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The precisely tailored refractive index of optical materials is the key to utilizing and manipulating light during its propagation through the matrix, thereby improving their application performances. In this paper, mesoporous metal fluoride films with engineered composition (MgF 2 :LaF 3 ) are demonstrated to achieve finely tunable refractive indices. These films are prepared using a precursor-derived one-step assembly approach via the simple mixing of precursor solutions (Mg(CF 3 OO) 2 and La(CF 3 OO) 3 ); then pores are formed simultaneously during solidification owing to the inherent instability of La(CF 3 OO) 3 . The mesoporous structures are realized through Mg(CF 3 OO) 2 and La(CF 3 OO) 3 ions, which interacted with each other based on their electrostatic forces, providing a wide range of refractive indices (from 1.37 to 1.16 at 633 nm). Furthermore, it is systematically several MgF 2(1-x) -LaF 3(x) layers with different compositions (x = 0.0, 0.3, and 0.5) to form the graded refractive index coating that is optically consecutive between the substrate and the air for broadband and omnidirectional antireflection. An average transmittance of ≈98.03% (400-1100 nm) is achieved with a peak transmittance of ≈99.04% (at 571 nm), and the average antireflectivity is maintained at ≈15.75% even at an incidence of light of 65° (400-850 nm)., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Heterostructures formed by anatase nanotitania and bidimensional semiconducting materials are expected to become the next-generation photocatalytic materials with an extended operating range and higher performances. The capability of fabricating optically transparent photocatalytic thin films is also a highly demanded technological issue, and increasing the performances of such devices would significantly impact several applications, from self-cleaning surfaces to photovoltaic systems. To improve the performances of such devices, WS 2 /TiO 2 heterostructures obtained by incorporating two-dimensional transition metal dichalcogenides layers into titania mesoporous ordered thin films have been fabricated. The self-assembly process has been carefully controlled to avoid disruption of the order during film fabrication. WS 2 nanosheets of different sizes have been exfoliated by sonication and incorporated in the mesoporous films via one-pot processing. The WS 2 nanosheets result as well-dispersed within the titania anatase mesoporous film that retains a mesoporous ordered structure. An enhanced photocatalytic response due to an interparticle electron transfer effect has been observed. The structural characterization of the heterostructure has revealed a tight interplay between the matrix and nanosheets rather than a simple additive co-catalyst effect.

Noble metal nanostructured films are of great interest for various applications including electronics, photonics, catalysis, and photocatalysis. Yet, structuring and patterning noble metals, especially those of the platinum group, is challenging by conventional nanofabrication. Herein, an approach based on solution processing to obtain metal-based films (rhodium, ruthenium (Ru) or iridium in the presence of residual organic species) with nanostructuration at the 20 nm-scale is introduced. Compared to existing approaches, the dual functionality of block-copolymers acting both as structuring and as reducing agent under inert atmosphere is exploited. A set of in situ techniques has allowed for the capturing of the carbothermal reduction mechanism occurring at the hybrid organic/inorganic interface. Differently from previous literature, a two-step reduction mechanism is unveiled with the formation of a carbonyl intermediate. From a technological point of view, the materials can be solution-processed on a large scale by dip-coating as polymers and simultaneously structured and reduced into metals without requiring expensive equipment or treatments in reducing atmosphere. Importantly, the metal-based films can be patterned directly by block-copolymer lithography or by soft-nanoimprint lithography on various substrates. As proof-of-concept of application, the authors demonstrate that nanostructured Ru films can be used as efficient catalysts for H 2 generation into microfluidic reactors., (© 2021 Wiley-VCH GmbH.)

The electrochemical synthesis of mesoporous ruthenium (Ru) films using sacrificial self-assembled block polymer micelles templates, and its electrochemical surface oxidation to RuO x is described. Unlike standard methods such as thermal oxidation, the electrochemical oxidation method described here retains the mesoporous structure. Ru oxide materials serve as high-performance supercapacitor electrodes due to their excellent pseudocapacitive behavior. The mesoporous architectured film shows superior specific capacitance (467 F g -1 Ru ) versus a nonporous Ru/RuO x electrode (28 F g -1 Ru ) that is prepared via the same method but omitting the pore-directing polymer. Ultrahigh surface area materials will play an essential role in increasing the capacitance of this class of energy storage devices because the pseudocapacitive redox reaction occurs on the surface of electrodes., (© 2020 Wiley-VCH GmbH.)

We report the formation of mesoporous films consisting of SBA-15 particles grown directly onto substrates and their usage as catalysts in esterification of acetic acid and ethanol. The film thickness was altered between 80 nm and 750 nm by adding NH₄F to the synthesis solution. The salt also affects the formation rate of the particles, and substrates must be added during the formation of the siliceous network in the solution. Various substrate functionalizations were tested and hydrophobic substrates are required for a successful film growth. We show that large surfaces (> 75 cm²), as well as 3D substrates, can be homogenously coated. Further, the films were functionalized, either with acetic acid through co-condensation, or by coating the films with a thin carbon layer through exposure to furfuryl alcohol fumes followed by carbonization and sulfonation with H₂SO₄. The carbon-coated film was shown to be an efficient catalyst in the esterification reaction with acetic acid and ethanol. Due to the short, accessible mesopores, chemical variability, and possibility to homogenously cover large, rough surfaces. the films have a large potential for usage in various applications such as catalysis, sensing, and drug delivery.

We demonstrate that polymeric films templated from liquid crystals (LCs) provide basic design principles for the synthesis of mesoporous films with predetermined pore alignment. Specifically, we used LC mixtures of reactive [4-(3-acryloyoxypropyloxy) benzoic acid 2-methyl-1,4-phenylene ester (RM257)] and nonreactive [4-cyano-4'-pentylbiphenyl (5CB)] mesogens confined in film geometries. The LC alignment was maintained by functionalization of the surfaces contacting the films during polymerization. Through photopolymerization followed by extraction of the unreacted mesogens, films of area in the order of 10 cm 2 were obtained. We found that, when restricted to an area either through a mechanical or a configurational constraint, open and accessible pores were incorporated into the films. The average direction of the pores could be determined by the LC director during polymerization, and the average diameter of the pores can be tuned in the range of 10-40 nm by varying the reactive monomer concentration. The polymeric films synthesized here can potentially be used for the ultrafiltration purposes. We demonstrated successful separations of proteins and nanoparticles from aqueous media using the polymeric films. The films exhibited 2 orders of magnitude higher flux when the pores were aligned parallel to the permeate direction compared to the perpendicular direction. Overall, the outcomes of this study provide basic tools for the synthesis of porous polymeric films with predetermined pore directions that can potentially be suitable for separations, drug delivery, catalysts, and so forth.

Creating CsPbBr 3 perovskite nanocrystals with bright blue emission is challenging because their optical properties depend sensitively on structure. Growing perovskites in mesoporous templates bypasses some of these purification issues because the size of the nanocrystal is governed by the dimensions of the pores. Mesoporous silica consisting of aligned channels with tunable diameter can be easily synthesized and used as a template. When the perovskite solution evaporates and retreats, some of the liquid remains trapped in the interconnecting pores by discontinuous dewetting. The precursor crystallizes, generating stable ca. 3.1 nm blue-emitting perovskite nanocrystals. The mesoporous template also serves as a protective barrier to preserve the optical properties of the CsPbBr 3 from atmospheric conditions. Compared to the bulk crystals and the powder composite, the strong blue-shift of the emission peak in the film is accompanied by a decrease in the longer lifetime component and an 8-fold increase in the external quantum efficiency., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Mesoporous Ni and Cu-Ni (Cu 20 Ni 80 and Cu 45 Ni 55 in at. %) films, showing a three-dimensional (3D) porous structure and tunable magnetic properties, are prepared by electrodeposition from aqueous surfactant solutions using micelles of P-123 triblock copolymer as structure-directing entities. Pores between 5 and 30 nm and dissimilar space arrangements (continuous interconnected networks, circular pores, corrugated mesophases) are obtained depending on the synthetic conditions. X-ray diffraction studies reveal that the Cu-Ni films have crystallized in the face-centered cubic structure, are textured, and exhibit certain degree of phase separation, particularly those with a higher Cu content. Atomic layer deposition (ALD) is used to conformally coat the mesopores of Cu 20 Ni 80 film with amorphous Al 2 O 3 , rendering multiphase "nano-in-meso" metal-ceramic composites without compromising the ferromagnetic response of the metallic scaffold. From a technological viewpoint, these 3D nanoengineered composite films could be appealing for applications like magnetically actuated micro/nanoelectromechanical systems (MEMS/NEMS), voltage-driven magneto-electric devices, capacitors, or as protective coatings with superior strength and tribological performance.

The precise control of primary reactions in solutions is one of the most significant steps for the nanoscale design of inorganic solids in multidisciplinary fields. However, further growth of the inorganic species to give bulkier species disturbs such designs. The surfactant-assisted synthesis of mesoporous materials is a good strategy for addressing such concerns because pores formed by supramolecularly mediated processes are surrounded by nanometer-sized continuous frameworks. Many experiments are generally conducted to optimize the reaction conditions for the synthesis of highly ordered mesostructures. Herein, to minimize such trial-and-error efforts, a new and practical concept is proposed for the precise design of porous materials. By adjusting the reactivity between bisphosphonates and metal sources through molecular design of the starting bisphosphonate compound, it was possible to synthesize mesoporous films with unique compositions by a surfactant-assisted approach., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanofluidics based on nanoscopic porous structures has emerged as the next evolutionary milestone in the construction of versatile nanodevices with unprecedented applications. However, the straightforward development of nanofluidically interconnected systems is crucial for the production of practical devices. Here, we demonstrate that spontaneous infiltration into supramolecularly templated mesoporous oxide films at the edge of a sessile drop in open air can be used to connect pairs of landmarks. The liquids from the drops can then join through the nanoporous network to guide a localized chemical reaction at the nanofluid-front interface. This method, here named "open-pit" nanofluidics, allows mixing reagents from nanofluidically connected droplet reservoirs that can be used as reactors to conduct reactions and precipitation processes. From the fundamental point of view, the work contributes to unveiling subtle phenomena during spontaneous infiltration of fluids in bodies with nanoscale dimensions such as the front broadening effect and the oscillatory behavior of the infiltration-evaporation front. The approach has distinctive advantages such as easy fabrication, low cost, and facility of scaling up for future development of ultrasensitive detection, controlled nanomaterial synthesis, and novel patterning methods.

In the present work, 2.4 nm gold nanoparticles (Au NPs) are uniformly dispersed on mesoporous titania thin films which are structurally tuned by controlling the calcination temperature. The gold content of the catalyst is as high as 27.8 wt %. To our knowledge, such a high loading of Au NPs with good dispersity has not been reported until now. Furthermore, the reaction rate of the gold particles is enhanced by one order of magnitude when supported on mesoporous titania compared to non-porous titania. This significant improvement can be explained by an increase in the diffusivity of the substrate due to the presence of mesopores, the resistance to agglomeration, and improved oxygen activation., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Enhancement of Raman scattering signal through graphene is an important property that could be exploited for producing innovative sensing devices with advanced properties. Because the enhancement of Raman scattering is due to only a chemical mechanism, the amplification of the signal is lower than that one produced by excitation of localized surface plasmons. The combination of a highly selective technique, which is molecular imprinting, with graphene-mediated enhanced Raman scattering, represents a new synergistic approach that we have developed in the present work. The careful material design has allowed obtaining a porous composite embedding exfoliated graphene and molecular cavities specifically designed for recognizing Rhodamine 6G. The molecularly imprinted porous samples have shown a signal enhancement that increases as a function of the number of molecular cavities, which are also accountable for the molecular recognition properties. Environmental ellipsometric porosimetry has shown no substantial difference between molecularly imprinted and not-imprinted films confirming that the signal enhancement of the imprinted samples is due to the molecular cavities. Interestingly, the most efficient sample has shown a Raman enhancement per cavity that exceeds the value of 1 × 10 12 and a remarkable molecular selectivity allowing for a Rhodamine 6G signal amplification 4.5 higher than structural analogues such as Rhodamine B and methylene blue. The robust and flexible matrix ensures a good recyclability of the samples without lack of linear response. These results prove the great potential of molecular imprinting as a general strategy to provide selectivity to GERS-active substrates for a new generation of sensing devices.

In this work, we introduce a facile method based on host-guest chemistry to synthesize a range of nanostructured TiO 2 materials using supramolecular templates of a dendron-jacketed block copolymer (DJBCP). The DJBCP is composed of amphiphilic dendrons (4'-(3,4,5-tridodecyloxybenzoyloxy)benzoic acid, TDB) selectively incorporated into a P4VP block of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) via hydrogen bonding. The PS-b-P4VP host acts as a structure-directing template, while the guest molecules (TDB) assist the self-assembly nanostructures and zone-axis alignment, resulting in the nanostructured template of vertically oriented cylinders formed via successive phase transformations from Im3̅m to R3̅m to P6mm upon thermal annealing in the doctor-blade-cast film. The guest molecules subsequently direct the titania precursors into the P4VP domains of the templates via supramolecular guest exchange during immersion of the film in a designated precursor solution containing a P4VP-selective solvent. The subsequent UV irradiation step leads to the formation of PS-b-P4VP/TiO 2 hybrids. Finally, removal of the host template by calcination leaves behind mesoporous channels and makes sacrifices to be a carbon source for carbon-doping TiO 2 materials. Various TiO 2 nanoarchitectures, namely, vertical and wiggly micrometer-length channels, inverse opals, fingerprint-like channels, heterogeneous multilayers, and nanotubes, have been fabricated by highly tunable DJBCP nanostructures.

A new method of producing high-quality perovskite films via sequential deposition is presented, introducing a PbX2 capping layer that is endowed with a network of interconnected nanopores. The mesoporous lead halide architecture provides a powerful tool to accomplish rapid and complete transformation of lead halide into the perovskite for high-efficiency solar cells., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The formation of highly ordered chiral organic/inorganic films with high density and long-range orientation is important in constructing chiral devices, such as broadband polarization devices, liquid-crystal displays, or negative-reflection materials. A feasible strategy is presented to fabricate three-dimensional mesostructured chiral DNA-silica assemblies into large-scale oriented arrangements. The highly ordered film was aligned by a mica crystal substrate with the bridging effect of suitable divalent metal ions, followed by the growth of the DNA-silica composite by bottom-up assembly with a "quartet templating" method. This simple and effective route would perform well in the alignment and arrangement of highly charged biomolecules, such as polypeptides, proteins, viruses, and their inorganic assemblies, and furthermore could allow the fabrication of chiral optical materials with long-range ordering., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A hybrid material comprising metal nanoparticles embedded in functionalized mesoporous thin films was constructed, and its use as a selective SERS-based sensor was demonstrated. The presence of specific functional groups in the pore network allows control over the surface chemistry of the pores, tuning the selectivity for specific molecules. Amino-functionalized hybrid mesoporous thin films were used in a proof of concept experiment, to discern the presence of methylene blue (MB) in mixtures with acid blue (AB), with no need for any sample pretreatment step. Selective detection of MB was possible through entrapment of AB in the mesoporous matrix, based on its high affinity for amino groups. The sensor selectivity can be tuned by varying the solution pH, rendering a pH responsive surface and thus, selective SERS-based sensing. The developed sensors allow specific detection of molecules in complex matrixes.

Highly transparent mesoporous titanium dioxide (TiO2; anatase) thin films were prepared at room temperature via ultraviolet (UV) irradiation of hybrid polymer-TiO2 nanoparticle thin films. This approach utilized a UV-curable polymer in conjunction with the photocatalytic activity of TiO2 to form and degrade the organic component of the composite films in one step, producing films with well-controlled porosity and refractive index. By adjustment of the loading of TiO2 nanoparticles in the host polymer, the refractive index was tuned between 1.53 and 1.73. Facile control of these properties and mild processing conditions was leveraged to fabricate robust one-dimensional photonic crystals (Bragg mirrors) consisting entirely of TiO2 on silicon and flexible poly(ethylene terephthalate) substrates. The mesoporous Bragg mirrors were shown to be effective chemical vapor sensors with strong optical responses.