Hironori Ohashi

Ultrafine Gold Clusters Incorporated into a Metal–Organic Framework

Similar tozeolites, the structures of MOFs are usually microporous. Inaddition, there are advantages in the easily tunable sizes,shapes, and surrounding environments of the pores inMOFs; these endow MOFs with broader properties and ap-plications. Therefore, it is reasonable to apply porous MOFsas supports and/or hard templates for preparation of smallAu NPs. The porous structures in MOFs are expected tolimit the migration and aggregation of Au NPs. However, todate, all reported Au NPs are larger than 1.5 nm because ofthe poor understanding of the ruling factors of the size ofAu particles.

Base‐Free Direct Oxidation of 1‐Octanol to Octanoic Acid and its Octyl Ester over Supported Gold Catalysts

The choice of a suitable support for gold nanoparticles (Au NPs) enabled the direct oxidation of unreactive aliphatic alcohol, 1-octanol, to octanoic acid and octyl octanoate in the absence of a base. Under optimized conditions, Au NPs supported on NiO (Au/NiO) exhibited remarkably high catalytic activities and excellent selectivities to octanoic acid (e.g., 97 %) at full conversion. In contrast to Au/NiO, Au/CeO₂ selectively produced octyl octanoate as a major product in a base-free aqueous solution with a maximum selectivity of 82 % under optimized conditions.

Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts

Transformation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts using molecular oxygen as the sole oxidant is developed. Several metal oxide supported Pd catalysts were used to activate the C–H bond in cyclohexanones to produce cyclohexenones and phenols through oxidation. Although the selectivity of cyclohexenones was difficult to control, phenols were obtained in excellent yield with a broad substrate scope. A novel catalytic system, using ZrO2 supported Pd(OH)2, was proposed for the synthesis of aryl ethers, and the products were obtained in moderate to excellent yields. Orthoesters, such as trimethyl orthoformate (TMOF), triethyl orthoformate (TEOF), and triisopropyl orthoformate (TIPOF), enabled nucleophilic addition and elimination after activation of cyclohexanones over a Pd catalyst to produce the corresponding aryl ethers. TIPOF was also used as the dehydrating reagent to promote the reaction of cyclohexanones with alcohols for the preparation of versatile aryl ethers.

Adsorption kinetics of silicic acid on akaganeite.

As part of a series of studies on the interaction between ferric ions and silicic acid in the hydrosphere, the adsorption of silicic acid on akaganeite was investigated kinetically at various pH values. The adsorption of silicic acid increased with increasing pH over an initial pH range of 4-11.5. In the kinetic experiment, the Cl(-) was released from akaganeite much faster than silicic acid was adsorbed. From this result, we concluded that chloride ions bound on the surface of akaganeite are released and Fe-OH or Fe-O(-) sites are formed, which then acts as an adsorption site for silicic acid. The uptake mechanism of silicic acid by akaganeite is significantly different from that by schwertmannite, despite the presence of the same tunnel structure.

Sorption behavior of the Pt(II) complex anion on manganese dioxide (δ-MnO2): a model reaction to elucidate the mechanism by which Pt is concentrated into a marine ferromanganese crust

It is difficult to directly investigate the chemical state of Pt in marine ferromanganese crusts (a mixture of hydrous iron(III) oxide and manganese dioxide (δ-MnO2)) because it is present at extremely low concentration levels. This paper attempts to elucidate the mechanism by which Pt is concentrated into marine ferromanganese crust from the Earth’s continental crust through ocean water. In this investigation, the sorption behavior of the Pt(II) complex ions on the surface of the δ-MnO2 that is a host of Pt was examined as a model reaction. The δ-MnO2 sorbing Pt was characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) to determine the chemical state of the Pt. Hydrolytic Pt(II) complex ions were specifically sorbed above pH 6 by the formation of a Mn-O-Pt bond. XPS spectra and XANES spectra for δ-MnO2 sorbing Pt showed that the sorbed Pt(II) was oxidized to Pt(IV) on δ-MnO2. The extended X-ray absorption fine structure (EXAFS) analysis showed that the coordination structure of Pt sorbed on δ-MnO2 is almost the same as that of the [Pt(OH)6]2− complex ion used as a standard. Therefore, the mechanism for the concentration of Pt in marine ferromanganese crust may be an oxidative substitution (penetration of Pt(IV) into structure of δ-MnO2) by a reduction-oxidation reaction between Pt(II) in [PtCl4-n(OH)n]2− and Mn(IV) in δ-MnO2 through a Mn-O-Pt bond.

Interaction of Au(III) and Pt(IV) complex ions with Fe(II) ions as a scavenging and a reducing agent: a basic study on the recovery of Au and Pt by a chemical method.

In order to develop a chemical technique for the recovery of gold (Au) and platinum (Pt) in the metallic state from spent catalysts, e.g., catalysts for environmental protection and automobile and petroleum catalysts, the coprecipitation behaviors of Au(III) and Pt(IV) complex ions with Fe(OH)(2) as a scavenging and reducing agent were investigated. The Au(III) complex ions were found to be stoichiometrically and rapidly reduced to metallic Au due to electron transfer in acidic aqueous solution prior to coprecipitation with Fe(OH)(2). Conversely, Pt(IV) complex ions were reduced only after coprecipitation with Fe(OH)(2) due to electron transfer through a Pt(IV)-O-Fe(II) bond on the solid Fe(OH)(2). Using this chemical technique, Au and Pt can be selectively and effectively recovered in the metallic state.

Silica deposition induced by isolated aluminum ions bound on chelate resin as a model compound of the surface of microbes

To elucidate the mechanism of silica biodeposition in hot spring water, which is induced by Al(3+) ions bound to the surface of microbes, a chelate resin (Chelex 100) was used as a model compound of the surface of microbes. No silicic acid was adsorbed on the Na type Chelex 100, whereas silicic acids were significantly adsorbed to the Al type Chelex 100. In the Al type Chelex 100, the Al(3+) ions were present as 1:1 tridentate complex with iminodiacetate (IDA) group. After adsorption of silicic acid to Al type Chelex 100, a IDA-Al-O-Si-(OH)(3) site formed. The site acted as a template for the successive adsorption of silicic acids to form silica sheets around Al type Chelex 100 particles. In conclusion, Al(3+) ions bound to the surface of microbes play a key role as a trigger for the biodeposition of silica in hot spring water.

Efficient Decarbonylation of Furfural to Furan Catalyzed by Zirconia‐Supported Palladium Clusters with Low Atomicity

Decarbonylation of furfural to furan was efficiently catalyzed by ZrO2 -supported Pd clusters in the liquid phase under a N2 atmosphere without additives. Although Pd/C and Pd/Al2 O3 have frequently been used for decarbonylation, Pd/ZrO2 exhibited superior catalytic performance compared with these conventional catalysts. Transmission electron microscopy and X-ray absorption fine structure measurements revealed that the size of the Pd particles decreased with an increase in the specific surface area of ZrO2 . ZrO2 with a high surface area immobilized Pd as clusters consisting of several (three to five) Pd atoms, whereas Pd aggregated to form nanoparticles on other supports such as carbon and Al2 O3 despite their high surface areas. The catalytic activity of Pd/ZrO2 was enhanced with a decrease in particle size, and the smallest Pd/ZrO2 was the most active catalyst for decarbonylation. When CeO2 was used as the support, a decrease in Pd particle size with an increase in surface area was also observed. Single Pd atoms were deposited on CeO2 with a high surface area, with a strong interaction through the formation of a Pd-O-Ce bond, which led to a lower catalytic activity than that of Pd/ZrO2 . This result suggests that zero-valent small Pd clusters consisting of more than one Pd atom are the active species for the decarbonylation reaction. Recycling tests proved that Pd/ZrO2 maintained its catalytic activity until its sixth use.

Preparation of gold clusters on metal oxides by deposition-precipitation with microwave drying and their catalytic performance for CO and sulfide oxidation

Abstract Gold clusters and small nanoparticles supported on metal oxides could be prepared by deposition-precipitation followed by microwave irradiation as a drying method and then calcination. The drying method influenced the size of the Au particles. Au(III) was partly reduced during conventional oven drying, resulting in Au aggregates. In contrast, Au(III) was preserved during microwave drying owing to rapid and uniform heating, and the Au diameter was minimized to 1.4 nm on Al2O3. This method can be applied to several metal oxide supports having different microwave absorption efficiencies, such as MnO2, Al2O3, and TiO2. These catalysts exhibited higher catalytic activities for CO oxidation at low temperature and for selective aerobic oxidation of sulfide than those prepared by conventional methods.