Yasuaki Tokudome

Layered double hydroxide (LDH)-based monolith with interconnected hierarchical channels: enhanced sorption affinity for anionic species

Monolithic layered double hydroxides (LDHs) with interconnected channels have been expected to enhance sorption rate as well as increase accumulation of anions. Although powder molding can form easily-handled LDH compacts, interconnected channel formation therein has not been achieved. Herein, we demonstrate cm-scale monolithic LDH-based composites with interconnected hierarchical channels via a spontaneous sol–gel reaction. The synthesis was performed on Mg–Al hydrotalcite-type LDHs starting from metal chlorides aqueous/ethanolic solution with poly(ethylene oxide) incorporated. Addition of propylene oxide triggers a sol–gel reaction to form monolithic xerogels with a formula of [Mg0.66Al0.33(OH)2Cl0.33·2.92H2O]·3.1Al(OH)3. LDH crystals together with aluminum hydroxide crystals homogeneously build up gel skeletons with well-defined hierarchical channels. The interconnected channel in μm range (macrochannel) are formed as a phase-separated structure, whereas the channel in nm range (nanochannel) are as interstices of primary particles. The channel architectures are preserved in the course of rehydration process, affording enhanced sorption affinity for anion species in the process. Both of macro and mesochannels as well as high charge density of the obtained LDHs (Mg/Al = 2.0) contribute to enhanced anion sorption in the monolithic xerogels. The materials obtained here opens up applications of high performance adsorbents and ion-storage free from diffusion limitation.

Switchable and reversible water adhesion on superhydrophobic titanate nanostructures fabricated on soft substrates: photopatternable wettability and thermomodulatable adhesivity

A titanate nanotube (TNT) film is demonstrated to provide a switchable and adhesive hydrophobic surface. The surface adhesivity is reversibly switched from adhesive to repellent by mild heating and spontaneous rehydration. A persistent superhydrophobic/superhydrophilic pattern can be fabricated on the TNT films coated on soft substrates.

Hierarchical Nested Wrinkles on Silica−Polymer Hybrid Films: Stimuli-Responsive Micro Periodic Surface Architectures

Stimuli-response on hierarchically-structured surface wrinkles is required for advanced filtration, catalysis and sensing applications. Although conventional processes can form hierarchical surface wrinkles, incorporation of stimuli-responsive features has not been achieved, limiting the potential multi-scale functionality of wrinkles. Here, we demonstrate a novel process that can fabricate stimuli-responsive surface hierarchical structures on silica−polymer hybrid films through precisely controlled UV-polymerization and sol-gel condensation. Starting from uniform hybrid films, UV excitation of the film surface triggers the formation of micrometre-scale wrinkles with dual periodicity. Hierarchical nested wrinkle (NW) structures with controllable periodic lengths at discrete size scales of < 10 µm and > 23 µm show a shape-memory effect with changes in the surrounding humidity. Moreover, the individual responses of wrinkles with different periodicities can be controlled independently. As a proof-of-concept application, we demonstrate that the NW structures are an active size-selective adsorption/release surface for micrometre-sized particles.

Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry

Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.

Transparent and robust siloxane-based hybrid lamella film as a water vapor barrier coating.

Water vapor barriers are important in various application fields, such as food packaging and sealants in electronic devices. Polymer/clay composites are well-studied water vapor barrier materials, but their transparency and mechanical strength degrade with increasing clay loading. Herein, we demonstrate films with good water vapor barrier properties, high transparency, and mechanical/thermal stability. Water vapor barrier films were prepared by the solution crystallization of siloxane hybrid lamellae. The films consist of highly crystallized organic/inorganic hybrid lamellae, which provide high transparency, hardness, and thermal stability and inhibit the permeation of water vapor. The water permeability of a 6 μm thick hybrid film is comparable to that of a 200 μm thick silicon rubber film.

Combining Top-Down and Bottom-Up Routes for Fabrication of Mesoporous Titania Films Containing Ceria Nanoparticles for Free Radical Scavenging

Nanocomposite thin films formed by mesoporous titania layers loaded with ceria nanoparticles have been obtained by combining bottom-up self-assembly synthesis of a titania matrix with top-down hard X-ray lithography of nanocrystalline cerium oxide. At first the titania mesopores have been impregnated with the ceria precursor solution and then exposed to hard X-rays, which triggered the formation of crystalline cerium oxides within the pores inducing the in situ growth of nanoparticles with average size of 4 nm. It has been observed that the type of coordinating agent in the solution plays a primary role in the formation of nanoparticles. Different patterns have been also produced through deep X-ray lithography by spatially controlling the nanoparticle growth on the micrometer scale. The radical scavenging role of the nanocomposite films has been tested using as a benchmark the UV photodegradation of rhodamine 6G. After impregnation with a rhodamine 6G solution, samples with and without ceria have shown a remarkably different response upon exposure to UV light. The dye photodegradation on the surface of nanocomposite films appears strongly slowed down because of the antioxidation effect of ceria nanoparticles.

Positioning of the HKUST-1 metal–organic framework (Cu3(BTC)2) through conversion from insoluble Cu-based precursors

A Cu-based metal–organic framework (HKUST-1 or Cu3(BTC)2, BTC = 1,3,5-benzene tricarboxylate) has been synthesized from insoluble Cu-based precursors and positioned on substrates. Patterning of HKUST-1 was achieved through a two-step process: (1) the positioning of the insoluble Cu-based ceramic precursors on substrates using a sol–gel solution, and (2) the subsequent conversion into HKUST-1 by treatments with an alcoholic solution containing 1,3,5-benzene tricarboxylic acid (H3BTC) at room temperature for 10 min. This technique has been found to be suitable for both inorganic and polymeric substrates. The HKUST-1 pattern on a polymer film can be easily bent without affecting the positioned MOFs crystals. This approach would allow for versatile and practical applications of MOFs in multifunctional platforms where the positioning of MOFs is required.

Molecularly imprinted La-doped mesoporous titania films with hydrolytic properties toward organophosphate pesticides

The present work is aimed at developing a titania-based mesoporous film with catalytic properties toward organophosphate pesticides by combining two different approaches: the molecular imprinting and the self-assembly with a supramolecular template. The mesoporosity of the material has been obtained by using a tri-block copolymer (Pluronic F127) as a micellar template while the molecular imprinted cavities have been templated by a complex between La3+ and bis-4-nitro-phenyl-phosphate. The template removal allowed opening, in one step, both the mesopores and the imprinted cavities with a simultaneous estimation of the active sites. The catalytic activity of the molecularly imprinted and not imprinted films toward the pesticide Paraoxon® has been evaluated by means of UV-Vis spectroscopy titration of the 4-nitro-phenolate released by the Paraoxon® hydrolysis. The analysis of the initial rates of molecularly imprinted and not imprinted films has shown that the presence of a very low number of molecular cavities improves the catalytic properties of the imprinted film when compared to the not imprinted films and the background hydrolysis.

Fabrication of hierarchically porous monolithic layered double hydroxide composites with tunable microcages for effective oxyanion adsorption

Removal of toxic substances from industrial wastes is an urgent issue for realizing a sustainable society. Layered double hydroxides (LDHs) are expected to be an effective adsorbent for toxic anions, especially oxyanions, because of their high anion adsorption capacity and reusability. Monolithic LDH materials with rational meso- and macropores are expected to show high adsorption capacity/rate towards targeted toxic substances owing to their large specific surface area and liquid transport property. Besides fabricating hierarchical pores, size control of microcages in LDH crystals is required to achieve selective removal of oxyanions. Herein, we prepared hierarchically porous monolithic LDH composites with tunable microcages by changing the combination of cationic species in the LDH crystal. Monolithic Mg–, Mn–, Fe–, Co– and Ni–Al type LDH composites with hierarchical pores were successfully prepared via an epoxide-mediated sol–gel reaction accompanied with phase separation. The monolithic Co–Al type LDH composite with hierarchical pores exhibited the highest CrO42− adsorption capacity because its microcage size easily fits the CrO42− size. Also Co–Al type LDH composites adsorbed different oxyanions, depending on their affinity with the LDH, in a SO42−, CrO42−, MoO42− and HVO42− co-existing solution. The pore size controllability in discrete length-scales of micrometers, nanometers, and picometers offers LDHs with tailored surface chemistries and physical properties desirable for effective and selective oxyanion adsorption.

Layered double hydroxide composite monoliths with three-dimensional hierarchical channels: structural control and adsorption behavior

Hierarchically porous layered double hydroxide (LDH) materials have potential in anion-exchange, adsorption and catalysis applications, because of their large surface areas and liquid transportation capabilities. The preparation of monolithic LDH–Al(OH)3 composites with hierarchical μm and nm-scale channels and their adsorption behavior is reported. Monolithic gels were synthesized via sol–gel processing, from metal salt precursor solutions. μm-scale macrochannels spontaneously formed by inducing phase separation during sol–gel transition. nm-scale mesochannels were accommodated as interstices between primary/secondary particles. In this study, these hierarchical channel sizes were controlled. The macrochannel size was controlled by tuning the degree of phase separation. The mesochannel size was controlled independently, by tuning the crystallite size of LDH under different solvothermal conditions. The relationship between pore characteristics and adsorption behavior of tailored hierarchically porous LDH–Al(OH)3 monolithic gels were investigated by using dye molecules as adsorbates. Monolithic gels with larger macrochannels and mesochannels exhibit faster adsorption rate and higher affinity, respectively. LDH–Al(OH)3 monolithic gels with hierarchical channels may have potential in some applications such as biosensing, water purification and catalysis.