Swelling and delamination of inorganic homoionic montmorillonite clay in water-polar organic mixed solvents.

The smectite group of clay minerals (smectites) consists of negatively charged clay layers and interlayer exchangeable cations. They are spontaneously delaminated in water to form single clay layers when the interlayer cations are small alkaline cations such as Na+ or Li+. This phenomenon known as osmotic swelling has fundamental importance in constructing novel clay-based nanomaterials. However, osmotic swelling of smectites has not been systematically investigated in organic solvents although this phenomenon should be useful for developing novel clay-organic nanocomposites. We report herein that montmorillonite, a typical smectite, with monovalent and divalent inorganic interlayer cations shows osmotic swelling accompanied by delamination of clay layers in water-acetonitrile and water-2-propanol mixed solvents, although inorganic interlayer cations have been believed to be inappropriate for delamination of smectites in organic solvents. The delamination is confirmed by a combination of macroscopic sample appearances, XRD patterns, and SEM images. Montmorillonite with interlayer Na+ or Li+ ions shows osmotic swelling in pure water and the mixed solvents but not in pure organic solvents. Montmorillonite with alkaline earth dications in the interlayer spaces is swollen in water-organic mixed solvents but not in either pure water or organic solvents alone. Partial delamination in several systems can be clarified from SEM images even though the sample appearances and XRD patterns do not give firm evidence. Such non-uniform swelling behavior of montmorillonite is related to the disordered stacking of the aluminosilicate layers with different morphologies in the clay powders as observed by SEM.

Real-Time Monitoring of Adsorption-Induced Scrolling of Colloidal Inorganic Nanosheets.

Inorganic nanotubes have attracted much attention due to their unique physicochemical properties. Nanotubes can be prepared by scrolling exfoliated nanosheets under ambient conditions. However, how the nanosheet scrolled in its colloidal state has not been experimentally visualized. In this paper, we directly observed the scrolling process of nanosheets upon adsorption of organic cations. Exfoliated flat nanosheets of niobate and clay in aqueous colloids were found to scroll by adding organic cations, such as exfoliation reagents, to the colloids. Employment of cationic stilbazolium dye enabled in situ observation of the dye adsorption and scrolling by optical microscopy based on changes in color and morphology of the nanosheets. The scrolling was promoted for nanosheets adsorbed with a stilbazolium dye with a longer alkyl chain, suggesting that the interaction between the hydrophobic parts of the dye cations is the driving force of the scrolling. This finding should encourage research on the formation of nanotubes from nanosheets and also provides important guidelines for the selection of appropriate exfoliation reagents when exfoliating nanosheets from layered crystals.

Formation of a Giant Anisotropically Ordered Assembled Structure of Inorganic Nanosheets through an Optically Induced Stream.

Formation of a desirable submillimeter-scaled assembled structure of particles in the colloid is a difficult subject in colloidal chemistry. Herein, a submillimeter-scaled ordered assembled structure consisting of highly anisotropic two-dimensional plate-like particles, niobate nanosheets, was obtained through an optical manipulation technique that was assisted by a scattering-force-induced stream. A 532 nm continuous wave laser beam with a power of 400 mW was used to illuminate a liquid crystalline niobate nanosheet colloid from the bottom side of a sample cell, inducing the stream of oriented nanosheets toward the upper side of the sample cell. As a result, a 200 µm ordered assembled structure consisting of oriented nanosheets was formed. The assembled structure was also characterized by two-dimensional anisotropy, reflecting that the highly anisotropic morphologies of each nanosheet and the shape of that structure were dependent on the polarization of incident illumination. This study has revealed a new noncontact and on-demand way to obtain submillimeter-scaled ordered anisotropic colloidal assembled structures of nanosized particles such as nanosheets, contributing to fundamental materials science and expanding the utilities of nanosheets.

Impacts of negatively charged colloidal clay particles on photoisomerization of both anionic and cationic azobenzene molecules.

Although smectite-type clays are used as heterogeneous media for photofunctional guest molecules, the guest species are limited to cationic or polar molecules because of the intrinsic negative electric charges of clay particles. Nevertheless, in this study, aqueous clay colloids are reported to affect the photoisomerization kinetics of anionic and cationic azobenzene molecules dissolved in the colloids. Under UV-light irradiation, the clay colloids decelerate trans-to-cis isomerization, while under visible-light irradiation, the clay colloids accelerate cis-to-trans isomerization. In addition, the sol-gel transition of clay colloids affects the kinetics. The results considerably expand the applicability of clay colloids as matrixes for functional organic species.

Electrically Induced Alignment of Semiconductor Nanosheets in Niobate-Clay Binary Nanosheet Colloids toward Significantly Enhanced Photocatalysis.

Aqueous binary colloids of niobate and clay nanosheets, prepared by the exfoliation of their mother layered crystals, are unique colloidal systems characterized by the separation of niobate and clay nanosheet phases, where niobate nanosheets form liquid crystalline domains with the size of several tens of micrometers among isotropically dispersed clay nanosheets. The binary colloids show unusual photocatalytic reactions because of the spatial separation of photocatalytically active niobate and photochemically inert clay nanosheets. The present study shows structural conversion of the binary colloids with an external electric field, resulting in the onsite alignment of colloidal nanosheets to improve the photocatalytic performance of the system. The colloidal structure is reshaped by the growth of liquid crystalline domains of photocatalytic niobate nanosheets and by their electric alignment. Niobate nanosheets are assembled by the domain growth process and then aligned by AC voltage, although clay nanosheets do not respond to the electric field. Photocatalytic decomposition of the cationic rhodamine 6G dye, which is selectively adsorbed on clay nanosheets, is examined for the niobate-clay binary nanosheet colloids with or without domain growth and electric field. The fastest decomposition is observed for the electrically aligned colloid without the domain growth, whereas the sample with the domain growth and without the electric alignment shows the slowest decomposition. The results demonstrate the improvement of the photocatalytic performance by changing the colloidal structure, even though the sample composition is the same.

Universal Access to Two-Dimensional Mesoporous Heterostructures by Micelle-Directed Interfacial Assembly.

Two-dimensional (2D) mesoporous heterostructures combining ultrathin nanosheet morphology, periodic porous surface structures, and diverse hybrid compositions have become increasingly important for renewable energy storage and electronics. However, it remains a great challenge to develop a universal method to prepare 2D mesoporous heterostructures. Herein, we report a composite-micelle-directed interfacial assembly method to synthesize heterostructures of an ultrathin 2D material covered with mesoporous monolayers assembled on both sides. To demonstrate the concept, we first fabricated a new sandwichlike carbon@MXene@carbon mesoporous heterostructure through the self-assembly of exfoliated MXene nanosheets and block copolymer F127/melamine-formaldehyde resin composite micelles and subsequent thermal treatment. Finally, we demonstrate that the carbon@MXene@carbon mesoporous heterostructured nanosheets manifest remarkably enhanced electrochemical performance as a cathode material for lithium-sulfur batteries.

Mesoscopic Architectures Made of Electrically Charged Binary Colloidal Nanosheets in Aqueous System.

Inorganic layered materials can be converted to colloidal liquid crystals through exfoliation into inorganic nanosheets, and binary nanosheet colloids exhibit rich phase behavior characterized by multiphase coexistence. In particular, niobate-clay binary nanosheet colloids are characterized by phase separation at a mesoscopic (∼several tens of micrometers) scale whereas they are apparently homogeneous at a macroscopic scale. Although the mesoscopic structure of the niobate-clay binary colloid is advantageous to realize unusual photochemical functions, the structure itself has not been clearly demonstrated in real space. The present study investigated the structure of niobate-clay binary nanosheet colloids in detail. Four clay nanosheets (hectorite, saponite, fluorohectorite, and tetrasilisic mica) with different lateral sizes were compared. Small-angle X-ray scattering (SAXS) indicated lamellar ordering of niobate nanosheets in the binary colloid. The basal spacing of the lamellar phase was reduced by increasing the concentration of clay nanosheets, indicating the compression of the liquid crystalline niobate phase by the isotropic clay phase. Scattering and fluorescence microscope observations using confocal laser scanning microscopy (CLSM) demonstrated the phase separation of niobate and clay nanosheets in real space. Niobate nanosheets assembled into domains of several tens of micrometers whereas clay nanosheets were located in voids between the niobate domains. The results clearly confirmed the spatial separation of two nanosheets and the phase separation at a mesoscopic scale. Distribution of clay nanosheets is dependent on the employed clay nanosheets; the nanosheets with large lateral length are more localized or assembled. This is in harmony with larger basal spacings of niobate lamellar phase for large clay particles. Although three-dimensional compression of the niobate phase by the coexisting clay phase was observed at low clay concentrations, the basal spacing of niobate phase was almost constant irrespective of niobate concentrations at high clay concentrations, which was ascribed to competition of compression by clay phase and restoring of the niobate phase.

Electric-Alignment Immobilization of Liquid Crystalline Colloidal Nanosheets with the Aid of a Natural Organic Polymer.

Inorganic nanosheets obtained by exfoliation of a layered crystal in water form colloidal liquid crystals, and their alignment can be controlled by an electric field. In order to realize the immobilization of the electrically aligned niobate nanosheets without external forces, an aqueous gelator, agar, is introduced to the niobate nanosheet system to utilize the thermosensitive sol-gel transition property of agar. Alignment of nanosheets in a niobate-agar system is performed by applying an electric field above the sol-gel transition temperature, and then, the sample is cooled down, followed by cooling below the transition temperature with the electric field turned off. The aligned structure is kept for more than 24 h after the removal of the electric field. The concentration of agar is a key parameter for both the orientation of nanosheets and the retention of the orientation.

Microscope Observation of Morphology of Colloidally Dispersed Niobate Nanosheets Combined with Optical Trapping.

Although inorganic nanosheets prepared by exfoliation (delamination) of layered crystals have attracted great attention as 2D nanoparticles, in situ real space observations of exfoliated nanosheets in the colloidally dispersed state have not been conducted. In the present study, colloidally dispersed inorganic nanosheets prepared by exfoliation of layered niobate are directly observed with bright-field optical microscopy, which detects large nanosheets with lateral length larger than several micrometers. The observed nanosheets are not strictly flat but rounded, undulated, or folded in many cases. Optical trapping of nanosheets by laser radiation pressure has clarified their uneven cross-sectional shapes. Their morphology is retained under the relation between Brownian motion and optical trapping.

Flow-Induced Assembly of Colloidal Liquid Crystalline Nanosheets Toward Unidirectional Macroscopic Structures.

Multiscale structures of anisotropic nanoparticles up to macroscopic scales are important in order to produce practical materials through nanotechnology. As an example of such structures, hierarchical organization of colloidal liquid crystals of niobium oxide nanosheets yields stripe textures observable by naked eyes. The stripes are generated by the growth of liquid crystalline domains (tactoids) and the alignment of the tactoids under an electric field and gravity applied in the directions orthogonal to each other. The nanosheets forming the tactoids are unidirectionally aligned along the flow induced by gravity, and the aligned tactoids are stretched to be connected each other to form the stripes. Time evolution of the stripes indicates that they are generated during the settlement of the nanosheets. The nanosheets are debundled with the settlement, and thus the stripes are gradually degenerated during the settlement. Larger tactoids cause faster nanosheet settlement and stripe degeneration. The electric field applied orthogonally to gravity has roles of pinning the nanosheets to slow down their settlement and retains the stripes for several hours.

Hydrogels Containing Prussian Blue Nanoparticles Toward Removal of Radioactive Cesium Ions.

Recent reports have demonstrated the practical application of Prussian blue (PB) nanoparticles toward environmental clean-up of radionuclide 173Cs. Herein, we prepared a large amount of PB nanoparticles by mixing both iron(III) chloride and sodium ferrocyanide hydrate as starting precursors. The obtained PB nanoparticles show a high surface area (440 m2. g-1) and consequently an excellent uptake ability of Cs ions from aqueous solutions. The uptake ability of Cs ions into poly(N-isopropylacrylamide (PNIPA) hydrogel is drastically increased up to 156.7 m2. g-1 after incorporating our PB nanoparticles, compared to 30.2 m2 . g-1 after using commercially available PB. Thus, our PB-containing PNIPA hydrogel can be considered as an excellent candidate for the removal of Cs ions from aqueous solutions, which will be useful for the remediation of the nuclear waste.

Asymmetric Supercapacitors Using 3D Nanoporous Carbon and Cobalt Oxide Electrodes Synthesized from a Single Metal-Organic Framework.

Nanoporous carbon and nanoporous cobalt oxide (Co3O4) materials have been selectively prepared from a single metal-organic framework (MOF) (zeolitic imidazolate framework, ZIF-67) by optimizing the annealing conditions. The resulting ZIF-derived carbon possesses highly graphitic walls and a high specific surface area of 350 m(2)·g(-1), while the resulting ZIF-derived nanoporous Co3O4 possesses a high specific surface area of 148 m(2)·g(-1) with much less carbon content (1.7 at%). When nanoporous carbon and nanoporous Co3O4 were tested as electrode materials for supercapacitor application, they showed high capacitance values (272 and 504 F·g(-1), respectively, at a scan rate of 5 mV·s(-1)). To further demonstrate the advantages of our ZIF-derived nanoporous materials, symmetric (SSCs) and asymmetric supercapacitors (ASCs) were also fabricated using nanoporous carbon and nanoporous Co3O4 electrodes. Improved capacitance performance was successfully realized for the ASC (Co3O4//carbon), better than those of the SSCs based on nanoporous carbon and nanoporous Co3O4 materials (i.e., carbon//carbon and Co3O4//Co3O4). The developed ASC with an optimal mass loading can be operated within a wide potential window of 0.0-1.6 V, which leads to a high specific energy of 36 W·h·kg(-1). More interestingly, this ASC also exhibits excellent rate capability (with the highest specific power of 8000 W·kg(-1) at a specific energy of 15 W·h·kg(-1)) combined with long-term stability up to 2000 cycles.

Polymeric micelle assembly with inorganic nanosheets for construction of mesoporous architectures with crystallized walls.

Here we propose a novel way to construct mesoporous architectures through evaporation-induced assembly of polymeric micelles with crystalline nanosheets. As a model study, we used niobate nanosheets exfoliated by the direct reaction of K4Nb6O17⋅3 H2O crystals with an aqueous solution of propylamine. The electrostatic interaction between negatively charged nanosheets and positively charged polymeric micelles enable us to form composite micelles with the nanosheets. Removal of the micelles by calcination results in robust mesoporous oxides with the original crystalline structure.

Synergistic photocatalytic hydrogen evolution over oxide nanosheets combined with photochemically inert additives.

Photocatalytic hydrogen evolution over semiconducting niobate nanosheets is synergistically improved by coexisting photochemically inactive additives of clay particles and sodium chloride without precise nanoscopic structural regulation. In addition, the Pt cocatalyst loaded on the clay particles works better than that photodeposited on the photocatalytic nanosheets.

Multiphase coexistence and destabilization of liquid crystalline binary nanosheet colloids of titanate and clay.

A plate-plate binary colloid system of photocatalytically active titanate and inert clay nanosheets shows macroscopically separated multiphase coexistence. Two liquid crystalline phases and one isotropic phase coexist at high titanate and low clay concentrations whereas the colloids are destabilized at high clay concentrations.

Single- and double-layered organically modified nanosheets by selective interlayer grafting and exfoliation of layered potassium hexaniobate.

Organically modified niobate nanosheets are promising building blocks for the design of advanced hybrid materials. Nanosheets with controlled thickness and surface composition are important for precise structural design of the nanosheet-based materials. In this work, single-layered and double-layered niobate nanosheets functionalized by phenylphosphonate moieties were selectively prepared by interlayer grafting of A-type and B-type intercalation derivatives of potassium hexaniobate (K4Nb6O17·3H2O) with phenylphosphonic acid (PPA), followed by exfoliation by ultrasonication in acetonitrile. The interlayer grafting of PPA was monitored using X-ray diffraction (XRD), Fourier transform infrared (FTIR), and solid-state NMR spectroscopy, and the thicknesses of the exfoliated nanosheets were measured by atomic force microscopy (AFM). Transparent hybrid films were obtained by incorporating the single- and double-layered nanosheets into an epoxy matrix.

Panoscopic organization of anisotropic colloidal structures from photofunctional inorganic nanosheet liquid crystals.

Colloidal liquid crystals of inorganic nanosheets with thickness of around 1 nm and lateral dimensions of several micrometers prepared by exfoliation of a layered niobate are converted to hierarchically organized arrays whose structures are controlled from the nano to macroscopic length scale through the growth of liquid crystalline domains called tactoids as the secondary building blocks followed by controlled application of external fields. Growth of the tactoids is attained by incubation of the liquid crystals at room temperature. The tactoids are then assembled into higher-order structures with characteristic lengths of sub-mm to mm under the simultaneous application of an ac electric field and gravity, whose directions determine the final textural motif of the arrays. Whereas a net-like texture is observed when applying the electric and gravitational forces in the same direction, a striped texture where the nanosheets are unidirectionally aligned is observed when the electric field is applied in the direction perpendicular to gravity. The use of well-grown tactoids is key to the macroscopic structural control. Since the niobate nanosheets have wide band-gap semiconducting nature, the nanosheet stripe arrays exhibit photocatalysis that reflected the alignment of the nanosheets with respect to the polarized direction of impinging light.

Pickering emulsions prepared by layered niobate K4Nb6O17 intercalated with organic cations and photocatalytic dye decomposition in the emulsions.

We investigated emulsions stabilized with particles of layered hexaniobate, known as a semiconductor photocatalyst, and photocatalytic degradation of dyes in the emulsions. Hydrophobicity of the niobate particles was adjusted with the intercalation of alkylammonium ions into the interlayer spaces to enable emulsification in a toluene-water system. After the modification of interlayer space with hexylammonium ions, the niobate stabilized water-in-oil (w/o) emulsions in a broad composition range. Optical microscopy showed that the niobate particles covered the surfaces of emulsion droplets and played a role of emulsifying agents. The niobate particles also enabled the generation of oil-in-water (o/w) emulsions in a limited composition range. Modification with dodecylammonium ions, which turned the niobate particles more hydrophobic, only gave w/o emulsions, and the particles were located not only at the toluene-water interface but also inside the toluene continuous phase. On the other hand, interlayer modification with butylammonium ions led to the formation of o/w emulsions. When porphyrin dyes were added to the system, the cationic dye was adsorbed on niobate particles at the emulsion droplets whereas the lipophilic dye was dissolved in toluene. Upon UV irradiation, both of the dyes were degraded photocatalytically. When the cationic and lipophilic porphyrin molecules were simultaneously added to the emulsions, both of the dyes were photodecomposed nonselectively.

Aspect-ratio-dependent phase transitions and concentration fluctuations in aqueous colloidal dispersions of charged platelike particles.

Phase transitions of aqueous colloidal dispersions of charged platelike particles of niobate nanosheets were investigated as a function of the aspect ratio (r(asp)) and particle volume concentration (φ(p)) by means of small-angle neutron scattering and small-angle x-ray scattering. The results elucidated the following three pieces of evidence: (1) the macroscopic phase separation of the dispersions into an isotropic phase and a liquid crystalline (LC) phase under the conditions of (a) varying r(asp) (1.3×10(-4) ≤ r(asp) ≤ 2.5×10(-3)) at a constant φ(p) = 0.01 and (b) varying φ(p) (0.01 ≤ φ(p) ≤ 0.025) at a constant r(asp) = 2.5×10(-3), a mechanism of which is proposed in the text, where r(asp) ≡ d/ ̅L, with d and ̅L being thickness and the average lateral size of the plates, respectively; (2) the r(asp)-induced phase transition of the LC phase from a nematic phase to a highly periodic layered phase, the line shapes of the scattering peaks of which were examined by Caillé's analysis, upon increasing r(asp) under the condition (a); (3) the LC phase having remarkable concentration fluctuations of the particles which are totally unexpected for the conventional lyotropic molecular LC but which are anticipated to be general for the platelike colloidal particles.

Photoinduced electron accumulation in colloidally dispersed wide band-gap semiconductor nanosheets.

We investigated photoinduced electron accumulation in a colloidal system of layered hexaniobate that is known as a photocatalytically active wide band-gap semiconductor, and attempted to control the photoresponse by introducing additives into the colloid. The inorganic nanosheets were obtained by exfoliation of the layered oxide. UV-irradiation of the colloids led to electron accumulation in the nanosheets to generate reduced niobate species. Propylammonium ions introduced as the exfoliating reagent and present as the counter ions of niobate nanosheets were indicated as the electron donor that stabilized the electron-accumulating state. Yield and half-life of the reduced niobate species greatly increased by adding an appropriate amount of photochemically inert clay nanosheets, while they increased only a little by the addition of molecular electron donors such as EDTA and triethanolamine. Moreover, the molecular species diminished the enhancement effect of the clay nanosheets. The results suggested that the photochemical event was not explained by direct interactions between the semiconductor nanosheets and the additives at molecular level but governed by indirect interactions between the colloid components regulated by the colloid structure.