Effects of incorporation of Ag into a kesterite Cu2ZnSnS4 thin film on its photoelectrochemical properties for water reduction.

Kesterite Cu2ZnSnS4 (CZTS) thin films in which the Cu site was partially replaced with Ag were prepared by spray deposition on an Mo-coated glass substrate. Successful replacement of Cu components in the CZTS lattice with Ag up to an Ag/(Cu + Ag) ratio of 0.20 was achieved. Samples with relatively low contents of Ag (Ag/(Cu + Ag) ratios of 0.05 and 0.10) showed obvious grain growth compared to that of bare CZTS, whereas samples with higher Ag contents showed an appreciable decrease in grain sizes. Photoelectrochemical properties for water reduction (H2 production), which was examined after surface modifications with an In2S3/CdS double layer and Pt catalyst for H2 evolution, depended strongly on such morphological differences; a maximum conversion efficiency, i.e., half-cell solar to hydrogen efficiency, of 2.4% was achieved by the photocathode based on the film with an Ag/(Cu + Ag) ratio of 0.10. Minority carrier dynamics examined by photoluminescence measurements indicated that such an active sample of PEC H2 production had a relatively long carrier lifetime, suggesting that the suppression of carrier recombination at grain boundaries in the bulk of these kesterite films is one of the important factors for enhancing PEC functions.

Effects of TiCl4 treatment on the structural and electrochemical properties of a porous TiO2 layer in CH3NH3PbI3 perovskite solar cells.

The effects of surface treatment with TiCl4 on the structural and electrochemical properties of a porous titanium oxide (pTiO2) layer deposited on a fluorine-doped tin oxide (FTO)/glass substrate covered with a dense TiO2 layer (pTiO2/dTiO2/FTO/glass) were systematically investigated in order to obtain an optimum pTiO2 layer for use in CH3NH3PbI3 perovskite solar cells. As confirmed by thermal desorption spectroscopy (TDS) analyses, the amount of surface hydroxyl groups in pTiO2 varied when the pTiO2/dTiO2/FTO/glass sample was treated with solutions with different concentrations of TiCl4 (i.e., 20, 50, 80, and 100 mM). Photoelectrochemical (PEC) analyses of the pTiO2/dTiO2/FTO/glass samples after TiCl4 treatment showed significant increments of photocurrent densities compared to the pTiO2/dTiO2/FTO/glass sample without TiCl4 treatment regardless of the concentration of TiCl4 used in the solution. Electrochemical impedance spectroscopy (EIS) analyses of the TiCl4-treated pTiO2/dTiO2/FTO/glass samples also indicated a lower recombination probability with an increase in TiCl4 concentration. The results suggest that TiCl4 treatment resulted in passivation of defect sites on the surface of the TiO2 nanoparticles as well as improvement of the interconnectivity between the TiO2 nanoparticles in pTiO2. In contrast, the power conversion efficiencies (PCEs) and short circuit current densities of CH3NH3PbI3 perovskite solar cells based on these pTiO2/dTiO2/FTO/glass samples exhibited volcano-like patterns depending on the TiCl4 concentration used for the pTiO2 treatment: the highest PCE was obtained by using pTiO2/dTiO2/FTO/glass treated with 50 mM of TiCl4 solution. Structural analysis of the CH3NH3PbI3 perovskite part performed by X-ray diffraction (XRD) indicated that the formation of CH3NH3PbI3 perovskite was inhibited by the presence of surface hydroxyl groups in the pTiO2 film without TiCl4 treatment. TiCl4 treatment using TiCl4 solutions with concentrations up to 50 mM enhanced the formation of the CH3NH3PbI3 perovskite layer, whereas TiCl4 treatment using TiCl4 solutions with concentrations higher than 50 mM was detrimental due to the formation of nanoparticulate TiO2 aggregates that induce poor porosity and act as recombination sites.

Photoelectrochemical water reduction over wide gap (Ag,Cu)(In,Ga)S2 thin film photocathodes.

The effects of partial replacement of Cu with Ag in a Cu(In,Ga)S2 (CIGS) thin film on its structural, optical, electrostructural, and photoelectrochemical (PEC) properties were investigated, in order to improve its performance for PEC water reduction under sunlight illumination. Results from X-ray diffraction (XRD) analyses revealed the successful partial replacement of Cu with Ag to form solid-solutions with different Ag/(Ag + Cu) ratios (A(x)CIGS, x = Ag/(Ag + Cu) = 0.1, 0.2, 0.3 and 0.4), as confirmed by a gradual change in the (112) reflections to smaller 2θ angles with increasing Ag/(Ag + Cu) ratio. Analyses of the photoabsorption properties of the materials using photoacoustic spectroscopy indicated changes in the band gap energies associated with increasing the Ag/(Ag + Cu) ratio. In addition, valence band maximum potentials of A(x)CIGS were deepened gradually with increasing Ag/(Ag + Cu) ratio. After modifying these A(x)CIGS films with a CdS ultrathin (ca. 70 nm) layer and a Pt catalyst, the PEC water reduction properties were evaluated in an electrolyte solution with the pH adjusted to 6.5, under simulated sunlight (AM 1.5G) radiation. Compared to the CdS- and Pt-modified Ag-free A(x)CIGS (A(0)CIGS) films, appreciable enhancements in the PEC properties were observed for electrodes based on A(x)CIGS (x > 0) films, and the best PEC performance was obtained for the electrode based on the A(0.2)CIGS film. However, the electrode derived from the A(x)CIGS film with Ag/(Ag + Cu) ratios higher than 0.3 showed diminished PEC properties due to the partial conversion of its semiconducting properties from p-type to n-type.

[A Case Report of Spontaneous Cerebrospinal Fluid Otorrhea].

Spontaneous cerebrospinal fluid(CSF)otorrhea is less common than CSF leakage caused by trauma, and rarely occurs in adults. We report an adult case of CSF otorrhea. A 71-year-old woman with no traumatic or otologic history was hospitalized due to bacterial meningitis. After hospitalization, CSF leakage started suddenly from the left external ear canal. A high resolution CT scan with intrathecal administration of contrast material revealed CSF leakage in the left ear canal and multiple bone erosions in both the tegmen mastoideum and the posterior fossa aspect of the petrous bone. We performed closure and surgery via the middle fossa approach. We identified a bone defect in the tegmen mastoideum but could not detect any obvious abnormality in the dura mater. We placed both a pericranial flap and a free abdominal fat on the middle base of the skull as sealing materials. There was no recurrence of CSF otorrhea following surgery. In this surgery, the use of a multilayered closure technique is very important to avoid the recurrence of CSF leakage.

Pt/In2S3/CdS/Cu2ZnSnS4 Thin Film as an Efficient and Stable Photocathode for Water Reduction under Sunlight Radiation.

An electrodeposited Cu2ZnSnS4 (CZTS) compact thin film modified with an In2S3/CdS double layer and Pt deposits (Pt/In2S3/CdS/CZTS) was used as a photocathode for water splitting of hydrogen production under simulated sunlight (AM 1.5G) radiation. Compared to platinized electrodes based on a bare CZTS film (Pt/CZTS) and a CZTS film modified with a CdS single layer (Pt/CdS/CZTS), the Pt/In2S3/CdS/CZTS electrode exhibited a significantly high cathodic photocurrent. Moreover, the coverage of the In2S3 layer was found to be effective for stabilization against degradation induced by photocorrosion of the CdS layer. Bias-free water splitting with a power conversion efficiency of 0.28% was achieved by using a simple two-electrode cell consisting of the Pt/In2S3/CdS/CZTS photocathode and a BiVO4 photoanode.

Clinical outcomes of prostate cancer patients in Yokosuka City, Japan: A comparative study between cases detected by prostate-specific antigen-based screening in Yokosuka and those detected by other means.

OBJECTIVES: To investigate whether prostate-specific antigen-based screening reduced the prostate cancer mortality rate in Yokosuka, Japan. METHODS: We carried out a cohort study, in which we compared clinical outcomes between patients detected by prostate-specific antigen-based screening (S group n = 524) versus those detected by other means (NS group n = 1044). Clinical and pathological factors were evaluated using Cox regression analyses and the Kaplan-Meier method. RESULTS: A total of 1.5% (8/524) of patients in the S group and 6.7% (70/1044) of those in the NS group died from prostate cancer during follow up. A total of 8.0% (42/524) of patients in the S group and 11.4% (119/1044) in the NS group died from other causes. The 10-year cancer specific survival rates of the S and NS groups were 97% and 86%, respectively (P < 0.001). The median age was significantly lower in the S group than the NS group: 71 and 73 years, respectively (P < 0.001). The rate of Gleason score 8-10 was significantly lower in the S group than the NS group: 9.7% and 16.7%, respectively (P < 0.001). The rate of patients with metastasis or prostate-specific antigen 100 ng/mL or more was significantly lower in the S group than the NS group: 7.8% and 23.0%, respectively (P < 0.001). On multivariate analysis, Gleason score 8-10 compared with Gleason score 6 was independently associated with cancer-specific survival (hazard ratio 4.808, 95% confidence interval 1.044-22.14, P = 0.044). CONCLUSIONS: Prostate-specific antigen-based population screening in Yokosuka City might help to reduce the prostate cancer mortality rate.

Enhancement of solar hydrogen evolution from water by surface modification with CdS and TiO2 on porous CuInS2 photocathodes prepared by an electrodeposition-sulfurization method.

Porous films of p-type CuInS2, prepared by sulfurization of electrodeposited metals, are surface-modified with thin layers of CdS and TiO2. This specific porous electrode evolved H2 from photoelectrochemical water reduction under simulated sunlight. Modification with thin n-type CdS and TiO2 layers significantly increased the cathodic photocurrent and onset potential through the formation of a p-n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H2 production under the present reaction conditions.

Process Accumulated 8% Efficient Cu2 ZnSnS4 -BiVO4 Tandem Cell for Solar Hydrogen Evolution with the Dynamic Balance of Solar Energy Storage and Conversion.

A process accumulated record solar to hydrogen (STH) conversion efficiency of 8% is achieved on the Cu2 ZnSnS4 -BiVO4 tandem cell by the synergistic coupling effect of solar thermal and photoelectrochemical (PEC) water splitting with the dynamic balance of solar energy storage and conversion of the greenhouse system. This is the first report of a Cu2 ZnSnS4 -BiVO4 tandem cell with a high unbiased STH efficiency of over 8% for solar water splitting due to the greenhouse device system. The greenhouse acts as a solar thermal energy storage cell, which absorbs infrared solar light and storage as thermal energy with the solar light illumination time, while thermoelectric device (TD) converts thermal energy into electric power, electric power is also recycled and added onto Cu2 ZnSnS4 -BiVO4 tandem cell for enhanced overall water splitting. Finally, the solar water splitting properties of the TD-Cu2 ZnSnS4 -BiVO4 integrated tandem cell in pure natural seawater are demonstrated, and a champion STH efficiency of 2.46% is presented, while a large area (25 cm2 ) TD-Cu2 ZnSnS4 -BiVO4 integrated tandem device with superior long-term stability is investigated for 1 week, which provides new insight into photoelectrochemical solar water splitting devices.

Research on the Influence of the Interfacial Properties Between a Cu3 BiS3 Film and an Inx Cd1- x S Buffer Layer for Photoelectrochemical Water Splitting.

The ternary compound photovoltaic semiconductor Cu3 BiS3 thin film-based photoelectrode demonstrates a quite promising potential for photoelectrochemical hydrogen evolution. The presented high onset potential of 0.9 VRHE attracts much attention and shows that the Cu3 BiS3 thin films are quite good as an efficient solar water splitting photoelectrode. However, the CdS buffer does not fit the Cu3 BiS3 thin film: the conduction band offset between CdS and Cu3 BiS3 reaches 0.7 eV, and such a high conduction band offset (CBO) significantly increases the interfacial recombination ratio and is the main reason for the relatively low photocurrent of the Cu3 BiS3 /CdS photoelectrode. In this study, the Inx Cd1- x S buffer layer is found to be significantly lowered the CBO of CBS/buffer and that the In incorporation ratio of the buffer influences the CBO value of the CBS/buffer. The Pt-TiO2 /In0.6 Cd0.4 S/Cu3 BiS3 photocathode exhibits an appreciable photocurrent density of ≈12.20 mA cm-2 at 0 VRHE with onset potential of more than 0.9 VRHE , and the ABPE of the Cu3 BiS3 -based photocathode reaches the highest value of 3.13%. By application of the In0.6 Cd0.4 S buffer, the Cu3 BiS3 -BiVO4 tandem cell presents a stable and excellent unbiased STH of 2.57% for over 100 h.

Effect of heterojunction structures on photoelectrochemical properties of ZnTe-based photocathodes for water reduction.

Photoelectrochemical (PEC) properties of ZnTe-based photocathodes with various structures were investigated to clarify the effective structure for the water reduction reaction. Samples with n-ZnO/ZnTe/p-ZnTe and n-ZnS/ZnTe/p-ZnTe heterostructures showed superior PCE properties to the samples without a heterojunction. In particular, the n-ZnS/ZnTe/p-ZnTe sample exhibited a large photocurrent even at a low applied potential in an electrolyte containing Eu3+ ion as an electron scavenger. Appreciable H2 evolution with a constant rate (approximately 87 µmol cm-2 h-1) was also observed over the sample loaded with Pt deposits under visible-light irradiation (>420 nm): faradaic efficiency of almost 100% was obtained, indicating no unfavorable side reaction occurred in the sample.

Fabrication of CuInS2 films from electrodeposited Cu/In bilayers: effects of preheat treatment on their structural, photoelectrochemical and solar cell properties.

Polycrystalline CuInS(2) films were fabricated by sulfurization of electrodeposited Cu and In metallic precursor films in a Cu-rich composition at 520 °C in H(2)S (5% in Ar). Structural analyses revealed that the adherence of the thus-formed CuInS(2) film to the Mo substrate was strongly dependent on heating profiles of the Cu/In bilayer film: a CuInS(2) film with poor adherence having many crevices was formed when the Cu/In bilayer film was heated monotonously from room temperature to 520 °C in Ar within 25 min followed by sulfurization, whereas CuInS(2) films with good adherence were obtained when the Cu/In films were pretreated at 110 °C in Ar for 10-60 min just before increasing the temperature up to 520 °C for sulfurization. It was also clarified that the CuInS(2) film obtained without 110 °C pretreatment had pinholes inside the film, whereas the CuInS(2) films formed after 110 °C pretreatment showed no notable pinholes. Photoelectrochemical responses of these CuInS(2) films in an electrolyte solution containing Eu(III) indicated that the CuInS(2) films obtained after 110 °C pretreatment had higher external quantum efficiency (EQE) values than those of films obtained without 110 °C pretreatment, mainly due to better adherence of 110 °C pretreated CuInS(2) films to the Mo substrate than the CuInS(2) film obtained without 110 °C pretreatment. The performance of solar cells with an Al:ZnO/Zn(S,O)/CdS/CuInS(2)/Mo structure also depended on the structural characteristics of the CuInS(2) films, i.e., preliminary conversion efficiencies of ca. 5% were obtained for devices based on the CuInS(2) films obtained after 110 °C pretreatment, whereas the device prepared by the CuInS(2) film without 110 °C pretreatment showed the conversion efficiency less than 1.5%.

Determination of oxygen sources for oxidation of benzene on TiO2 photocatalysts in aqueous solutions containing molecular oxygen.

Photocatalytic oxidation of benzene to CO(2) was studied in aqueous solutions using different kinds of TiO(2) powders, and isotopic oxygen tracers (H(2)(18)O and (18)O(2)) were used to investigate the oxidation process. Phenol was produced as a main intermediate in solution. When anatase powders, which showed high activity for oxidation of benzene, were used, 70-90% of oxygen introduced into phenol was from water. On the other hand, when rutile powders were used, only 20-40% of the oxygen was from water. The rest was from molecular oxygen in both cases. The rate of phenol production by using molecular oxygen was nearly the same between anatase and rutile powders. Hence, the high activity of anatase powders for oxidation of benzene to CO(2) is attributed to their high activity for oxidation of benzene to phenol, which is considered to be the rate-determining step, using water as the oxygen source. The processes using water and molecular oxygen as the oxygen sources are ascribed, respectively, to oxygen transfer and hole transfer processes in the initial step of benzene oxidation.

Catalytic activity and regeneration property of a Pd nanoparticle encapsulated in a hollow porous carbon sphere for aerobic alcohol oxidation.

A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions.

Multicomponent sulfides as narrow gap hydrogen evolution photocatalysts.

A series of mixed crystals composed of Cu(2)ZnSnS(4), Ag(2)ZnSnS(4) and ZnS was prepared by co-precipitation of the corresponding metal ions in aqueous sodium sulfide followed by annealing in a sulfur atmosphere. Ideal solid solutions of Cu(2)ZnSnS(4) and Ag(2)ZnSnS(4) with a kesterite structure ((Cu(x)Ag(1-x))(2)ZnSnS(4) (0 ≤x≤ 1)) were successfully obtained by this procedure, as confirmed by their X-ray diffraction (XRD) patterns and energy-diffuse X-ray (EDX) analyses. On the other hand, the solubility of ZnS in these kesterite compounds was found to be limited: the upper limit of the ratio of ZnS to (Cu(x)Ag(1-x))(2)ZnSnS(4) was less than 0.1, regardless of the Cu-Ag ratio in (Cu(x)Ag(1-x))(2)ZnSnS(4). Based on the results for dependence of their photoabsorption properties on atomic compositions, a plausible band structure is discussed. Evaluation of the photocatalytic activity for H(2) evolution of these mixed crystals from an aqueous solution containing S(2-) and SO(3)(2-) ions upon loading Ru catalysts under simulated solar radiation (AM 1.5) revealed that active compounds for this reaction should contain both dissolved ZnS and Ag components. The dissolved ZnS in (Cu(x)Ag(1-x))(2)ZnSnS(4) gave upward shifts of their conduction band edges. Moreover, the presence of Ag in the solid solution provided n-type conductivity, leading to efficient migration of photogenerated electrons to the surface to induce water reduction into H(2).

[Verrucous carcinoma of penis: a case report].

We report a case of verrucous carcinoma of the penis. A 62-year-old man, who presented with penile swelling and pain, was referred to our hospital. Although, penile tumor biopsy revealed no evidence of malignancy, the patient presented with penile swelling and discharge. The penis was surgically resected and urinary diversion was performed. The pathological examination of the resected glans revealed verrucous carcinoma of penis. Furthermore, in situ hybridization revealed human papilloma virus (HPV) infection. This clearly showed that the verrucous carcinoma of the penis resulted from the HPV infection. The patient has survived for 14 months after surgery without local recurrence or metastasis.

Synthesis of nano-sized tungsten oxide particles encapsulated in a hollow silica sphere and their photocatalytic properties for decomposition of acetic acid using Pt as a co-catalyst.

Nano-sized tungsten oxide (WO3) particles, each of which was encapsulated as a core in a hollow silica sphere (WO3@SiO2), were synthesized using calcium tungstate particles as the starting material. The calcium tungstate particles, each of which was covered with a silica shell, were converted to tungstic acid by nitric acid treatment and then to WO3 by heat treatment to obtain WO3@SiO2. A hollow space was formed in WO3@SiO2 between the WO3 core and the SiO2 shell as a result of shrinkage of WO3 during the heat treatment. The thus-obtained WO3@SiO2 was 40 nm in diameter, the WO3 core was 10 nm in diameter, and the silica shell, which was permeable to gas and liquid, was 10 nm in thickness. WO3@SiO2 absorbed visible light to the wavelength of 454 nm, which enabled photocatalytic reaction under visible light; Pt was loaded on the WO3 cores in the photocatalytic reactions. In contrast to Pt-loaded bulk WO3 photocatalysts without an SiO2 shell, Pt-loaded WO3@SiO2 showed continuous and complete decomposition of gaseous acetic acid in air under visible as well as UV irradiation.

Preparation of a CuGaSe2 single crystal and its photocathodic properties.

Chalcopyrite CuGaSe2 single crystals were successfully synthesized by the flux method using a home-made Bridgman-type furnace. The grown crystals were nearly stoichiometric with a Se-poor composition. Although a wafer form of the thus-obtained single crystal showed poor p-type electrical properties due to such unfavorable off-stoichiometry, these properties were found to be improved by applying a post-annealing treatment under Se vapor conditions. As a result, an electrode derived from the Se-treated single crystalline wafer showed appreciable p-type photocurrents. After deposition of a CdS ultrathin layer and a nanoparticulate Pt catalyst on the surface of the electrode, appreciable photoelectrochemical H2 evolution was observed over the modified electrode under photoirradiation by simulated sunlight with application of a bias potential of 0 VRHE.

Environmentally friendly Cu2ZnSnS4-based photocathode modified with a ZnS protection layer for efficient solar water splitting.

High-quality Cu2ZnSnS4 (CZTS) thin films prepared by spray pyrolysis on a Mo-coated glass substrate were used for solar water splitting in this study. Modification of a CdS layer under CZTS improved the photocatalysis efficiency by forming a pn junction between CdS and CZTS, effectively separating the photoexcited carriers without recombination. However, the photocorrosive nature of CdS induces poor stability of the CdS/CZTS photocathode. Surface protection of a CdS-covered CZTS photocathode by a ZnS layer resulted in efficient photoelectrochemical water splitting with a maximum half-cell solar to hydrogen (HC-STH) efficiency of 2.1% and without showing appreciable degradation. The ZnS layer acts as a mediator for efficient electron transport to Pt deposits and as a protective layer, preventing contact between the CdS layer and the outer electrolyte solution.

Brainstem Venous Congestion Caused by Perimedullary Drainage in Anterior Cranial Fossa Dural Arteriovenous Fistula.

BACKGROUND: Myelopathy develops relatively rarely in intracranial dural arteriovenous fistula (DAVF); it has only been reported in posterior cranial fossa DAVF. Herein, we report the first, to our knowledge, case of anterior cranial fossa (ACF) DAVF with myelopathy. CASE DESCRIPTION: A 75-year-old man presented with dizziness, nausea, and gait disturbance. T2-weighted magnetic resonance imaging revealed a hyperintense area in the left cerebellum and medulla; a flow void was also detected around the medulla. The patient was first diagnosed with spinal DAVF, but the shunt point was detected at the anterior ethmoidal artery, flowing from the olfactory vein to the basal vein of Rosenthal and anterior/posterior spinal veins. The shunt point was clipped during craniotomy, and neurologic symptoms improved. CONCLUSIONS: Myelopathy because of intracranial DAVF potentially involves diagnostic pitfalls. Even in ACF DAVF, there is a possibility of myelopathy caused by perimedullary venous drainage.