Assessment of the Crystallization Process of CaO-Al2O3-SiO2 Glass Probed with Tb3+ Luminescence.

The ratio of the intensity of Tb3+ fluorescence at 543 nm because of an electric dipole transition (5D4-7F5) relative to that at 437 nm due to a magnetic dipole transition (5D3-7F4) was determined to be proportional to the amount of metastable CaAl2Si2O8 crystals precipitated in CaO-Al2O3-SiO2 glass. The present results indicate that Tb3+ luminescence can be used as a probe to evaluate the crystallization of glass.

Hydrogen Production System by Light-Induced α-FeOOH Coupled with Photoreduction.

Solar-driven catalysts on semiconductors to produce hydrogen are considered as a means to solve environmental issues. In this study, H2 production coupling with oxygen consumption by noble metal-free α-FeOOH was demonstrated even though the conduction band edge was lower than the reduction potential of H+ to H2 . For activation of α-FeOOH, an electron donor, Hg-Xe irradiation, and low pH (ca. 5) were indispensable factors. The H2 production from H2 O was confirmed by GC-MS using isotope-labeled water (D2 O) and deuterated methanol. The α-FeOOH synthesized by coprecipitation method showed 25 times more active than TiO2 . The photocatalytic activity was stable for over 400 h. Our study suggests that α-FeOOH known as rust can produce H2 by light induction.

Hydrogen Production System by Light-Induced α-FeOOH Coupled with Photoreduction.

Invited for the cover of this issue is Tetsuya Yamada, Ken-ichi Katsumata and co-workers at Tokyo Institute of Technology and Tokyo University of Science. The image depicts rust producing hydrogen and purifying the pollutants at the same time by photocatalytic reaction. Read the full text of the article at 10.1002/chem.201903642.

Multifunctionality in coating films including Nb-doped TiO2 and Cs x WO3: near infrared shielding and photocatalytic properties.

Various types of coating films were obtained from hydrothermally synthesized Nb-doped TiO2 (NTO) and Cs x WO3 (CWO) nanoparticles. The coating films possessed multifunctionality including near infrared (NIR) absorption and photocatalysis abilities. The NTO and CWO nanoparticles were synthesized by a unique solvothermal reaction in which water induced by an esterification reaction between alcohol and carboxylic acid can act as a hydrolyzing agent for metal precursors. NTO was synthesized by the unique solvothermal reaction for the first time. The reaction accompanied by the reduction of Ti4+ to Ti3+ led to the formation of nanoparticles with both NIR absorption and photocatalytic properties. The effect of the ethanol-acetic acid ratio on the morphology of the obtained NTO was investigated, and the larger amount of acetic acid led to a larger nanoparticle size, indicating the size controllability. The two types of coating film, including CWO and NTO nanoparticles, were obtained for comparison: (1) coexistent coating film: one side of the quartz glass was coated with a dispersion, including both CWO and NTO nanoparticles, and (2) double-sided coating film: a quartz glass coated with a CWO dispersion on one side and an NTO dispersion on the other side. The double-sided coating led to higher multifunctionality. Furthermore, the optimized condition for the double-sided coating was investigated by using various NTO particles obtained using different ethanol-acetic acid ratios.

Synthesis of Mesoporous TiO2/Boron-Doped Diamond Photocatalyst and Its Photocatalytic Activity under Deep UV Light (λ = 222 nm) Irradiation.

There is a need for highly efficient photocatalysts, particularly for water purification. In this study, we fabricated a mesoporous TiO2 thin film on a boron-doped diamond (BDD) layer by a surfactant-assisted sol-gel method, in which self-assembled amphiphilic surfactant micelles were used as an organic template. Scanning electron microscopy revealed uniform mesopores, approximately 20 nm in diameter, that were hexagonally packed in the TiO2 thin film. Wide-angle X-ray diffraction and Raman spectroscopy clarified that the framework crystallized in the anatase phase. Current⁻voltage (I⁻V) measurements showed rectification features at the TiO2/BDD heterojunction, confirming that a p⁻n hetero-interface formed. The as-synthesized mesoporous TiO2/BDD worked well as a photocatalyst, even with a small volume of TiO2 (15 mm × 15 mm × c.a. 1.5 µm in thickness). The use of deep UV light (λ = 222 nm) as a light source was necessary to enhance photocatalytic activity, due to photo-excitation occurring in both BDD and TiO2.

Different hollow and spherical TiO2 morphologies have distinct activities for the photocatalytic inactivation of chemical and biological agents.

The inactivation of Escherichia coli and Qß phage was examined following their photocatalytic treatment with TiO2 hollows and spheres that had been prepared by electrospray, hydrothermal treatment, and calcination. The crystal structures of the hollows and spheres were assigned to TiO2 anatase, and the surface areas of the hollows and spheres were determined to be 91 and 79 m(2) g(-1), respectively. Interestingly, TiO2 spheres exhibited higher anti-pathogen performance than TiO2 hollows, a difference we ascribe to the prevention of light multi-scattering by microorganisms covering the surfaces of the TiO2 particles. The photocatalytic decomposition of dimethyl sulfoxide (DMSO) in the presence of TiO2 hollows and spheres was examined in order to study the dependence of photocatalytic activity on TiO2 morphology for the size scale of the reactants. TiO2 hollows provided greater photocatalytic decomposition of DMSO than did TiO2 spheres, in contrast to the pattern seen for pathogen inactivation. Fabrication of photocatalysts will need to vary depending on what substance (e.g., organic compound or biological agent) is being targeted for environmental remediation.

Study on the Effect of Pt Intercalation into Layered Niobate Perovskite for Photocatalytic Behavior.

A novel photocatalyst consisting of an intercalated perovskite H(1-2x)Pt(x)LaNb2O7 was fabricated by ion exchange. Synchrotron X-ray diffraction and X-ray photoelectron spectroscopy results confirmed that Pt(2+) exists within the interlayer space of the layered perovskite. H(1-2x)Pt(x)LaNb2O7 composed of layered niobate perovskite and intercalated Pt(2+) completely degraded a 20 ppm phenol solution in 3 h under irradiation by Xe light, which exhibits photocatalytic activity superior to those of RbLaNb2O7, Pt-deposited RbLaNb2O7, and HLaNb2O7. From first-principles density functional theory simulation, high photocatalytic activity of H(1-2x)Pt(x)LaNb2O7 is attributed to the emergence of a new O 2p-Pt 5d hybridized band on top of the valence band.

Preparation of iron oxide-impregnated spherical granular activated carbon-carbon composite and its photocatalytic removal of methylene blue in the presence of oxalic acid.

The spherical granular activated carbon-carbon composites (GAC-Fe) with different iron oxide contents (Fe mass% = 0.6-10) were prepared by a pore volume impregnation method. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2-adsorption results confirm the presence of amorphous iron oxide, pyrolytic carbon, and graphitized globular carbon nanoparticles covered with amorphous carbon in the CAG-Fe. The rate of photodegradation of methylene blue (MB) in aqueous solution under UV light in the presence of oxalic acid correlates with porosity of the prepared materials. The total MB removal includes the combination of adsorption and photodegradation without the addition of H2O2. The results of total organic carbon (TOC) analysis reveal that the decolorization of MB in aqueous solution containing oxalic acid corresponds to the decomposition of organic compounds to CO2 and H2O.

Effect of Vanadium Oxide on the Crystallization of CaO-Al2O3-SiO2 Glass.

This study investigated the effect of vanadium oxide on the crystallization of CaO-Al2O3-SiO2 (CAS) glass. Specifically, this study subjected CAS glass-ceramics (GCs) with precipitated hexagonal platy particles of metastable CaAl2Si2O8 (CAS GC-H), a layered crystal, that was prepared using metallic molybdenum (Mo) particles as nucleation agents. When the parent glass of CAS GC-H was crystallized with the addition of vanadium oxide in the 0.052-0.21 wt % range, the obtained platy particles of metastable CaAl2Si2O8 displayed an increase in the aspect ratio from 20 to 15 compared with conventional CAS GC-Hs. In addition, no crystallization occurred in the CAS glass with vanadium oxide in the 0.052-0.21 wt % range in the absence of metallic Mo particles. Meanwhile, a CAS glass containing 1.0 wt % vanadium oxide without the addition of metallic Mo particles showed the precipitation of metastable CaAl2Si2O8. Therefore, these results indicated that the aspect ratio of layered crystals in glass was controlled by the addition of a relatively small content of vanadium oxide, and a new nucleation agent for the precipitation of metastable CaAl2Si2O8 in CAS glass using a relatively high content of vanadium oxide was developed.

Interfacial molecular regulation of TiO2 for enhanced and stable cocatalyst-free photocatalytic hydrogen production.

On the basis of the inherent property limitations of commercial P25-TiO2, many surface interface modification methods have attracted substantial attention for further improving the photocatalytic properties. However, current strategies for designing and modifying efficient photocatalysts (which exhibit complicated manufacturing processes and harsh conditions) are not efficient for production that is low cost, is nontoxic, and exhibits good stability; and therefore restrict practical applications. Herein, a facile and reliable method is reported for in situ amine-containing silane coupling agent functionalization of commercial P25-TiO2 by covalent surface modification for constructing a highly efficient photocatalyst. As a consequence, a high efficiency of H2 evolution was achieved for TiO2-SDA with 0.95 mmol h-1 g-1 (AQE ∼45.6 % at 365 nm) under solar light irradiation without a co-catalyst. The amination modification broadens the light absorption range of the photocatalyst, inhibits the binding of photogenerated carriers, and improves the photocatalytic efficiency; which was verified by photochemical properties and DFT theoretical calculations. This covalent modification method ensures the stability of the photocatalytic reaction. This work provides an approach for molecularly modified photocatalysts to improve photocatalytic performance by covalently modifying small molecules containing amine groups on the photocatalyst surface.

Regioselective Approach to Characterizing Increased Edge Availability in Layered Crystal Materials following Layer Expansion: Reaction of Kaolinite with Octadecyltrimethylammonium Salts.

In this paper, the regioselective reactions of kaolinite and methoxy-modified kaolinite (MeO-Kaol), methanol-expanded kaolinite, with octadecyltrimethylammonium salts are compared. This study mainly concerns the reactions of kaolinite or MeO-Kaol with octadecyltrimethylammonium chloride (C18TAC) in methanol and the subsequent exhaustive washing of the resultant products with ethanol. X-ray diffraction patterns of the products reveal no intercalation of C18TAC between pristine kaolinite layers. Additionally, intercalation and subsequent deintercalation of C18TAC proceed in the product using MeO-Kaol. In the Fourier-transform infrared spectra, the intensities of CH2 stretching bands of the product prepared using MeO-Kaol drastically increase compared to those using kaolinite. In addition, CH2 stretching bands of the product using kaolinite are hardly observed without enlarging the spectrum. The product using MeO-Kaol also displays mass loss in the range of 200-300 °C in the thermogravimetric curve and a nitrogen content with 0.15 mass% estimated using the CHN analysis. These results therefore demonstrate an increase in the available reactive edges in the layered crystal material following an expansion of the stacked layers.

Effect of kaolinite edge surfaces on formation of Tb3+-doped phosphor by solid-state reaction.

This study assessed the effect of kaolinite edge surfaces on solid-state reactions. Specifically, Tb3+-doped metastable CaAl2Si2O8 showing green phosphorescence was prepared via a solid-state reaction between expanded kaolinite, a methoxy-modified kaolinite, having Tb3+ ions adsorbed on its edge surfaces and CaCO3. This material cannot be obtained by the conventional grinding of kaolinite, CaCO3 and Tb2O3, indicating that the use of kaolinite edge surfaces is advantageous as a means of achieving certain solid-state reactions.

Microstructural Control of CaO-Al2O3-SiO2 Glass Ceramics by Oxidation and Mixing with Nucleation Agents.

Microstructural control of CaO-Al2O3-SiO2 (CAS) glass ceramics (GCs) was achieved by oxidation and mixing with nucleation agents. CAS GCs were precipitated with hexagonal platy particles of metastable CaAl2Si2O8 layered crystals (CAS GC-H), which are typically prepared under a reductive atmosphere that forms metallic Mo or W particles as nucleation agents. The average particle size of crystals decreased significantly from 50 to 11 µm when the CAS GC-H containing metallic W particles was prepared under an oxidative atmosphere. Compared to this CAS-GC-H, the crystal particle size increased from 8-20 to 10-30 µm when the CAS GC-H was prepared by mixing glass cullet containing metallic Mo and that containing metallic W particles. These results indicate that one microstructure of CAS GC-H is controlled on the micrometer scale from a parent glass with one composition by varying the experimental conditions related to the glass melting state.

Effect of carbon on the co-presence of metallic tungsten as a nucleation agent and Eu2+ in glass: crystallization of CaO-Al2O3-SiO2 glass probed with Eu2+ luminescence.

This study demonstrated simple redox control in glasses by improving the method used to added glass raw materials. Specifically, the effect of carbon on the co-presence of metallic tungsten (W) particles as nucleation agents and Eu2+ ions in CaO-Al2O3-SiO2 (CAS) glass was investigated via their crystallization to form CAS glass-ceramics (GCs). In this study, the glass specimens were prepared by mixing glass cullet containing metallic W particles and Eu2+ ions, respectively, with a glass batch containing carbon. Whereas the glass specimen was yellowish because of the presence of Eu2+ when carbon was not added during the remelting process, the glass specimen prepared with carbon was black because of the presence of metallic W particles. In addition, this specimen displayed the 470 nm emission band in its fluorescence spectrum recorded under 393 nm excitation, which was attributed to the presence of Eu2+. According to the fluorescence and transmission spectra, the glass specimen showed a darker coloration and more intense 470 nm emission band compared with the specimen prepared by the conventional melting method that included a remelting process. These results indicated that metallic W and Eu2+ were reduced with greater efficiency by the melting method that involved mixing the glass cullet and batch. In addition, the heat-treated glass specimen prepared by the aforementioned mixing method contained a greater amount of metastable CaAl2Si2O8 with increasing heat treatment time as revealed by X-ray diffraction analysis and scanning electron microscopy observation. The intensity of the 470 nm emission band decreased with increasing intensity of the band at 420 nm because of the incorporation of Eu2+ into the crystalline phase, and the increase in intensity of the 420 nm band was lineally proportional to the volume fraction of the crystallized glass specimens. The results therefore indicated that the co-presence of metallic W particles as nucleation agents and Eu2+ as a probe for tracking the crystallization process was achieved by the addition of carbon during the remelting process of mixed cullet containing W and Eu2+ through crystallization of the CAS glass. The results thus demonstrate the importance of improving the method used to added glass raw materials.

Enhanced Hydrogen Production at Optimum pH for the Recovery Cycle of ß-FeOOH.

In the photo-Fenton reaction, highly reactive oxygen species are generated on UV irradiation of ß-FeOOH, which contributes significantly to hydrogen production. The production process was performed by adjusting the pH of the solution. The effect of acid concentration on hydrogen production was analyzed in this study, and the difference in the amount of hydrogen gas produced in each sample with different pH values was determined. X-ray powder diffraction (XRD) measurements of the samples corresponding to the peaks of ß-FeOOH were compared with the reference data, and crystallite sizes were calculated by the Scherrer equation using XRD patterns. The rod-like structure of the sample particles was revealed by scanning electron microscopy. A higher amount of hydrogen was produced at lower pH, and these results confirmed that pH plays an important role in hydrogen production.

Photoreduction of Copper Ions Using Silica-Surfactant Hybrid and Titanium (IV) Oxide under Sulfuric Acid Conditions.

Photoreduction of Cu2+ ions to Cu metal by titanium(IV) oxide (TiO2) was conducted in the presence of a silica-surfactant hybrid under sulfuric acid conditions. After irradiation, a dark-red color, reflections due to Cu metal in the X-ray diffraction pattern, and peaks due to Cu 2p1/2 and 2p3/2 in the X-ray photoelectron spectrum indicated the precipitation of Cu metal in the product. In addition, an increase in the Brunauer-Emmett-Teller specific surface area from 36 and 45 m2/g for the silica-surfactant and TiO2, respectively, to 591 m2/g for the product, and a decrease in the intensity of the C-H stretching band in the Fourier-transform infra-red spectra implied the removal of surfactant during the reaction. These characteristics were never observed when TiO2 was used solely. Therefore, this study indicated that the photoreduction of Cu2+ ions to Cu metal by TiO2 was facilitated under the sulfuric acid medium, where the surfactants extracted from silica-surfactant hybrids by protons in the acidic condition were successfully photo-oxidized by TiO2. Thus, this study presents a new application of the conversion of a silica-surfactant hybrid into mesoporous silicas.

Complete decomposition of sulfamethoxazole during an advanced oxidation process in a simple water treatment system.

A simple water treatment system consisting of a deep UV light (λ = 222 nm) source, a mesoporous TiO2/boron-doped diamond (BDD) photocatalyst, and a BDD electrode was prepared and used to decompose sulfamethoxazole (SMX) in an advanced oxidation process. The mesoporous TiO2/BDD photocatalyst used with the electrochemical treatment promoted SMX decomposition, but the mesoporous TiO2/BDD photocatalyst alone had a similar ability to decompose SMX as photolysis. Fragments produced through photocatalytic treatment were decomposed during the electrochemical treatment and fragments produced during the electrochemical treatment were decomposed during the photocatalytic treatment, so performing the electrochemical and photocatalytic treatments together effectively decomposed SMX and decrease the total organic carbon concentration to a trace.

Porous ceramics mimicking nature-preparation and properties of microstructures with unidirectionally oriented pores.

Porous ceramics with unidirectionally oriented pores have been prepared by various methods such as anodic oxidation, templating using wood, unidirectional solidification, extrusion, etc. The templating method directly replicates the porous microstructure of wood to prepare porous ceramics, whereas the extrusion method mimics the microstructures of tracheids and xylems in trees. These two methods are therefore the main focus of this review as they provide good examples of the preparation of functional porous ceramics with properties replicating nature. The well-oriented cylindrical through-hole pores prepared by the extrusion method using fibers as the pore formers provide excellent permeability together with high mechanical strength. Examples of applications of these porous ceramics are given, including their excellent capillary lift of over 1 m height which could be used to counteract urban heat island phenomena, and other interesting properties arising from anisotropic unidirectional porous structures.

Expansion of orderly stacked metakaolinite layers and order destruction using a kaolinite-tetraphenylphosphonium chloride intercalation compound.

The expansion of metakaolinite layers with stacking order and the order destruction were examined by the heat treatment of a kaolinite-tetraphenylphosphonium chloride intercalation compound (Kaol-TPhPCl) at 540 °C under a nitrogen atmosphere followed by the manual grinding of the product using a mortar and a pestle. Fourier-transform infrared spectroscopy and solid-state 27Al nuclear magnetic resonance spectroscopy with magic angle spinning revealed the kaolinite dehydroxylation. Moreover, the absence of kaolinite diffraction lines and the appearance of the 1.85 nm diffraction line in the X-ray diffraction pattern, together with the observation of the hexagonal plate-like morphology in the field-emission scanning electron microscopy, indicated the kaolinite amorphization with the orderly-stacked layers. These results, along with the disappearance of the 1.85 nm diffraction line upon the manual grinding of heat-treated Kaol-TPhPCl, clearly indicated the formation of expanded metakaolinite layers with stacking order and the subsequent order destruction by manual grinding.

Effects of kaolinite layer expansion and impurities on the solid-state reaction of kaolinite.

Expanded kaolinite without impurities was found to serve as a suitable raw material for the rapid formation of metastable CaAl2Si2O8 with the suppression of byproduct formation. This was accomplished based on the solid-state reaction of the kaolinite with calcium carbonate promoted by mechanical grinding.