 via chemical coassembly of decane with CTAB in Stöber-like solution. The wafer-sized thin film materials with highly uniform perpendicular mesopores for easy mass transport and loading may be useful in nanofiltration,25-26 catalyst supports27-28 and hard templating for growths of other functional nanomaterials.29-32 For example, gold nanoparticle arrays grown on MSTF are successfully demonstrated in SERS applications.29 Additionally, mesoporous silica thin films with large vertical mesochannels have been applied to efficient separation of proteins.27 For high temperature (>550 ℃) applications, high-quality and large-quantity SWCNTs can be synthesized via water-assisted chemical vapor deposition (CVD).33 However, a continuous introduction of water, aqueous precursors and moisture may cause server degradation of MSTF over long term due to its amorphous nature of silica .34-36

Crystalline mesoporous thin film materials, i.e. alumina11-14 and titania,16 with vertical mesochannels are suitable candidates for high-temperature applications. For catalysis purposes, zeolites37-39 possess more abundant acidic sites and microporosity than alumina40-41 and titania.41 Recently, mesoporous zeolites have been synthesized in various methods.42-50 However, mesopore formation via soft-templates or post-etching process always causes poor control of pore shape and size uniformity.42-43 Thus far, desired mesoporous zeolite thin films with vertical nanochannels have not been succeeded yet.51-52 In this work, we demonstrate a successful synthesis of highly-ordered reticular mesoporous zeolite thin films (MZTFs) onto Si wafers and FTO via facile chemical approach of manipulating assemblies of zeolite precursors and three structure directing agents (SDAs), namely cetyltrimethylammonium bromide(CTAB), sodium decyl sulfate(SDS) and decane in a Stöber-like solution. The synthetic approach was rationally adapted from our recent method of growing mesoporous silica thin films (MSTFs) composed of amorphous silica.24 Consequently, the newly synthesized MZTF possesses much higher hydrothermal stability which will be useful in many applications. Understanding detailed process of the self-assembly of the surfactant-zeolite seed system on the surface is important. We also studied closely the formation mechanism of MZTF by various techniques including GISAXS, TEM and SEM.

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RESULTS AND DISCUSSION

Control on Nanochannel Shapes. β-zeolite seeds (BZS)53 were employed as an aluminosilicate precursor to enhance thermal and hydrothermal stability toward hightemperature applications.34-35 In Figure 1, low- and high-

Figure 1. (a) Low-, (b) high-magnification top-view SEM images of MZTFs in using of BZS (Si/Al = 66) and SD10S (155 μM) at 50 °C. Inset: FFT/GISAXS patterns, and its (c) in-plane 1D signals.

magnification SEM images reveal zeolite thin film materials with vertical nanochannels and reticular 2D cellular foam pore shapes. All the zeolite walls appear to be straight instead of curving as observed in our previous MSTF. The vertical orientation of nanochannels is confirmed in combination of top-view SEM and vertical Bragg profiles in grazing-incidence small-angle X-ray scattering (GISAXS). Fast Fourier transform (FFT, inset) and in-plane 1D signals in X-ray scattering (Figure 1c) suggest a non-periodical packing between all adjacent mesochannels. To better understand effects of the anionic surfactant SDS, various concentrations (77.6-310 μM) of SD10S were introduced in the synthetic solution to modulate molecular interactions as well as to control shapes and sizes of mesochannels. Without using SDS, direct assemblies of beta zeolite precursors with CTAB and decane only result in partially oriented nanochannels (Figure S1), morphologically differently from results of ensemble vertical orientation of silica nanochannels of MSTF.24 To better control the vertical orientation and minimize randomness, co-surfactants with various chain lengths and functional groups have been individually introduced to modulate charge densities at solid-liquid interfaces.54 Two structure directing agents, including CTAB, decane and SDS, providing practical intermolecular interactions, are not only served as soft-templates to guide formation of mesostructures but also utilized as nucleating reagents that assist transformation of pre-crystalline precursors (BZS) into solid phases. Among the surfactants studied, the sodium decyl and dodecyl sulfates (SD10S and SD12S)55 could significantly improve the orientation, shapes and sizes of nanochannels (Figure S2-3). In Figure 2, representative SEM results reveal a trend of pore enlargement and shape developments from spherical to reticular mesochannels upon SD10S introduction. The

Figure 2. Top-view SEM images of MZTFs made from beta zeolite seeds with different concentrations of SD10S. (a) 77.6 μM, (b) 155 μM, (c) 310 μM. The histograms are distributions of pore diameters and the inset ones are statistics of n-polygon distributions of reticular nanochannels.

average pore sizes (with standard deviations) are measured as 7.4 (± 1.5), 8.4 (± 2.1), as well as 11.3 (± 3.1) nm, with concentrations of SD10S at 77.6, 155, and 310 μM (Figure S4). An analysis of distributions of polygon sides of 2D cellular foams (f(n)) (e.g. numbers of neighbors) can help one to understand the nature of 2D reticular foam structure. Both the distribution of pore size and polygon side are shown in Figure 2. A shape factor (μ2), as second moment of f(n) for nearness to perfect hexagon is defined as,56 ∞

𝜇2 = ∑ (𝑛 ― 6)2𝑓(𝑛) 𝑛=3

Euler's theorem requires that the mean value of n () is exactly six, on the assumption of 3-fold vertices. One can see in Figure 2c that this theorem is roughly followed (e.g. the value of f(5) is about equal to that of f(7)). For the samples in Figure 2a and Figure 2b, the distribution of f(n) is skewed to pentagons, due to 4-fold vertices. A perfect packing of hexagonally shaped nanochannels would result in a value of μ2 close to zero which requires relative uniform shapes and sizes of reticular nanochannels. The values of μ2 for the three samples in Figure 2a, b, c are 0.28, 0.59 and 0.83 respectively indicating increasing amounts of SD10S tends to favor sharp vertices that lead to deviation from


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hexagons. A linear regression of correlating pore sizes to shape factor (μ2) and SDS concentrations (Figure S4) further confirms an important role of anionic SDS in controlling the reticular shapes in mesopore formation. These mesopores are templated by ternary-surfactants and separated by 1-2 nm zeolite frameworks, resulting into nanochannels with defined thickness and shapes. We hypothesize that the CTAB/SDS pairs are more favorably organized along a flat surface (thus reticular shapes) than pure CTAB which prefers curved surface (spherical shape). As SDS concentration increases, the curvature of CTABSDS micelles decreases as well as the volume of the micelles increases, thus resulting into enlarged pore sizes. To better understand the micelle formation, MZTF synthesis temperature was lowered to 40 ℃ (Figure S5) and anionic surfactants with different alky-chain lengths were thus compared (Figure S2, S6). With a designated amounts and ratios of SD12S to CTAB (Figure S7-8) pre-added into Stöber-like solution, the pore-size distributions and shapes of on-substrate nanochannels significantly become highly ordered and uniform (Figure 3a, b) with coherent grain

Figure 3. (a) Low-, (b) high-magnification top-view SEM images of MZTFs in using of BZS (Si/Al = 66) and SD12S (563 μM) at 40 °C. Inset: FFT/GISAXS patterns, and its (c) in-plane 1D signals.

domain sizes beyond micrometer regimes (Figure 3a). Fast Fourier transform (FFT) and GISAXS (inset) patterns clearly indicate nearly-perfect hexagonal packing with hexagonal diffraction peaks in reciprocal space. GISAXS further reveals highly-ordered in-plane d-spacing correlated in 1:√3:2 ratios (Figure 3c, 0.08, 0.14, 0.16 Å-1), as well as a direct evidence of multiple out-of-plane signals corresponding to perpendicular growth orientation above substrates.

Figure 4. Representative SEM images of thin films before (a for MZTF, b for MSTF) and after (c for MZTF, d for MSTF) hydrothermal stability tests at 100 °C for 3h. (e) DR-IR spectrum of MZTF (upper) and MSTF (bottom).

essentially maintains its structure while MSTF’s structure is mostly lost. For MZTF after a hydrothermal test, the reticular frameworks still remain.34-36, 44-45, 58-60 In contrast, the nanochannels in MSTF collapse and dissolve as a consequence of the hydrothermal treatment, resulting concave morphology without retention of its original morphology. The IR spectrum of two thin film materials (MZTF and MSTF individually made from zeolite seeds and TEOS) are compared in Figure 4e. IR spectrum of MZTF in Figure 4e shows distinct 538, 557, 605 cm-1 34-36, 53 peaks in the range 520-600 cm-1, suggesting the coexistence of fiveand six-member rings (5R, 6R) of T-O-T (T = Si, Al) in zeolites while the IR spectrum of MSTF only shows simple band features below 550 cm-1, similar to those of amorphous materials, e.g. MCM-41.34-35 Specific vibrations for 5R and 6R provide the most direct evidence to rationalize crystallinity and microposity. Both evidences support our first demonstration of zeolite thin film materials having vertical nanochannels as well as crystalline frameworks, showing the crystalline properties as in previous porous thin film materials, e.g. MOFs,22-23 titania15-19 and alumina.11-12 The straight boundary nature in the reticular foam also agree with a highly crystalline nature of the wall.

Evidences of microporosity. Microporosity in βzeolite (BEA) is created by crystalline frameworks of zeolite primary and secondary building units after removal of TEAOH templated in microporous channels and cage cavities.34-36, 42, 53, 57 Thus, a hydrothermal stability property and specific IR vibration modes would suggest the existence of microporosity as well as microcrystalline structures similar to BEA. In Figure 4a-d, we show the SEM micrographs of hydrothermal stability tests (100 °C, 3h) on MZTF (a, c) and MSTF (b, d). One can see that after treating under boiling water for three hours, MZTF



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Table 1. Comparisons of physical properties of MZTF, MSTF, MZN and β-zeolite Characterizations

Morphology (SEM/TEM)

Mesopores after hydrothermal

Structure (IR/Raman)

MZTF

reticulara

retentionc

crystallinec

MSTF

cylindrical24

collapsec

amorphousc

MZN

coral-likeb

β-Zeolite

irregular

Materials & Morphology Thin films

BET analysise Ar (87 K)

N2(77 K)

crystallined

0.4-1.7 nm

4-8 nm

crystalline

0.4-0.8 nm

none

Powder a Figure

3. b Figure 5. c Figure 4. d Figure S10. e Figure 6. More discussion about Raman spectrum is included in Figure S10.

Mesoporous Zeolite Nanoparticles. Crystalline zeolites with meso- and microporosity have long attracted attentions for their advanced catalysis applications since early 2000. During the synthesis of MZTF, mesoporous zeolite nanoparticles (MZNs, Figure 5) were obtained at

Figure 6. (a) Ar and (b) N2 isotherms of MZN (black) and commercial zeolite beta (red). (c) Pore size distributions via NLDFT methods at 87 K (Ar isotherm) and (d) BJH methods at 77 K (N2 isotherm).

Figure 5. Representative (a, b) HRTEM and (c, d) SEM images of MZNs.

the same time (in the solution suspension) as by-products. They can be taken as an informative reference to explore structural features in MZTF and MSTF. XRD (Figure S9) of MZN sample shows broad features centered at 6.32° and other board peaks in wide angles regimes, which can be tentatively assigned to an irregular BEA micropore system (later discussed in Ar isotherm). The MZN also presents microporous and mesoporous characters, including high surface area (SBET = 803-1079 m2/g, Table S1), abundant micropore volume (Vmicro/Vtot = 4.5-10.2%, Table S1) and extended pore size distributions (PSD) from microporous to mesoporous ranges. The PSDs of MZN and commercial microporous BEA were determined and compared via Ar (87 K) and N2 (77 K) isotherms in Figure 6c, d. Argon is a more liable gas than N2 to determine micropores due to smaller cross-section (0.142 nm2 v.s. 0.162 nm2) and

absence of quadrupole moment.61 Recently, non-local density functional theory (NLDFT) with combined advantages of Ar adsorption isotherm results are utilized to determine micropores in zeolites.53, 62 Both MZN and commercial BEA materials show similar PSDs in the microporous regions (0.4-0.8 nm, Figure 6c) while MZN has an extended PSD to the mesoporous regions (2-10 nm, type IV). Comparison of all structural characterizations between MSTF, MZTF and their powder by-powders are listed in Table 1. We conclude the co-existence of microporosity and mesoporosity in MZNs (the by-products during MZTF formation), indicative of crystalline properties in nature. Structural Transformation of MZTF. The uniformity and morphology of nanochannels (a.k.a. mesochannels) are further examined in high-resolution SEM. The top-view HRSEM (Figure 7a, b) and their FFT (insets) images


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Figure 7. Representative (a), (b) top-view and (c), (d) crosssectional HRSEM images of MZTFs with insets of individual GISAXS patterns before (left) and after 540 °C calcination in air (right).

confirm structural retention of such these highly-ordered hexagonal and large-area mesochannels after 540 °C calcination process. There was no significant change to the hexagonal pore structure or FFT patterns from top-view SEM images of MZTF upon calcination (Figure 7a-b, insets). GISAXS of the MZTF before (Figure 7c) and after (Figure 7d) calcination shows that the perpendicular ordered channel structures are essentially maintained. However, small difference between cross-section SEM and GISAXS (Figure 7c, d and insets) indicate subtle changes in mesochannel orientation and thin film thickness. Previously, mesochannel formation, transformation and thickness reduction have all been reported in crystalline thin film materials of anatase titania16 and γ-alumina.12 To examine in-plane hexagonal packing and the out-of-plane phase transformation,63 two experiments, azimuthalresolved GIXRD (Figure 8a, b) and microtome-TEM observation (Figure 8c), were performed. From the TEM microtomed images of as-made MZTF (before calcination treatment), one can see that very few monolayer and most bi-layer film structures are observed (Figure 8c), suggestive of a layer-by-layer growth model for the interfacial micelles. We then re-examine peak intensity upon rotating the azimuthal angle of the in-plane scattering features. Grazing-incidence X-ray diffraction patterns (GIXRD,

Figure 8. (a) Scattering experiment setup for GISAXS and GIXRD. (b) Azimuthal GIXRD spectra (φ scan) at incidence angle (α) of 0.883°. (c) Microtome-TEM image of as-made MZTF having highly ordered mesochannels of mono- (upper) and bi-layers (bottom). Scale bar is 50 nm

Figure 8b) of as-made MZTF reveal two sets of in-phase azimuthal profiles upon full rotation scans (φ, ± 180°) of the sample stage with an incidence angle (α) of 0.883° at in-plane detection position (2θ) of 1.01°. The phase difference between red and blue fitting curves (Figure 8b) suggests a 62.5° staggered geometry between top and bottom layers, regardless of X-ray depth penetration at varied incidence angles. Upon varying the incidence angles (0.883-1.629o), all azimuthal scans indicate similar profiles while the absolute and relative intensities of the azimuthal scanning profiles are altered (Figure S11). The coherence length along mesochannel orientation can be estimated by Scherrer equation according to a smearing broad signal along out-of-plane direction (Figure S12). The calculated coherence length (8.2 nm) agreed with an observed monolayer (~11 nm) in a selected microtome specimen (Figure 8b, upper). Based on the coherence length and thickness estimation in TEM (20.8 nm), a bilayer packing of on-substrate mesopores and corresponding body centered tetragonal phase space group (𝐼𝑚3𝑚 in Figure 9d)12, 64 is thus proposed. This bodycentered tetragonal phase rationally explains the occurring

Scheme 1. Illustration of growth of MZTF via chemical co-assembly and phase transformation.



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chosen to produce Ag2S nanoparticles. In merit of silanol chemical reactivity, MZTF can be tuned into positively charged surface via modification of 3-aminopropyl trimethoxysilane (APTMS), resulting aminofunctionalized surface which attracts and interacts with anionic complexes. MZTFs composed of perpendicular mesochannels, robust zeolite frameworks, large surface

Figure 9. Representative SEM images of (a) MZTF and (b) MZTF having Moiré pattern. (c) 1D pattern from integrated GISAXS signal along in-plane direction. (d) The reflection plane fitting of MZTF (body-centered tetragonal, 𝐼𝑚3𝑚). The lattice constants were fitted as 63.05 and 57.53 Å with linear regression coefficients of determination (R2) of 0.9996.

of bi-layers staggered in angles approximately of π/3 (60°), occasionally resulting unique Moiré pattern in Figure 9b and Figure S13. GIXRD patterns at different incidence angles also reveal an existing of two different azimuthal layers (Figure 8b, S11). The evidences of bilayer and Moiré patterns in as-made MZTF suggests a growth mechanism of a layer-by-layer deposition for zeolite-incorporated micelles (Scheme 1). After calcination, the bi-layer bodycentered tetragonal (𝐼𝑚3𝑚) is gradually transformed into perpendicular nanochannels with 2D hexagonal packing (Figure 7d inset) and reduced thickness (~10.6 nm, Figure S14). Similar to those crystalline titania and alumina thin films, the zeolite thin films with the perpendicular nanochannels are robust substrates for nanoparticle formation under harsh pyrolysis reactions at elevated temperature (Figure S15). Spatial Confinement of Nanoparticles. Silver sulfide (Ag2S) is a narrow bandgap semiconductor with various promising applications, including optoelectronics, electronic conductors, superionic conductors, photocatalyst and photodegradation, as well as thermoelectric materials. Other applications such as heterostructure catalysts, antibacterial materials, biomarkers and plasmonic materials are also welldeveloped. Incorporation of Ag2S nanodots, nanowires and clusters into mesoporous65-66 and microporous materials is strategically important for applications of heterogeneous catalysis.67 Recent developments of incorporating Ag2S into mesoporous substrates were conditionally succeeded via ion-exchange processes.65-66 Instead of using the ionexchange method, a more convenient method of using a single-source-precursor68 and thermal decomposition was

Figure 10. Representative (a) SEM image/FFT (inset) and (b) HRSEM image/FFT (inset) of Ag2S@MZTF. (c) statistical analysis of nanoparticles diameters from SEM image (upper, 5.3 ± 1.1 nm, N = 500) and HRSEM image (lower, 4.8 ± 1.3 nm, N = 171). EDS mapping images of (d) Ag, (e) S, and (f) merged Ag/S for Ag2S@MZTF specimen.

area and abundant porosity are utilized to grow Ag2S nanoarrays on substrates (insets of Figure 10a, b). The nanoparticle sizes were measured via both SEM (5.3±1.1 nm, Figure 10c) and HRSEM (4.8 ± 1.3 nm, Figure 10c, S15). The measured sizes of Ag2S nanoparticles are smaller than the sizes of MZTF mesopores (6.7 ± 1.1 nm, Figure S16-19). Additionally, these Ag2S nanoparticles are randomly scattered without major aggregation, revealed in HRSEM (Figure S21) as well as EDS mapping of Ag, S and merged Ag/S signals (Figure 10d-f). Both HRSEM and EDS results demonstrate a successful example of confining Ag2S nanoparticles inside the mesochannels with a moderate filling density (φ = 46.6 %, Figure S20, 21). Additionally, MZTFs can be chemically grown onto various substrates, including FTO-glass and gold-coated Si wafers (Figure S22), for practice uses. Further catalytic reactions and sensing applications are currently underway.

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CONCLUSIONS

Compared to amorphous thin film materials, newly developed MZTF with reticular hexagonal nanochannels and crystalline framework demonstrate enhanced hydrothermal stability and microporosity. The superior properties indicate formation of zeolite frameworks verified by IR-active ring-stretching modes. GISAXS, GIXRD, and microtome-TEM images confirm the unique bi-layer model growth mechanism with the space group ( 𝐼𝑚3𝑚) for a body-centered tetragonal packing of mesopores. Upon calcination, these mesopores are transformed into perpendicular nanochannels with reticular shape maintained. A wafer-sized thin film


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material with the perpendicular nanochannels (6.7 ± 1.1 nm) are utilized to fabricate on-substrate Ag2S nanoparticle arrays with confined diameters (4.8 ± 1.3 nm). The reticular zeolite thin film materials are highly desired for catalytic reactions and sensing applications as results of their perpendicular, hydrothermally stable, and accessible nanochannels.

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EXPERIMENTAL SECTION

Chemicals. Cetyltrimethylammonium bromide (or cetyltrimethylammonium bromide, CTAB, 99+%, Acros Organics), Decyl sodium sulfate (SD10S, ≥ 98.5%, Acros Organics), Dodecyl sulfate sodium salt (SD12S, 99%, Acros Organics), tetraethylammonium hydroxide (TEAOH, 20% in aqueous solution, Acros Organics), tetraethyl orthosilicate (TEOS, ≥ 99%, Aldrich), fumed silica (Aldrich), decane (99+%, Acros Organics), ethyl alcohol (or ethanol, ≥ 99.5%, Shimakyu’s Pure Chemical), sodium aluminate (NaAlO2, Riedel-de Haen), and aqueous ammonium hydroxide solution (28-30%, Acros Organics) were purchased and used without further purification. Deionized water was filtered in a Millli-Q integral water purification system (Merck Millipore). One-side polished p-type B-doped silicon wafer (4”, 1-20 Ω-cm, Summit-Tech Resource Corp.) and ITO/FTO glass (20×20×0.7 mm, 7Ω/10Ω, Global Tech International) were pre-cleaned with ethanol several times via sonication and rising processes at room temperature. Synthesis of Mesoporous Zeolite Thin Films (MZTF). Synthesis conditions of mesoporous zeolite thin films (MZTF) was adapted from a modified procedure of MSTF.24 The β-zeolite seeds (Si/Al = 66) were prepared by mixing NaAlO2 (0.246 g), fumed silica (12.0 g), TEAOH (39 g), and NaOH (0.30 g) in H2O (32.4 g) under stirring at 50 °C for 5-8 h. Then, the mixture was hydrothermally treated at 100 °C in an autoclave for 18-24 h. In the modified synthesis, an oil-in-water emulsion was prepared by mixing CTAB (0.193 g), SD12S (0.015 g), ethanol (6.0 g) and decane (600 µL) in NH3 aqueous solution (0.6 M, 80 g) at 40-50 °C. A detail comparison of MZTFs under slightly modified synthesis conditions are listed in Table SI-2. Then, a polished silicon or FIO/ITO wafer was directly immersed into the solution, followed by two additions (separated by 5 min) of β-zeolite seed (BZS) precursor69 aqueous solution (1.0 mL at each step, 20% by volumes) under stirring at 40°C overnight. The molar ratios of CTAB:SD12S:H2O:NH3:decane:ethanol:BZS were calculated to be 1:0.1:8800:94:5.9:250:2.0. As-synthesized mesoporous zeolite thin films on substrates were purged with N2 prior to SEM and GISAXS analyses. MZTF specimens were rinsed by ethanol and calcined in the air at 540 °C for 9 h to remove organic surfactants. Anchoring Ag2S NPs onto MZTF. The calcined MZTFs were degassed at 160 °C for 2 h and immersed in an alcoholic APTMS solution (1%, v/v) at 40 °C for 24 h.70 The functionalized MZTFs were cleaned via sonication in ethanol for 5 min, dried in vacuum at RT for 1 h, and then

soaked in silver thiosulfate complex solution (0.251 M sodium thiosulfate and 0.065 M silver nitrate)68 at 25 °C for 16 h. The adsorption process was conducted in dark to avoid photo-decomposition. The complex-adsorbed MZTFs were rinsed with water, dried in ambient condition, and then annealed at 160 °C in air for 90 min, resulting formation of Ag2S nanoparticles arrays. Characterization. Synchrotron-based and in-house GISAXS (Grazing Incidence Small Angle X-ray Scattering) are both utilized in this work. Synchrotron scattering was conducted at BL23A station at National Synchrotron Radiation Research Center (NSRRC) in Hsinchu, Taiwan. The incidence X-ray energy of 15 keV (0.83 Å) and the sample-to-detector distance of 2.80 m result in a q-range of 0.01-0.62 Å-1 that is equivalent to real space distance of 62.8-1.013 nm. The angle of incidence of each X-ray beam was varied between 0.1 and 0.3°. The scattering data extraction was performed in an X-ray scattering image analysis package (POLAR) installed in NSRRC. Alternatively, in-house scattering experiments were conducted by a grazing-incidence geometry (NanoViewer, Rigaku) that includes a two-dimensional (2D) area detector (Rigaku, 100K PILATUS). The instrument in the Department of Chemical and Materials Engineering, National Central University (Taoyuan, Taiwan) is equipped with a 31 kW mm-2 generator (rotating anode X-ray source with a Cu Kα radiation of λ = 0.154 nm). The scattering vector, q (q = 4π/λsinθ), along with the scattering angles θ in these patterns were calibrated using silver behenate (CAS number of 2489-05-6). Top-view and edge-view micrographs were taken on a FESEM (field emission scanning electron microscope, Hitachi S-4800, Hitachi SU8200 and Hitachi SU-8240) operated at accelerating voltages of 2 kV, 5 kV and 10kV, respectively for HRSEM, SEM, and EDS. The MZTF specimen was loaded onto a plate holder with conducting carbon tape adhered at the bottom and silver paint coated at the edges of wafers. The whole specimen was baked at 60 °C overnight prior to SEM imaging. Energy dispersive spectroscopy (EDS) mapping was conducted in Hitachi S-4800. HRSEM images were captured via combination of secondary electron (SE) and backscattered electron (BSE) detectors. Cross-sectional specimens by Focus Ion beam (FIB) and TEM imaging were prepared by MA-TEK (http://www.ma-tek.com/englobal/) in Hsinchu, Taiwan. The thin film samples were deposited with a thick layer of amorphous carbon for specimen protection. The ion source (gallium) accelerated at a voltage of 5-30 kV was employed to cut thin film into slice samples with dimensions of 100×100×50 nm inside the focus ion beam chamber (FIB/SEM, FEI Helios). The slice was laid down on a copper grid with the film lateral orientation parallel to the cross sectional view under TEM (FEI Tecnai G2 F20) imaging. Diffuse reflection Fourier transform infrared (FTIR) spectra of MZTFs/MSTFs adsorption are collected by the Bruker Vertex 70 FTIR spectrometer equipped with heatable, evacuable Pike DiffusIR diffuse reflection accessory with an efficient optical design diffuse reflection. Spectra are recorded in an 800−400 cm−1 range with a resolution of 2 cm−1 under



accumulated 128 scans. Raman spectra of MZNs are collected by Renishaw inVia Reflex Micro-Raman with 532 nm laser. Spectra are recorded in a 600-200 cm−1 range under 1 scan with 10 seconds exposure time. Grazing Incidence X-ray Diffraction (GIXRD) measurement was conducted with D8 DISCOVER with GADDS (Bruker AXS Gmbh, Karlsruhe, Germany) in the National Cheng Kung University (NCKU). Grazing-incidence X-ray diffraction patterns of as-made MZTF upon full rotation scans (φ, ± 180°) at an X-ray incidence angle (α = 0.883-1.629o) with detection is rationally collected at an in-plane diffraction peak at 2θ = 1.01°. N2 and Ar adsorption-desorption isotherms were collected desorption isotherms were collected on Micromeritics ASAP 2020 Plus apparatus at 77 and 87 K. Samples were degassed at 0.05 torr at 250 °C for 20 h prior to the adsorption experiments. Specific surface areas were calculated by BET (Brunauer-Emmett-Teller) method with N2 adsorption-desorption isotherms in linear relative pressure range from 0.05 to 0.14. The mesopore size distribution plots were obtained from the analysis of N2 adsorption isotherm using the BJH (Barrett-JoynerHalenda) method. The micropore size distribution plots were obtained from the analysis of Ar adsorption isotherm using the NLDFT method.

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ASSOCIATED CONTENT

Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Additional MZTFs, MZNs and Ag2S@MZTF experimental results, including SEM images, GISAXS patterns, Azimuthal GIXRD spectra, EDS linescanning analysis and pore sizes determination calculations of MZTFs; XRD, Raman spectra and N2 adsorption properties of MZNs as well as SEM/HRSEM images of Ag2S@MZTF and particle sizes distributions and the filling density of Ag2S.



AUTHOR INFORMATION

Corresponding Authors *E-mail: [email protected] (C.-Y.M.). *E-mail: [email protected] (Y.-H.L.).

ORCID *Chung-Yuan Mou: 0000-0001-7060-9899 *Yi-Hsin Liu: 0000-0001-7069-4536

Author Contributions ‡These authors contributed equally

Funding Sources This research is supported by the Higher Education Sprout Project of National Taiwan Normal University (NTNU) and the Taiwan Ministry of Science and Technology (MOST) under contract No.103-2113-M-003-011-MY2, 105-2113-M-003006-MY2 and 107-2113-M-003-004.

Notes

Page 8 of 11

The authors declare no competing financial interest.

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ACKNOWLEDGMENT

We acknowledge Dr. Yi-Qi Yeh and Dr. U-Ser Jeng (BL23A) at National Synchrotron Radiation Research Center (NSRRC) for assistance in GISAXS studies; Ching-Yen Lin, Ya-Yun Yang at Precious Instrument Center of National Taiwan University for assistance with SEM; Dr. Shieh at MA-TEK (Hsinchu, Taiwan) for FIB specimen and HRTEM; Mr. Chen at E-Hong Instrument Co. Ltd (Taipei, Taiwan) for HRSEM.

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REFERENCES

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