Masamoto Tafu

Synthesis of robust hierarchically porous zirconium phosphate monolith for efficient ion adsorption

Hierarchically porous monolithic materials are advantageous as adsorbents, catalysts and catalyst supports due to the better accessibility of reactants to the active sites and the ease of recycle and reuse. Traditional synthetic routes, however, have limitations in designing hierarchical porosity as well as the mechanically stable monolithic shape in inorganic phosphate materials, which are useful as adsorbents and catalysts. We present a low-temperature, one-step liquid phase synthesis of hierarchically porous zirconium phosphate (ZrP) monoliths with tunable compositions (from Zr(HPO4)2 (Zr : P = 1 : 2) to NaSICON (Na super ionic conductor)-type ZrP (Zr : P = 1 : 1.5)) as well as macropore size (from 0.5 to 5 μm). The as-synthesized ZrP monolith with a high reactive surface area (600 m2 g−1) and relatively high mechanical strength (Youngs modulus 320 MPa) was applied to ion adsorption. A simple syringe device inserted tightly with the ZrP monolith as a continuous flow setup was demonstrated to remove various toxic metal ions in aqueous solutions, which shows promising results for water purification.

Grafted Polymethylhydrosiloxane on Hierarchically Porous Silica Monoliths: A New Path to Monolith-Supported Palladium Nanoparticles for Continuous Flow Catalysis Applications

Polymethylhydrosiloxane has been grafted on the surface of a hierarchically porous silica monolith using a facile catalytic reaction between Si-H and silanol to anchor the polymer. This easy methodology leads to the functionalization of the surface of a silica monolith, where a large amount of free Si-H bonds remain available for reducing metal ions in solution. Palladium nanoparticles of 15 nm have been synthesized homogeneously inside the mesopores of the monolith without any stabilizers, using a flow of a solution containing Pd2+. This monolith was used as column-type fixed bed catalyst for continuous flow hydrogenation of styrene and selective hydrogenation of 3-hexyn-1-ol, in each case without a significant decrease of the catalytic activity after several hours or days. Conversion, selectivity, and stereoselectivity of the alkyne hydrogenation can be tuned by flow rates of hydrogen and the substrate solution, leading to high productivity (1.57 mol g(Pd)-1 h-1) of the corresponding cis-alkene.

Morphology control of brushite prepared by aqueous solution synthesis

Abstract Dicalcium phosphate dihydrate (DCPD, CaHPO4·2H2O), also known as brushite, is one of the important bioceramics due to not only diseases factors such as kidney stone and plaque formation but also purpose as fluoride insolubilization material. It is used medicinally to supply calcium, and is of interest for its unique properties in biological and pathological mineralization. It is important to control the crystal morphology of brushite since its chemical reactivity depends strongly on its surface properties; thus, its morphology is a key issue for its applications as a functional material or precursor for other bioceramics. Here, we report the effects of the initial pH and the Ca and phosphate ion concentrations on the morphology of DCPD particles during aqueous solution synthesis. Crystal morphologies were analyzed by scanning electron microscopy and X-ray diffraction. The morphology phase diagram of DCPD crystallization revealed that increasing the initial pH and/or ion concentration transformed DCPD morphology from petal-like into plate-like structures.

The evaluation of forest fire severity and effect on soil organic matter based on the L*, a*, b* color reading system

The evaluation of forest fire severity and effect on soil is very important when discussing the damage to the environment. The purpose of this study is to evaluate the effect forest fires have on the soil color using the CIE Lab system. The color changes in four kinds of soil samples caused by heating at different temperatures were investigated. It was found that the Δa* and Δb* values drastically decrease when samples were heated over the temperature range from 200 to 250 °C, that is above the ignition temperature of volatile matter. The Δa* and Δb* values show a good linear negative correlation with the atomic ratios of H/C and O/C. The results obtained from this study indicate that the proposed method is able to evaluate the dehydration and decarboxylation of soil caused by forest fires. We demonstrated this method using soil samples collected from unburned and burned areas in Kalimantan, Indonesia.

Effect of Anions on Morphology Control of Brushite Particles

Brushite (DCPD, CaHPO4·2H2O) crystals are of great significance in a range of fields including biology, medicine, chemistry, and materials science. One important issue is the control of their morphology; when the crystal growth conditions are changed, the morphology and surface crystal conditions also change. The chemical reaction behavior depends strongly on the surface condition of the particles. Here, we report the effect of coexisting anions on the morphology control of DCPD particles. We synthesized the particles through a liquid-phase reaction by mixing a starting solution of ammonium dihydrogen phosphate (NH4H2PO4) and calcium salts. Calcium nitrate (Ca (NO3)2) and calcium acetate (Ca (CH3COO)2) were used as the calcium sources to clarify the pH dependence of the morphology. We mixed the solutions with the same pH values and agitated them, and observed the products by scanning electron microscopy (SEM) and X-ray diffraction (XRD); the DCPD morphology varies from petal-like to parallelogram structures depending on the initial pH value of the solution and the combination of the starting mixture. The effect of the acetic acid anion is to increase the driving force for the generation of DCPD crystal nuclei.

Amine/Hydrido Bifunctional Nanoporous Silica with Small Metal Nanoparticles Made Onsite: Efficient Dehydrogenation Catalyst

Multifunctional catalysts are of great interest in catalysis because their multiple types of catalytic or functional groups can cooperatively promote catalytic transformations better than their constituents do individually. Herein we report a new synthetic route involving the surface functionalization of nanoporous silica with a rationally designed and synthesized dihydrosilane (3-aminopropylmethylsilane) that leads to the introduction of catalytically active grafted organoamine as well as single metal atoms and ultrasmall Pd or Ag-doped Pd nanoparticles via on-site reduction of metal ions. The resulting nanomaterials serve as highly effective bifunctional dehydrogenative catalysts for generation of H2 from formic acid.

Effect of Hydroxyapatite on Reaction of Dicalcium Phosphate Dihydrate DCPD) and Fluoride Ion

DCPD, dicalcium phosphate dihydrate (CaHPO4•2H2O) reacts with fluoride ion in an aqueous solution, and forms fluorapatite (FAp, Ca10(PO4)6F2). In previous study, we have found that DCPD does not react with fluoride ion directly, but show few hours of induction period by reaction with fluoride. In this study, effect of hydroxyapatite (HA, Ca10(PO4)6(OH)2) on the reactivity of DCPD with fluoride ion was investigated. By mixing HA with DCPD, it was appeared that the induction period of the reaction was shortened. Morphology of the obtained FAp was similar to HA paricles. We carried on coating of HA on the DCPD particle by soaking DCPD in simulated body fluid (SBF, Kokubo Solution). By coating HA on DCPD particles, particle morphology of the obtained FAp was consistency to the DCPD particles. These results suggest that the shape and particle size of FAp after reaction of DCPD is controllable by DCPD particle as template, and coating with HA.

The Extremely High Adsorption Capacity of Fluoride by Chicken Bone Char (CBC) in Defluoridation of Drinking Water in Relation to Its Finer Particle Size for Better Human Health

The ingestion of fluoride-contaminated water causes serious health issues in people all over the world. In the current study, the adsorption of fluoride onto chicken bone char (CBC) was investigated as a defluoridation technique. Finer-sized CBC with a diameter of 106–212 µm was used to investigate the fluoride adsorption capacity onto CBC. Results revealed that finer-sized CBC yielded an unusually high fluoride adsorption capacity of 11.2 mg/g at the equilibrium fluoride concentration of 10 mg/L. The study shows that CBC can be utilized in the defluoridation of drinking water and that finer-sized CBC enhances ion exchange to perform a higher adsorption capacity.

Immobilization of Fluoride and Heavy-Metals in Polluted Soil

Estimation and immobilization of fluoride and heavy-metals in contaminated soil are important approaches for the remediation of fluoride and heavy-metal polluted soil. In this review, firstly, we described recent achievements about the on-site estimation of various pollutants by simple chemical reaction without special skills for operators. The in-situ immobilization of fluoride was also described. For immobilization of fluoride, dicalcium phosphate dihydrate (DCPD) was selected as functional material because it reacts with fluoride ion effectively and forms stable fluorapatite (FAp). Both laboratory and field tests showed that the DCPD is useful to immobilize fluoride in polluted soil.

Chemical prosperity of various chemical gypsums from viewpoint of particle morphology

Dissolution rate of various chemical gypsums in the water was investigated by using batch experiment. The rate of the dissolution of the gypsum had good agreement for explanation of dissolution of plate particle. The rate constants of the experimental formula were different with particle morphology of the gypsums. When morphology of the particle was sheet-liked, the dissolution rate was 10 timed large than it of block-shaped particle. From result of observation of dissolution phenomena of the in the water, it was find that dissolution of the gypsum was preceded on long axis. From these results, particle morphology is seems to be important parameter for using chemical gypsums.