Distinction of electron pathways at titanium oxide/liquid interfaces in photocatalytic processes and co-catalyst effects.

Photocatalytic reactions include several different steps and routes for photoexcited carriers, and each dynamic is closely related to the reaction efficiency. Although commonly used time-resolved techniques can reveal the kinetics of photoexcited carriers, the reaction pathways are difficult to distinguish due to decay kinetics extending over many temporal orders and various contributions from the carriers and species involved. Herein, we report the distinction of the electron dynamics in the photocatalytic processes of titanium oxide through the combination of the transient grating method and maximum entropy analysis for the estimation of time constants. We were able to confirm three different carrier responses corresponding to an intrinsic recombination, an interfacial transfer or the decay of surface-trapped electrons, and the decay of polarons. Based on the responses, it appears that both gold and platinum work as good electron acceptors, but that only platinum shortened the lifetime of the polaron state due to the acceleration in the adsorption/desorption exchange of ions, which explains the shorter cycles of the photocatalytic reactions for platinum.

The cause for the low efficiency of dye sensitized solar cells with a combination of ruthenium dyes and cobalt redox.

It has been a concern that the cobalt redox cannot give a good performance for the dye-sensitized solar cells when it is used with ruthenium dyes. The electron dynamics measurements clarified the electron loss processes, and clarified the cause. The result indicated the direct interaction between the ruthenium dyes with the cobalt redox, and it reduced the charge injection from the triplet state of the dyes to the titanium oxide, and also it increased the electron recombination process with the cobalt redox species. Both the problems of injection and recombination were solved by using the ruthenium dye with alkyl chains keeping a distance between the dye and the cobalt redox.

Effect of electrolyte constituents on the motion of ionic species and recombination kinetics in dye-sensitized solar cells.

The dynamic motion of ions in electrolyte solutions and its effect on recombination was investigated by the heterodyne transient grating method in addition to transient absorption and transient photocurrent methods in dye sensitized solar cells. Realignment of ionic species at the electrode/electrolyte interface was observed after the electron injection in TiO2 on the order of µs. The process was affected by the total quantity of ionic species as well as cation species in the electrolyte. The recombination processes of the electrons were also affected by the constituents; the probability of the electron-electrolyte recombination decreased with decrease in I2 concentration; the dominant recombination process changed from the electron-electrolyte to the electron-dye recombination by decreasing I(-) concentration. It is concluded that sufficient I(-) is necessary for the suppression of the electron-dye recombination and that sufficient I2 is necessary for an efficient redox cycle, while low concentration of I3(-) ions at the electrolyte/TiO2 interface is preferable to suppress the electron-electrolyte recombination. The effect of the cation size in an electrolyte solution on the charge dynamics was also investigated, and it was revealed that the steric hindrance of cations changed the penetration of ionic species into the nanoporous dye/TiO2 electrode, causing a change in the electrostatic properties at the interface. The cation dependence indicated that the presence of large-sized cations suppressed the electron-electrolyte recombination by disturbing the approach of I3(-) paired with the cations.

Depth-selective microscopic observation of a photomobile liquid crystal polymer under UV illumination.

By using the depth selective imaging method, we studied the UV induced change in a photomobile liquid crystalline polymer film. With 1 µm depth resolution, each slice inside the film was selectively observed. A network-like structure mixed with the ordered and disordered regions of molecules in the middle of the film, and a rubbed polymer layer at the bottom of the film were observed. In each slice of the film, the phase change induced by UV light was observed strongly dependent on the director direction, which indicates the ordering change of the liquid crystalline molecules in the director direction. It took several tens of seconds for the ordering change caused by the collaborative interaction between the molecules. Furthermore, it was suggested that the UV induced change travelled from the bottom layer to the middle layer on the micron order.

The whole process of phase transition and relaxation of poly(N-isopropylacrylamide) aqueous solution.

We observed the whole dynamics from the phase transition to the molecular relaxation of a poly(N-isopropylacrylamide) (PNIPAM) aqueous solution using the heterodyne transient grating (HD-TG) method combined with the laser temperature-jump technique. The initial phase transition corresponding to coil to globule conformational transition occurred with a time constant of 96 ± 7 µs. Then, the globule molecules aggregated due to hydrophobic interaction, and the size of the aggregates increased sufficiently to scatter light (11 ± 1 ms) when the temperature achieved by heating was high enough to exceed the phase transition temperature. The aggregates loosened due to thermal diffusion with a time constant of 44 ± 5 ms. Even after that, the released globule molecules returned back to the coil state with a lifetime of 1.5-5 s, as we reported in a previous paper (H. Inoue et al., Phys. Chem. Chem. Phys., 2012, 14, 5620-5627).

Detection of non-absorbing charge dynamics via refractive index change in dye-sensitized solar cells.

The carrier dynamics in dye-sensitized solar cells was investigated by using the transient grating, in addition to the transient absorption method and transient photocurrent method on the order of microseconds to seconds. The signals for the same sample were obtained under a short-circuit condition to compare the carrier dynamics via refractive index change with the transient photocurrent measurement. Optically silent carrier dynamics by transient absorption have been successfully observed via a refractive index change. The corresponding signal components were originated from the charge dynamics at the solid/liquid interface, especially on the liquid side; rearrangement or diffusion motion of charged redox species occurred when the injected electrons were trapped at the TiO2 surface and when the electron-electrolyte recombination occurred at the interface. The assignments were confirmed from the dependence on the viscosity of the solvent and the presence of 4-tert-butyl pyridine. As the viscosity of the solvent increased, the rearrangement and the motion of the charged redox species were delayed. Since the rearrangement dynamics was changed by the presence of 4-tert-butyl pyridine, it affected not only the TiO2 surface but also the redox species close to the interface.

Carrier dynamics in quantum-dot sensitized solar cells measured by transient grating and transient absorption methods.

Carrier dynamics in quantum-dot sensitized solar cells (QDSSCs) was clarified by combining the information obtained by the heterodyne transient grating (HD-TG), transient absorption (TA) and transient photocurrent (TP) measurements under the short circuit conditions in the time range from microseconds to seconds. The HD-TG signal is sensitive to the ionic species at the electrode/electrolyte interface, and the electrons in the titanium oxide layer injected from quantum dots (QDs) were monitored by the TA signal, and the photocurrent as a final output was monitored by the TP signal. By using the compensating information, the whole picture of the charge dynamics was obtained in the time region after the initial electron injection from QDs into the titanium oxide layer. In the former part of this paper, the assignment of the responses for each measurement was clarified based on the previous paper on dye sensitized solar cells (S. Kuwahara, et al. Phys. Chem. Chem. Phys., 2013, 15(16), 5975-5981). In the latter part, the effect of the device parameters for actual QDSSCs, such as electrolyte concentrations, and coating times of surface passivation of QDs were investigated.

Depletion force optimization for high-purity gold nanotriangles prepared using different growth methods.

A homogeneous structural distribution in metal nanoparticle is commonly required for their application, and despite high-yield growth techniques, unavoidable structural heterogeneity remains a concern in metal nanoparticle synthesis. Gold nanotriangles (AuNTs) were synthesized using seed-mediated and seedless growth methods. Recent advancements in high-yield synthesis processes have enabled easy handling of AuNTs, which exhibit unique localized surface plasmon resonance characteristics due to their anisotropic triangular form. The flocculation and subsequent precipitation technique was used to purify AuNTs of different sizes synthesized using seed-mediated and seedless growth methods. The optimal conditions for obtaining high-purity AuNTs were explored by introducing a high concentration of cetyltrimethylammonium chloride. Additionally, the depletion force necessary for achieving high-purity AuNTs was calculated to reveal variations in the required depletion forces for AuNTs synthesized using different growth techniques. The alternations in the size distribution of AuNTs during the flocculation step were tracked using dynamic light scattering, and the surface charge of AuNTs synthesized through different growth methods was evaluated by ζ-potential. The high purity of the AuNTs produced using the seedless growth method required a larger depletion force than the seed-mediated grown AuNTs. The difference in the required depletion forces results from the difference in the electrostatic forces caused by the different growth methods.

Three-dimensional building of anisotropic gold nanoparticles under confinement in submicron capsules.

The low collision rate and contact time of gold nanoparticles (NPs) in solution afford a low welding probability, which hinders their welding structure, orientation, and dimension. Encapsulated anisotropic NPs, gold nanotriangles (AuNTs), were successfully assembled into a three-dimensional structure inside a permeable silica nanocapsule under light illumination to generate localized surface plasmon resonance (LSPR). AuNTs were trapped in the permeable silica nanocapsules and diffused in the nanospace because of copolymer release, which increased the contact probability of AuNTs and promoted the three-dimensional building of AuNTs. Electron energy loss mapping simulations revealed that the obtained three-dimensional AuNT structure exhibited spatially separated multiple LSPR modes with different energies of incident light, which are photophysically attractive beyond the facet-selective chemical growth of NPs, and postmodification for anchoring substances with site-selective attachment to the obtained structure will be applicable to expand the sensing design and class of substances for sensing.

Subnanometric stabilization of plasmon-enhanced optical microscopy.

We have demonstrated subnanometric stabilization of tip-enhanced optical microscopy under ambient condition. Time-dependent thermal drift of a plasmonic metallic tip was optically sensed at subnanometer scale, and was compensated in real-time. In addition, mechanically induced displacement of the tip, which usually occurs when the amount of tip-applied force varies, was also compensated in situ. The stabilization of tip-enhanced optical microscopy enables us to perform long-time and robust measurement without any degradation of optical signal, resulting in true nanometric optical imaging with high reproducibility and high precision. The technique presented is applicable for AFM-based nanoindentation with subnanometric precision.

Copper sulfide nanoribbon growth triggered by carbon nanotube aggregation via dialysis.

The growth of copper sulfide (Cu x S) nanoribbons, a class of Cu x S nanomaterials, was achieved by the aggregation of single-walled carbon nanotubes (SWCNTs) via a dialysis process. The obtained nanoribbon structure and its constituent elements on a film of SWCNT aggregates were confirmed by transmission electron microscopy (TEM) and scanning transmittance electron microscopy-energy dispersive X-ray spectroscopy. The subsequently obtained TEM images and Raman spectra revealed that nucleus synthesis and subsequent growth of Cu x S nanoribbons occurred during the aggregation of SWCNTs. The growth procedure described in this work provides an approach for the wet chemical synthesis of metal sulfide nanomaterials.

Role of constituents for the chirality isolation of single-walled carbon nanotubes by the reversible phase transition of a thermoresponsive polymer.

The simple sorting procedure and continuous use of poly(N-isopropylacrylamide) (PNIPAM), a well-known thermoresponsive polymer, have a high potential for the mass production of single-walled carbon nanotubes (SWCNTs) with a specific electronic structure. However, knowledge of efficient single-chirality sorting methods with mixed surfactant systems is not applicable. In this work, we explored experimental conditions by controlling the interaction among PNIPAM, sodium cholate (SC) and SWCNTs. An optimization of the PNIPAM and SC concentrations as well as the addition of sodium borate achieved the selective release of (6,4) nanotubes into the liquid phase after the PNIPAM phase transition. The sorting mechanism with PNIPAM was explained by the difference in the micelle configuration on the SWCNTs and the hydrophobic collapse of PNIPAM in the presence of a sodium salt. The one-step sorting procedure for obtaining SWCNTs with a single chirality via PNIPAM will help promote their widespread application.

A new AFM-HRTEM combined technique for probing isolated carbon nanotubes.

A new technique has been developed for characterizing individual carbon nanotubes (CNTs). This technique combines atomic force microscopy (AFM) measurements with an independent determination of the CNT structure obtained by using thin carbon grid membranes for high-resolution transmission electron microscopy (HRTEM) measurements. The membrane grids are easily transferred onto silicon oxide substrates, where they are observed by AFM and an optical charged-coupled device. Electrostatic force microscopy measurements are also performed on single- and double-walled CNTs whose structures had previously been determined by HRTEM. The results reveal that the diameter and outer tube length have a greater effect on determining the capacitance of the nanotubes than the presence of the inner tube of double-walled CNTs.

Quantum Yield Enhancement in Graphene Quantum Dots via Esterification with Benzyl Alcohol.

The quantum yield of graphene quantum dots was enhanced by restriction of the rotation and vibration of surface functional groups on the edges of the graphene quantum dots via esterification with benzyl alcohol; this enhancement is crucial for the widespread application of graphene quantum dots in light-harvesting devices and optoelectronics. The obtained graphene quantum dots with highly graphene-stacked structures are understood to participate in π-π interactions with adjacent aromatic rings of the benzylic ester on the edges of the graphene quantum dots, thus impeding the nonradiative recombination process in graphene quantum dots. Furthermore, the crude graphene quantum dots were in a gel-like solid form and showed white luminescence under blue light illumination. Our results show the potential for improving the photophysical properties of nanomaterials, such as the quantum yield and band-gap energy for emission, by controlling the functional groups on the surface of graphene quantum dots through an organic modification approach.

Selective extraction of semiconducting single-walled carbon nanotubes with a thermoresponsive polymer.

The extraction of single-walled carbon nanotubes by exploiting the phase transition of poly(N-isopropylacrylamide), a thermoresponsive polymer, was performed to obtain homogenous electronic properties. The semiconducting single-walled carbon nanotubes were selectively extracted into the aqueous phase of a PNIPAM solution above the lower critical solution temperature.

Aqueous synthesis of protectant-free copper nanocubes by a disproportionation reaction of Cu2O on synthetic saponite.

Here, we report a synthesis of Cu nanocubes by photoreduction of CuSO4. Because synthetic saponite (one of the layered clay minerals) was used as the adsorbent, the nanocubes contained no capping agents or protectants, and the disproportionation reaction of Cu2O with H2SO4 was found to be the key for morphological control.

Investigation of Photoexcited Carrier Dynamics in Hematite and the Effect of Surface Modifications by an Advanced Transient Grating Technique.

Photoexcited carrier dynamics in a hematite film with and without amorphous NiFeO x on the surface was investigated using the heterodyne transient grating method. We found that two different electron/hole dynamics took place in the micro- and millisecond time regions and successfully assigned each component to the decay processes of electrons and holes trapped at surface states, respectively. It was also demonstrated that the amorphous NiFeO x coating plays a crucial role in increasing the survival of the holes at the surface trap states, which was caused by the decrease in the surface recombination rate.

Optimization of Experimental Parameters for the Performance of Solid-state Dye-sensitized Solar Cells.

The effects of various sample parameters for solid-state dye sensitized solar cells were studied with carrier dynamics measurements and electrochemical measurements. Although many parameters and processes have been decided based on the experience of researchers, the chemical and physical reasons for the selections have not been clarified. We studied the effect of the generally utilized materials and processing such as the blocking layer, titanium oxide thickness, surface treatment, and the selection of dyes and hole transfer materials. Based on our findings, we were able to rationally optimize the structure of the solid-state dye sensitized solar cells in terms of cell performance or the lifetime of charge carriers.

Study on photocatalytic organic reactions using photocatalytic microreactors.

Photocatalytic organic reactions were performed using automatic photocatalytic microreactor, where several open-end capillaries with photocatalytic materials coated inside were just soaked in a test tube including a reactant solution. Organic reactions of the alkyl radicals generated from carboxylic acids due to the photo-Kolbe reaction was studied, in analogy with the reactions using a photosensitizer. This methodology features the reusability of the reactor and an easy process for analysis due to easy separation of the reactant solution.

Local extraction and condensation under a microscope using the optically controlled phase separation of a thermoresponsive polymer.

In-situ extraction and condensation of various dyes were carried out in a phase-separation region of a thermoresponsive polymer aqueous solution generated by near infrared (NIR) laser heating under a microscope. The NIR laser irradiation was directed at a chromium line deposited on a glass substrate, thereby causing local heating of the solution due to the photothermal effect. A phase-separation region was formed by dehydration of the thermoresponsive polymer followed by ejection of water outside of the phase-separation region. When various dyes were included in the solution, some dye molecules were extracted into the phase-separation region, where they condensed. In the case of poly(N-isopropylacrylamide) (PNIPAM, 10 wt% in an aqueous solution) as the thermoresponsive polymer and crystal violet (CV) as the dye (0.1 mM), CV condensed by about 25 times. It was found that one of the necessary conditions for the extraction/condensation is the hydrophobicity of the dye molecule; however, the dominant cause for accumulating inside the PNIPAM chain is the molecular interaction between the amide group in the side chain of PNIPAM and the functional groups such as carbonyl or amino groups in the dye molecules.