Tatsuto Yui

Photochemical Reduction of CO2 Using TiO2: Effects of Organic Adsorbates on TiO2 and Deposition of Pd onto TiO2

Reduction of CO(2) using semiconductors as photocatalysts has recently attracted a great deal of attention again. The effects of organic adsorbates on semiconductors on the photocatalytic products are noteworthy. On untreated TiO(2) (P-25) particles a considerable number of organic molecules such as acetic acid were adsorbed. Although irradiation of an aqueous suspension of this TiO(2) resulted in the formation of a significant amount of CH(4) as a major product, it was strongly suggested that its formation mainly proceeded via the photo-Kolbe reaction of acetic acid. Using TiO(2) treated by calcination and washing procedures for removal of the organic adsorbates, CO was photocatalytically generated as a major product, along with a very small amount of CH(4), from an aqueous suspension under a CO(2) atmosphere. In contrast, by using Pd (>0.5 wt %) deposited on TiO(2) (Pd-TiO(2)) on which organic adsorbates were not detected, CH(4) was the main product, but CO formation was drastically reduced compared with that on the pretreated TiO(2). Experimental data, including isotope labeling, indicated that CO(2) and CO(3)(2-) are the main carbon sources of the CH(4) formation, which proceeds on the Pd site of Pd-TiO(2). Prolonged irradiation caused deactivation of the photocatalysis of Pd-TiO(2) because of the partial oxidation of the deposited Pd to PdO.

Crystallization of Tungsten Trioxide Having Small Mesopores: Highly Efficient Photoanode for Visible‐Light‐Driven Water Oxidation

(pore diameter, about 2–3 nm) can offer 1) a large internal surface area; and 2) ashorter solid-state carrier diffusion length in the nanosizedwall ( 15 nm) mesoporous systems. How-ever, particularly in case of WO

A visible-light harvesting system for CO2 reduction using a Ru(II) -Re(I) photocatalyst adsorbed in mesoporous organosilica.

A photocatalytic system for CO2 reduction exhibiting visible-light harvesting was developed by preparing a hybrid consisting of a supramolecular metal complex as photocatalyst and periodic mesoporous organosilica (PMO) as light harvester. A RuII–ReI binuclear complex (Ru–Re) with methylphosphonic acid anchor groups was adsorbed on acridone or methylacridone embedded in the walls of PMO mesochannels to yield the hybrid structure. The embedded organic groups absorbed visible light, and the excitation energy was funneled to the Ru units. The energy accumulation was followed by electron transfer and catalytic reduction of CO2 to CO on the Re unit. The light harvesting of these hybrids enhanced the photocatalytic CO evolution rate by a factor of up to ten compared with that of Ru–Re adsorbed on mesoporous silica without a light harvester.

Efficient light harvesting via sequential two-step energy accumulation using a Ru–Re5 multinuclear complex incorporated into periodic mesoporous organosilica

An efficient artificial light harvesting (LH) system was developed via sequential two-step energy accumulation. A periodic mesoporous organosilica with bridging biphenyl groups in the framework (Bp–PMO) was used as an LH antenna. The center of a linear-shaped Re(I) pentanuclear complex was connected to a Ru(II) trisdiimine complex through a covalent bond, these served as the first and second energy acceptors, respectively, (Ru–Re5). Hybridization was achieved with the non-ionic surfactant C12H25(OCH2CH2)4OH in an acetonitrile solution, and in the hybrid (Ru–Re5–Bp–PMO), the Ru–Re5 molecules were adsorbed in an orderly fashion in the mesopores of the Bp–PMO. Photons absorbed by 437 ± 43 of the Bp units were first accumulated in the five Re units in Ru–Re5 and then transferred to only one Ru unit, which emitted the light strongly.

Photoinduced electron transfer between the anionic porphyrins and viologens in titania nanosheets and monodisperse mesoporous silica hybrid films.

Photoinduced electron transfer between an anionic porphyrin derivative (tetrakis(p-carboxyphenyl)porphyrin; H(2)TCPP(4-)) and an electron accepting methyl viologen (MV(2+)) was investigated in two different nanoscale configurations, i.e., layered titania nanosheet (TNS) photocatalysts and ammonium-functionalized monodisperse mesoporous silica (AMMSS) particles. Cationic MV(2+) intercalated within the TNS interlayers while anionic H(2)TCPP(4-) was accommodated within AMMSS nanocavities to form (MV(2+)-TNS)/(H(2)TCPP(4-)-AMMSS) hybrid films. Upon irradiation with UV light and excitation of the TNS in the (MV(2+)-TNS)/(H(2)TCPP(4-)-AMMSS) hybrid films, the consumption of H(2)TCPP(4-) and the formation of a one-electron reduced MV(2+) (MV(+·)) were simultaneously observed. No consumption of H(2)TCPP(4-) was observed when an electrically insulating poly(styrene) (PS) was also introduced at the interface. These results suggest that photoinduced electron transfer occurred at the interface between the TNS and the AMMSS.

Fluorescence Control of Boron Enaminoketonate Using a Rotaxane Shuttle

The effect of rotaxane shuttling on the fluorescence properties of a fluorophore was investigated by exploiting fluorophore-tethered [2]rotaxanes. A fluorescent boron enaminoketonate (BEK) moiety was introduced in a rotaxane via transformation of an isoxazole unit generated as a result of an end-capping reaction using a nitrile N-oxide. The rotaxane exhibited a red shift of the fluorescence maximum along with a remarkable enhancement of the fluorescence quantum yield through wheel translation to the fluorophore.

Pyrene-to-porphyrin excited singlet energy transfer in LBL-deposited LDH nanosheets

Nano-ordered hybrid films of layered double hydroxide (LDH) nanosheets and two types of anionic dye molecules, i.e. tetrakis(4-carboxyphenyl)porphyrin (TCPP) and 1,3,6,8-pyrenetetrasulfonic acid (PTSA), were prepared by a layer-by-layer deposition (LBL) method. Photo-induced energy transfers (PET) between the PTSA and TCPP layers were investigated for two differently stacked structures of the TCPP/LDH/PTSA hybrid films, i.e. (a) PTSA/LDH multilayers independently stacked on the TCPP/LDH multilayers to form (TCPP/LDH)n/(PTSA/LDH)n and (b) TCPP/LDH and PTSA/LDH monolayers deposited alternately to form [(TCPP/LDH)/(PTSA/LDH)]n hybrid films, which were both prepared by varying the successive and alternate stacking of the (TCPP/LDH) and (PTSA/LDH) unit layers. A Foerster type resonance energy transfer is observed in the present hybrid films, where the efficiency of PET was strongly affected by changing the distance between the TCPP and PTSA molecules in the (TCPP/LDH)3/(PSS/LDH)m/(PTSA/LDH)3 hybrid films (m = 1−10) obtained by the insertion of the photochemically inert poly(styrenesulfonic acid) (PSS) and LDH hybrid layers, i.e. the insertion of (PSS/LDH)m between the (TCPP/LDH)3 and (PTSA/LDH)3 layers.

Monoclinic Ag2Mo2O7 nanowire: a new Ag-Mo-O nanophotocatalyst material.

We report a template-free facile technique that allows for the first ever synthesis of a monoclinic Ag2Mo2O7 nanowire (m-Ag2Mo2O7-NW), using a commercially available MoO3 particle. The nanowire possessed high crystallinity and structural homogeneity and strongly suggested that the nanowire was grown through an oriented aggregation mechanism in contrast to the case of a typical solution-phase method. The corresponding bulky counterpart showed no photoresponse; however, a complete structural transformation toward a nanowire triggered activity for O2 evolution in the presence of Ag(+) as an electron acceptor under visible-light irradiation.

Photochemical electron transfer though the interface of hybrid films of titania nano-sheets and mono-dispersed spherical mesoporous silica particles

Photochemical Electron Transfer (ET) between an organic dye, the porphyrin derivative TMPyP, and an electron acceptor, methyl viologen MV2+, have been investigated at the interface of two different inorganic films, i.e., layered titania nano-sheets (TNS) and a monolayer film of spherical and mono-dispersed mesoporous silica (sMPS) particles (ca. 0.5 μm). TMPyP ions were intercalated within the sMPS nano-cavities to form (TMPyP–sMPS) while MV2+ ions were intercalated into the TNS interlayers to form (MV2+–TNS). The (TMPyP–sMPS) and (MV2+–TNS) films were then stacked on a silica substrate in this order to form a (MV2+–TNS)/(TMPyP–sMPS) film and, upon UV light irradiation, ET could be induced. However, when this film was stacked inversely, i.e., for the (TMPyP–sMPS)/(MV2+–TNS) films on a silica substrate, no photoinduced ET were observed. Interestingly, however, even for this photo-inactive inversely stacked film, ET could be generated by inserting a gold vapor-deposited layer between the (MV2+–TNS) and (TMPyP–sMPS) films. The conjugation conditions at the interface of the inversely stacked (TMPyP–sMPS)/(MV2+–TNS) hybrid film were, thus, confirmed to strongly affect the photoinduced electron transfers and their efficiencies.

Intercalation of a Surfactant with a Long Polyfluoroalkyl Chain into a Clay Mineral: Unique Orientation of Polyfluoroalkyl Groups in Clay Layers

Eight novel polyfluorinated surfactants (C(n)F(2n+1)CONH(CH2)2 N(+)(CH3)2C16H33 Br(-); abbreviated as CnF-S, where n = 1, 2, 3, 4, 5, 6, 8, 10) were synthesized and their intercalation into cation-exchangeable clay was investigated. All of the polyfluorinated surfactants intercalated in amounts exceeding the cation exchange capacity (CEC) of the clay. The C4F-S and C5F-S surfactants exhibited intercalation up to 480% of the CEC as a saturated adsorption limit. On the basis of X-ray analysis, CnF-S surfactants intercalated between clay nanosheets to form a bilayer structure in which the surfactant molecules tilt at an angle of ∼60° with respect to the clay surface. The saturated adsorption limits and layer distances differed between surfactants with short (n = 1, 2) and long (n = 3-10) perfluoroalkyl chains. For long-chain surfactants, their saturated adsorption limits were independent of the perfluoroalkyl chain length and the layer distances systematically increased with increasing perfluoroalkyl chain length. These results suggest that the microscopic orientation differed between the short and long chains. X-ray analysis showed that the long-chain surfactants orient the perfluoroalkyl chains at a tilt of 41 ± 5° with respect to the clay layer. This value was in good agreement with polarized IR measurements of 42 ± 2° for this angle.