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● （pubYear = 2007） [20 records among 25] (20 hits)

■ TCS・2007 (full paper) ANISOT_A　 S. Ikeda, H. Kobayashi, Y. Ikoma, T. Harada, T. Torimoto, B. Ohtani and M. Matsumura, Size-Selective Photocatalytic Reactions by Titanium(IV) Oxide Coated with a Hollow Silica Shell in Aqueous Solutions, Phys. Chem. Chem. Phys., 9, 6319-6326 (2007).* [DOI] [HUSCAP] A novel core-shell composite photocatalyst, commercially available titanium(IV) oxide (TiO2) particles directly incorporated into a hollow amorphous silica shell, was fabricated by successive coating of TiO2 with a carbon layer and a silica layer followed by heat treatment to remove the carbon layer. The composite induced efficient photocatalytic reactions when relatively small substrates were used, such as methanol dehydration and decomposition of acetic acid, without any reduction in the intrinsic activity of original TiO2, but did not exhibit efficient photocatalytic activity for decomposition of large substrates, methylene blue and polyvinyl alcohol. The unique size-selective properties of the composites are due to their structural characteristics, i.e., the presence of a pore system and a void space in the silica shell and between the shell and medial TiO2 particles, respectively. The loading of alkylsilyl groups on the surface of the composite led to highly photostable floatability: the floated sample also induced efficient photocatalytic reaction for decomposition of acetic acid while retaining floatation at the gas/water interface.

■ FBP・2007 (letter) VISIBL_B　 F. Amano, K. Nogami, R. Abe and B. Ohtani*, Facile Hydrothermal Preparation and Photocatalytic Activity of Bismuth Tungstate Polycrystalline Flake-Ball Particles , Chem. Lett., 36, 1314-1315 (2007).* [DOI] [HUSCAP] ●タングステン酸ナトリウムと硝酸ビスマスから調製した懸濁水溶液の水熱反応によって，プレート上のタングステン酸ビスマスが球状に集合し，ほぼ一定の粒径をもつ「フレークボール」が生成することについての速報．「フレークボール」という名称はこの論文から． Micrometer-sized spherical particles of bismuth tungstate (Bi2WO6) with hierarchical architecture were prepared by facile hydrothermal reaction without using any surfactants and polymers as structure-directing agents. The particles were assemblies of polycrystalline flakes composed of rectangular platelets. The hierarchical polycrystalline particles of "flake-ball" shape exhibited relatively high photocatalytic activity for oxidative decomposition of acetic acid in aqueous suspensions.

■ TSU・2007 (article) OTHERS　 X. Chen, G. Matsuo, B. Ohtani and K. Tsuji, Polymerization Behaviors of Racemic and Chiral Amphiphilic Monomers in Organized Bilayer Membranes of Lamellar Liquid Crystalline Phase, J. Polym. Sci. Part A: Polym. Chem., 45, 4891-4900 (2007).* [DOI] A racemic amphiphilic monomer, n-dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S-DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H2O2 is used as an initiator. When the initiator is changed to an amphiphilic one, 4-(2-hydroxyethoxy) phenyl-(2-hydroxy-2-propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H2O2 is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H2O2 is a result of limited diffusion of the initiator into the lamellar bilayer structures.

■ ZGK・2007 (解説) REVIEW　 大谷文章，光触媒の原理　─その常識と誤解─，現代化学，440，36-41（2007） [LINK] 最近，「光触媒」という言葉は広く知られるようになった．光触媒は，光を吸収して化学反応を起こす固体材料であり，その原理についてはさまざまな解説書などで紹介されている．しかし，研究を進めるにあたっては，きちんとした科学的な理解が重要となる．ここでは，光触媒の原理について「一般書や通常の解説書では述べられていない」ことを含めて解説する．

■ ZFC・2007 (特集) REVIEW　 大谷文章・鳥本司・池田茂，構造を制御した光触媒による有機合成の試み，月刊ファインケミカル，36，57-65（2007） [LINK] コアとなる光触媒微粒子をシリカなどの薄膜シェルに内包させ，かつ，コアとシェルの間に空隙をもつ「中空コア─シェル型」光触媒を調製した．これを用いると，裸のコアだけからなる粒子や，コアとシェルが密着して空隙がない粒子では見られない，高効率で選択的な光触媒反応が進行することを見いだした．この「中空コア─シェル型」光触媒を中心にして光触媒反応による有機合成の試みについて解説する．

■ NSJ・2007 (full paper) ACTION　 K. Nishijima, B. Ohtani, X. Yan, T.-a. Kamai, T. Chiyoya, T. Tsubota, N. Murakami and T. Ohno*, Incident light dependence for photocatalytic degradation of acetaldehyde and acetic acid on S-doped and N-doped TiO2 photocatalyst, Chem. Phys., 339, 64-72 (2007).* [DOI] ●イオウ/窒素ドープ酸化チタンによる光触媒反応の作用スペクトル解析をふくむ共同研究 We have synthesized S (S4+)-doped and N (N3-)-doped TiO2 photocatalysts. S-doped and N-doped TiO2 loaded with Fe2O3 nanoparticles have also been prepared. These photocatalysts showed activity under a wide range of wavelengths of irradiation. Action spectra of photochemical reaction rate as a function of the incident light wavelength for oxidation of acetic acid on S-doped TiO2 was studied.The photocatalytic activities of S-doped and N-doped TiO2 photocatalysts loaded with Fe2O3 nanoparticles for oxidation of acetic acid in aqueous phase and acetaldehyde in gas phase are markedly improved compared to those of doped TiO2 without loading｜of Fe2O3 nanoparticles under a wide range of incident light wavelengths. The optimum amount of Fe2O3 nanoparticles loaded on S-doped TiO2 particles was different from that on N-doped TiO2 for oxidation of organic compounds. The relationship between reaction rate of photocatalytic oxidation of acetaldehyde on doped TiO2 loaded with Fe2O3 nanoparticles and amount of Fe2O3 nanoparticles is discussed.

■ ZMR・2007 (Review) REVIEW　 村上直也・大谷文章・横野照尚，二重励起光音響分光法による酸化チタン光触媒の過渡吸収評価，未来材料，7，44-49（2007） [LINK] ●励起光として（おもに紫外光）の連続光，検出光として断続光（変調光）を波長走査してもちいるのが「二重励起光音響分光法」で，その後開発された「『逆』二重励起光音響分光法」では，励起光を波長走査し，検出光として波長一定の変調光をもちいるため，「逆」と称している． 二重励起光音響分光法を酸化チタン粒子へ適用することにより，光触媒反応が起こるその場での光吸収評価を行った．これを用いることにより，酸化チタンの「結晶欠陥の密度」と「電子の移動度」という2つの物性評価を行った例について述べる．

■ AGZ・2007 (communication) ANISOT_A　 T. Torimoto*, A. Kudo, S. Kuwabata, M. Sakuraoka and B. Ohtani, Facile Synthesis of ZnS-AgInS2 Solid Solution Nanoparticles for a Color-Adjustable Luminophore, J. Am. Chem. Soc., 129, 12388-12389 (2007).* [DOI] Nanoparticles of ZnS−AgInS2 solid solution (ZAIS) were synthesized by the thermal decomposition of (AgIn)xZn2(1-x)(S2CN(C2H5)2)4 precursors in a hot oleylamine solution. X-ray powder diffraction analyses revealed that the resulting nanoparticle powders were not a mixture of ZnS and AgInS2 but a ZnS−AgInS2 solid solution in which the fraction of ZnS was enlarged with a decrease in the value of x, that is, an increase in the content of Zn2+ in the precursors used. The energy gap of ZAIS nanoparticles could be controlled by the composition of solid solution. Intense emission was observed at room temperature, regardless of the kind of the particles, the peak wavelength of PL being blue-shifted from 720 to 540 nm with a decrease in the value of x. The highest quantum yield of ca. 24% was obtained for nanoparticles prepared with x = 0.86, which was much higher than the quantum yields reported for I−III−VI2-based semiconductor nanoparticles, such as CuInS2 and ZnS−CuInS2 solid solution.

■ LCS・2007 (communication) ANISOT_B　 S. Ikeda*, Y. Ikoma, H. Kobayashi, T. Harada, T. Torimoto, B. Ohtani and M. Matumura, Encapsulation of titanium(IV) oxide particles in hollow silica for size-selective photocatalytic reactions, Chem. Commun., 3753-3755 (2007).* [DOI] A core-shell composite of TiO2 particles encapsulated in a hollow silica was fabricated, and the core-shell composite showed size-selective photocatalytic activity for decomposition of organics without reducing the intrinsic activity of the naked TiO2 core.

■ MT3AH・2007 (full paper) NONBOS　 K. Ikeda, M. Takase, Y. Sawai, H. Nabika, K. Murakoshi and K. Uosaki, Hyper-Raman Scattering Enhanced by Anisotropic Dimer Plasmons on Artificial Nanostructures, J. Chem. Phys., 127, 111103-111103 (2007).* [DOI] Silver nanodimers with a small gap of a few nanometers aligned on glass substrates were used to enhance hyper-Raman scattering of crystal violet dye molecules. When localized surface plasmon of the dimer array was resonantly excited along the interparticle axis, hyper-Raman intensity was significantly enhanced. Moreover, the spectral appearance was slightly different between the two excitation polarizations, suggesting a possibility of two resonance contributions at one-photon and two-photon energies. Since the plasmonic property of dimer arrays can be controlled by the dimer geometry, the dimer arrays are expected to be well-defined substrates for surface-enhanced hyper-Raman spectroscopy.

■ OHN・2007 (communication) ANISOT_C　 A. Ohnuma, R. Abe, T. Shibayama and B. Ohtani*, Heterodimeric particle assemblies: Preparation of anisotropically connected spherical silica particles via surface-bound gold nanoparticles, Chem. Commun., 3491-3493 (2007).* [DOI] [HUSCAP] Assemblies of heterodimeric particles were prepared through selective coupling of two kinds of spherical silica particles of different sizes by connection with gold nanoparticles attached anisotropically to the particles.

■ ZTT・2007 (レビュー) REVIEW　 鳥本司・大谷文章，コア・シェル型粒子の光化学的ナノ構造制御と機能材料への応用，光化学，38，103-110（2007）

■ TIC・2007 (full paper) VISIBL_E　 G. Wu, T. Nishikawa, B. Ohtani and A. Chen*, Synthesis and characterization of carbon doped TiO2 nanostructures with enhanced visible light response, Chem. Mater., 19, 4530-4537 (2007).* [DOI] Carbon-doped TiO2 micro-/nanospheres and nanotubes have been synthesized via a single source chemical vapor deposition in an inert atmosphere. Organic compound Ti(OC4H9)4 was used as the titanium, oxygen, and carbon source, while argon served as the carrier gas. The effect of the temperature, substrate, and the flow rate of the carrier gas is investigated. The diameter of the formed carbon-doped TiO2 spheres can be adjusted from 100 nm to several micrometers by varying the flow rate of the carrier gas. The as-prepared TiO2 nanotubes are highly ordered with a diameter of about 100 nm and a wall thickness of around 15 nm. The estimated optical band gap is 2.78 eV for the formed carbon-doped TiO2 microspheres and 2.72 eV for the synthesized carbon-doped TiO2 nanotubes, both of which are much smaller than that of bulk anatase TiO2 (3.20 eV). The photocurrent of the carbon-doped TiO2 spheres is much higher than that of commercial P-25, which is currently considered as one of the best TiO2 photocatalysts, especially under visible light irradiation. The possible mechanism of the formation of TiO2 spheres and nanotubes is also discussed.

■ ZOA・2007 (解説) REVIEW　 大谷文章，酸化チタン微粒子の構造と光触媒活性─光触媒反応の原理にもとづいた材料設計にむけて─，光アライアンス，18，43-49（2007） [LINK]

■ SSC・2007 (full paper) RECOMB　 N. Murakami, R. Abe, O.-O. Prieto-Mahaney, T. Torimoto and B. Ohtani*, Photoacoustic spectroscopic estimation of electron mobility in titanium(IV) oxide photocatalysts, Science and Technology in Catalysis 2006, 172, 429-432 (2007).* [LINK] [HUSCAP] ●光音響分光法において，励起用連続光によって光触媒中のトラップに蓄積された電子が表面に吸着された基質に移動速度を解析し，光触媒反応速度と比較した． Double-beam photoacoustic (PA) spectroscopy was employed in measurements of the decay of trivalent titanium (Ti3+) species, in titanium(IV) oxide (TiO2) photocatalysts, produced by trapping of photoexcited electrons. The PA signal attributed to Ti3+ rapidly decayed in the dark due to the electron transfer from Ti3+ to molecular oxygen (O2) adsorbed on the surface. The rate of decay was estimated for various TiO2 powders by analysis of the decay profile and compared with the rate of photocatalytic dehydrogenation of methanol in an aqueous solution. The observed positive correlation between them suggests that both decay of Ti3+ by O2 and photocatalytic dehydrogenation of methanol are governed by the mobility of photoexcited electrons.

■ BQD・2007 (book section) BOOKPT　 鳥本司・岡崎健一・大谷文章『光化学反応を用いる単分散半導体ナノ粒子の作製と光機能材料への応用』，山本重雄編「量子ドットの生命科学領域への応用─Application of Quantum Dot in Life Science」シーエムシー出版（東京），60-70 （2007） [LINK]

■ FPA・2007 (full paper) RECOMB　 N. Murakami, O.-O. Prieto-Mahaney, R. Abe, T. Torimoto and B. Ohtani*, Double-Beam Photoacoustic Spectroscopic Studies on Transient Absorption of Titanium(IV) Oxide Photocatalyst Powders, J. Phys. Chem. C, 111, 11927-11935 (2007).* [DOI] [HUSCAP] ●装置を自作し測定法を独自に開発した二重励起光音響分光法についてフルペーパー．解析手法について詳細に検討するとともに，種々の市販酸化チタンについて，再結合中心と考えられる電子トラップの密度を解析した結果をメチルビオロゲンを用いる光化学法の結果と比較することにより，光音響分光法の欠点である吸収の絶対値が得られない点を回避できることをしめした． In situ photoabsorption properties of titanium(IV) oxide (TiO2) powders under continuous ultraviolet irradiation were investigated by double-beam photoacoustic (PA) spectroscopy. This PA measurement enabled observation of two kinds of ultraviolet-light-induced intermediate species appearing on various kinds of TiO2 powder samples. Most of the samples (type 1) exhibited photoabsorption due to the production of trivalent titanium (Ti3+) species, while transient absorption assigned to trapped holes or surface peroxy species was also observed for anatase samples with a relatively large specific surface area (type 2). Time-resolved measurements and analyses of the kinetics of photoinduced Ti3+ species suggest that electrons accumulated in type-2 samples have high reactivity toward molecular oxygen compared to type-1 samples. Saturation limits of intensity of the PA signal attributed to Ti3+ species under deaerated conditions in the presence of surface-adsorbed methanol were estimated for both types of samples, and their linear relation with density of Ti3+ species estimated by a conventional photochemical technique was observed. This suggests that the present double-beam PA technique is an alternative feasible method for estimation of density of Ti3+ species, which is a potential measure of density of crystalline defects.

■ KTM・2007 (full paper) MECHAN　 Y. Kitamura*, N. Okinaka, T. Shibayama, O.-O. Prieto-Mahaney, D. Kusano, B. Ohtani and T. Akiyama, Combustion synthesis of TiO2 nanoparticles as photocatalyst, Powder Technology, 176, 93-98 (2007).* [DOI] This paper describes a new type of combustion synthesis of metal oxide nanoparticles, in which the adiabatic flame temperature of the solid｜phase reaction is beyond the boiling point of the product, and its implementation for the synthesis of titanium dioxide as photocatalyst. In this study, raw materials comprising titanium particles of different sizes and sodium perchlorate were intensively mixed and ignited by an electrical heating foil to produce titanium dioxide through the following reaction: Ti+NaClO4→TiO2+NaCl. The shape and crystal structure of the｜titanium dioxide product significantly depended on the particle size of the titanium used as raw material. That is, the smaller titanium particles｜(average size (AS) of 10 μm) resulted in rutile with an irregular shape, whereas the larger particles (AS of 25 μm) resulted in spheres of anatase. The photocatalytic activities of these samples were evaluated using the photocatalytic reactions of aqueous titanium dioxide suspensions containing methanol and acetic acid by irradiation at 298 K in argon atmosphere or in air. The activity of the rutile-rich sample was significantly larger than that of the anatase-rich one in both photocatalytic reactions.

■ HKT・2007 (解説) REVIEW　 大谷文章・阿部竜，可視光誘起光触媒反応　─白金担持酸化タングステン光触媒を用いる高効率可視光有機物分解─，光触媒，23，58-63（2007） [LINK]

■ ANA・2007 (full paper) MECHAN　 B. Ohtani*, Y. Azuma, D. Li, T. Ihara and R. Abe, Isolation of Anatase Crystallites from Anatase-Rutile Mixed Particles by Dissolution with Aqueous Hydrogen Peroxide and Ammonia, Trans. Mater. Res. Soc. Jpn., 32, 401-404 (2007).* [LINK] ●アナタース―ルチル混合結晶であるEvonik P25からアンモニア―過酸化水素混合溶液をもちいてアナタース結晶を単離することにはじめて成功 Pure anatase crystalline phase was isolated from Degussa P25, a frequently used titanium(IV) oxide (TiO2) photocatalyst containing both anatase and rutile crystallites, by dissolving rutile phase selectively through treatment with aqueous hydrogen peroxide (H2O2)-ammonia (NH3). X-ray diffraction analyses revealed that pure crystallites have almost the same particle sizes in original P25, indicating that the purification process did not change their size distribution. Specific surface area measurement and scanning electron microscopic analysis also suggest that relatively smaller anatase crystallites were left undissolved by the H2O2-NH3 treatment.

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