出版者・発行元：Advanced Engineering Materials  

Astronomical impacts by small solar system bodies (meteoroids, asteroids, comets, and transitional objects) are considered a mechanism for delivering amino acids and their polymerization to proteins in early Earth conditions. High-pressure torsion (HPT) is a new methodology to simulate such impacts and clarify the behavior of biomolecules. Herein, two amino acids, crystalline L-serine and L-glutamic acid that are detected in meteorites, are processed by HPT and examined by ex situ X-ray diffraction, Raman spectroscopy, nuclear magnetic resonance, Fourier-transform infrared spectroscopy, and in situ mechanical shear testing. No polymerization, chemical reactions, or phase transformations are detected after HPT, indicating that the stability and presence of these two amino acids in meteorites are quite reasonable. However, some microstructural and mechanical changes like crystal size reduction to the nanometer level, crystal defect formation, lattice expansion by vacancy formation, and shear strength enhancement to the steady state are found which are similar to the behaviors reported in metals and ceramics after HPT processing.

DOI： 10.1002/adem.202302267

Web of Science

Scopus

出版者・発行元：ACS Sustainable Chemistry and Engineering  

[FeFe]-hydrogenase (HydA) is an active biocatalytic enzyme for solar-to-hydrogen (H2) conversion. However, stability is a main challenge that limits practical applications. This work aims to encourage the efficiency of HydA by encapsulating it in the zeolitic imidazolate framework-8 (ZIF-8) as a synthetic protective shield. The construction of HydA@ZIF-8 nanoparticles, with an average diameter of 700-1000 nm, at ambient conditions can preserve HydA activity within a spatially confined microenvironment, as characterized by scanning electron microscopy and X-ray diffraction analysis. Based on MV•+-dependent H2 production activity and kinetic analysis, both the stability and efficiency of HydA@ZIF-8 surpass those of free HydA and whole-cell biocatalysts over a wider range of pH and temperature. The achievement of robust HydA@ZIF-8 construction represents a significant step forward in the development of biocatalysts for various future applications.

DOI： 10.1021/acssuschemeng.3c08560

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：公益社団法人　電気化学会  

A dense NiO-Fe2O3 (NiFe) pellet has been developed as a potential anode-support for thin-film solid oxide fuel cells (SOFCs). However, preparation of dense NiFe is very challenging. Hole-formed NiFe pellets or porous NiFe pellets are frequently formed, which cannot be used as a support (substrate) for thin-film SOFCs. Therefore, this hole-formed NiFe support is simply wasted. In this report, we attempt to re-qualify this NiFe support to be a valuable substrate, which can be used for fabricating thin-film SOFCs. By deposition of smaller NiFe particles to cover the hole-formed NiFe support, the surface of this NiFe pellet is modified. Large holes on the surface disappear. The newly formed NiFe support can be used for fabricating a single cell with La0.9Sr0.1Ga0.8Mg0.2O3−δ as thin-film electrolyte operated at intermediate temperature. Maximum power density generated from this cell is 0.45, 0.86 and 1.28 W cm−2 at 873, 923 and 973 K, respectively. (Figure Presented).

DOI： 10.5796/electrochemistry.23-00164

Web of Science

Scopus

CiNii Research

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Applied Catalysis B: Environmental  

NH3 is an important chemical fertilizer and expecting as H2 carrier. Several methods have been investigated for eco-friendly NH3 production under mild conditions instead of Haber-Bosch process using 400 °C, 20 MPa. Here, cyanobacterial Anabaena variabilis was utilized as a nitrogenase-producing biocatalyst that converts N2/H2O to NH3 under ambient conditions. Biocatalytic reactions revealed that MV•+ can penetrate cell membrane and transfer electrons generated in inorganic photocatalyst. We first reported photobiocatalytic NH3 production of cyanobacteria and TiO2. Comparing with natural system, NH3 formation rate of the hybrid system increased 81.3 times with an initial rate of 2031.7 nmol·h−1 and turnover number of 216.8.

DOI： 10.1016/j.apcatb.2023.123431

Web of Science

Scopus

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the Electrochemical Society  

Effects of channel size in NiO-YSZ porous substrate were studied on power density in solid oxide fuel cell mode and electrolysis current in steam electrolysis mode. It was found that the cell deposited on anode substrate with larger pore diameter shows a superior performance. The LSGM cell prepared on Ni-YSZ tube with average channel diameter of ca. 2.5 μm shows the maximum power density of 0.36 W cm−2 in SOFC mode and 0.42 A cm−2 at 1.6 V in SOEC mode at 873 K. Spike potential noise which may be caused by insufficient gas diffusion in NiO-YSZ porous substrate was observed under constant current electrolysis condition in case of NiO-YSZ tube with narrow channel and the spike noise is suppressed by increasing channel size. NiO-YSZ tube with large channel size is also effective for increasing long term stability in electrolysis mode.

DOI： 10.1149/1945-7111/ad2815

Web of Science

Scopus

researchmap

その他リンク： https://iopscience.iop.org/article/10.1149/1945-7111/ad2815/pdf

掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of Materials Chemistry C  

In this study, a hybrid photocatalyst with titanium oxide using reduced graphene nanoribbons (rGNR) was fabricated. The resulting 0.5 wt% platinum-loaded titanium oxide-supported reduced GNRs (Pt/TiO2/rGNR) exhibited an activity of 2.54 mmol h−1 g−1 which is 6.35 times higher than the 0.40 mmol h−1 g−1 of the titanium oxide photocatalyst. This activity was also higher than that of the starting material, multi-walled carbon nanotube (MWCNT)-supported titanium oxide (Pt/TiO2/MWCNT) as 0.80 mmol h−1 g−1. The resulting catalysts were characterized by X-ray photoelectron spectroscopy (XPS) and fluorescence lifetime spectroscopy, and the GNRs chemically reduced by NaBH4 (rGNR) had higher conductivity than the GNRs reduced by photogenerated electrons (pGNR) from titanium oxide. It was found using the photocatalytic reaction and photocurrent test that almost no photoresponsivity of reduced GNR character was exhibited. This result clarified that the reduced GNRs played the role of a mediator that promotes charge separation between photocatalysts and that effective hydrogen production in water was achieved.

DOI： 10.1039/d3tc03622g

Web of Science

Scopus

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Catalysis Today  

Photocatalytic hydrogen peroxide (H2O2) by oxygen and phosphorus co-doped graphitic carbon nitride (C3N4) with cobalt phosphate (CoP) cocatalyst is investigated. The photocatalyst powder of CoP-C3N4 1:n, n = 0–4, n is the weight ratio of cyanuric acid added) was synthesized by melamine cyanurate template method. Characterization of the catalyst was performed by X-ray diffraction analysis, and scanning electron microscopy, X-ray photoemission spectra, and fluorescence decay spectra. Oxygen doping was performed by the melamine and cyanuric acid template method, followed by phosphorus doping of the C3N4 backbone by the introduction of CoP. Co-doping of O and P atom facilitated charge transfer on the C3N4 backbone, while CoP facilitated charge separation at the C3N4 interface. The CoP-C3N4 (1:4) photocatalyst increased H2O2 production rate by 293 % compared to that of the cyanuric acid-free photocatalyst and also achieved the photocatalytic oxygen evolution from water. These results indicate that O,P co-doped CoP-C3N4 can perform sacrificial agent-free hydrogen peroxide under visible light irradiation.

DOI： 10.1016/j.cattod.2023.114400

Web of Science

Scopus

researchmap

出版者・発行元：2024 31st International Workshop on Active-Matrix Flatpanel Displays and Devices, AM-FPD 2024  

The structural modifications prevent molecular aggregation by adding a bulky spiro[fluorene-9,9'-phenanthrene ]-10' auxiliary acceptor (A1) and benzo[c][1,2,5]thiadiazole (A2) between the donor and π-bridge moiety. Additionally, the carbonyl group improves the capture of Li+ ions, delaying charge recombination. Moreover, sensitizer FZ-2's light absorption range is expanded and its energy conversion efficiency is improved under AM1.5 circumstances, reaching up to 5.72%, thanks to the enlarged π-conjugation. Co-sensitization testing under one sun revealed an effectiveness of 9.60% using N719 and FZ-2. Due to FZ-2's strong absorption efficiency at short wavelengths, which offsets N719's inadequacies in this range, the co-sensitization performance of FZ-2 and N719 is superior. Additionally, FZ-sensitizers demonstrate excellent photocatalytic hydrogen production efficiency. The hydrogen production activities of FZ-1 are 7430 μmol/g (1 hour) and 64004 μmol/g (12 hours), FZ-2 hydrogen production activities are 9190 μmol/g (1 hour) and 76582 μmol/g (12 hours). This suggests that FZ-2 is more effective at injecting charges into TiO2 and using them for water splitting. After 12 hours of photocatalytic water splitting stability tests, FZ-1 and FZ-2 exhibited TON of 4249 and 5378, respectively.

DOI： 10.23919/AM-FPD61635.2024.10615532

Scopus

掲載種別：研究論文（学術雑誌）   出版者・発行元：Solid State Ionics  

Mullite-phase bismuth gallate (Bi2Ga4O9) was successfully synthesized with partial substitution of bismuth with alkaline-earth cation, Mg2+, Ca2+, Sr2+, and Ba2+. The effect of this substitution on the electrical conductivity was investigated. In this study, substitution with Ca2+ of Bi site was further studied for increasing the ionic conductivity as well as the phase stability in reducing atmospheres. Substitution with Ca2+ was found to be the most effective and with 12.5 mol% of Ca2+ as the optimized doping amount. Conductivity and stability in reducing atmospheres was increased down to pO2 ≤ 10−19 atm while keeping the conductivity of σ = 2.6 × 10−2 S·cm−1 at 973 K largely independent of oxygen partial pressure. Oxygen permeation analysis estimates 76% of theoretical oxygen permeation rate at 973 K suggesting main charge carrier is oxide ion. Partial electronic conductivity was measured with the ion blocking method. Oxide ion conductivity is dominated over wide pO2 range excepting for hole conduction at high pO2. Density functional theory (DFT) analysis on oxide ion diffusion route suggests oxygen hoping through lattice vacancy is main pathway for oxide ion conductivity in this doped Bi2Ga4O9. Despite the low oxide ion conductivity in Mullite-phase oxide, it was found that Ca doped Bi2Ga4O9 shows good oxide ion conductivity over wide pO2 range.

DOI： 10.1016/j.ssi.2023.116343

Web of Science

Scopus

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of Materials Chemistry A  

BODIPY (boron-dipyrromethene) compounds are extensively utilized in various applications. Typically, their activity is modified by altering the functional groups at the α-, β-, and meso-positions of the substituents. However, no systematic information has been provided regarding the effects of substituted F- positions and hydrophobicity on the activity of BODIPY sensitizers in photosensitizing chemistry. Dyes (7a-7c) with different alkyl chain lengths were synthesized and compared with the unsubstituted compound 3 to discuss the effects of -F position substituents and the hydrophobicity of BODIPY dyes on photocatalytic activity. Density functional theory (DFT) calculations showed that -F-substitution induced an intramolecular charge transfer (ICT) effect, enhancing visible-light absorption. Longer alkyl chains provided a favourable second coordination sphere reaction environment for hydrogen production. Experimentally, dye 7c demonstrated the highest activity, with a hydrogen production rate of 496.5 μmol gcat−1 h−1, which is 3 times higher than that of 3, and a 9.6 times higher turnover frequency (TOF) than that of 3. The apparent quantum yield (AQY) at 650 nm was 1.4%. This study highlights the importance of -F position substitution and optimizing hydrophobicity to enhance the photocatalytic activity of metal-free organic dyes through the creation of a new second coordination sphere.

DOI： 10.1039/d3ta03682k

Web of Science

Scopus

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Advanced Energy and Sustainability Research  

The correlation between lattice strain induced by metal dispersion into grain and the cathodic overpotential is studied for increasing oxygen-dissociation activity and improving power density of solid oxide fuel cells (SOFC) at decreased temperature. Pt or Au dispersion in Pr1.90Ni0.71Cu0.21Ga0.05O4+d (PNCG) is prepared and the 3D tensile strain is successfully induced after sintering by a mismatch in thermal expansion coefficient. Due to higher hardness and melting temperature, Pt dispersion into bulk of PNCG introduces larger tensile strain than that by Au at the same amount. In particular, at 1 mol% Pt dispersion, large tensile strain of 0.67% is induced. Overpotential of 1 mol% Pt-PNCG cathode is 8 times smaller (35 mV) than that of PNCG (270 mV) at 800 °C and 300 mA cm−2, and it is found that the cathodic overpotential of PNCG is decreased with tensile strain on both Pt and Au dispersion. This cathodic activity enhancement appears to be related with the increased diffusivity of oxide ion in PNCG. In this study, cathodic overpotential is more significantly influenced by the induced tensile strain comparing with the intrinsic catalytic activity of the dispersed metal.

DOI： 10.1002/aesr.202300084

Web of Science

Scopus

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Solid State Ionics  

For increasing the performance of PCFC (Protonic Ceramic Fuel Cells), it is important to prepare high-quality thin films of electrolyte materials. In this study, the preparation condition of the thin film of BaZr0.8Yb0.2O2.9 (BZYb) by pulsed laser deposition (PLD) method was optimized and the electrical conductivities of the obtained films were measured. The thin film was prepared by PLD using two kinds of BZYb targets, which were prepared by solids state reaction and Pechini method. Both thin-film samples have the single phase of the cubic perovskitetype structure, however, morphology as well as the orientation of the BZYb film was significantly different. The thin film using the target material by Pechini method is a high crystalline orientation and partially oriented [211] direction. The electrical conductivities of the obtained thin films at reduction atmosphere are dominated by proton conductivity, which is almost the same as that of the bulk sample despite [211] orientation.

DOI： 10.1016/j.ssi.2023.116240

Web of Science

Scopus

researchmap

記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Applied Catalysis B: Environmental  

In the CO2 electrocatalytic reduction reaction (CO2RR) technology, high CO2 conversion rate is highly required for efficient CO2 utilization from the CO2 resource. In this study, we propose the strategy of combining UiO-66 metal organic framework (MOF) structure with Bi electrocatalyst for highly active CO2RR with selective formic acid production. The synthesized Bi/UiO-66 catalyst shows superior CO2 reduction property, 4.6 times higher current density at −0.7 V vs. reversible hydrogen electrode (RHE) than bare Bi without UiO-66 despite of low electrochemical surface area. Also, NH2 functionalized UiO-66 shows almost no effect on CO2RR as compared to without NH2 probably due to disassembled linkers during CO2RR. Various characterizations such as Fourier transform infrared (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) indicate carbonate species captured form of CO2 at Zr-MOF site should contribute the high CO2 conversion rate. Our findings demonstrate the feasibility of Zr-MOF as a Supporting material to achieve efficient CO2 reduction.

DOI： 10.1016/j.apcatb.2023.122400

Web of Science

Scopus

researchmap

記述言語：英語  

The amount of support salt in electrolytes determines the capacity of a dual-ion battery (DIB), and highly concentrated electrolytes are required for developing the high energy density DIB. In this study, hybrid aqueous tetraglyme (G4) electrolyte is investigated to develop high energy density aqueous DIB that is composed of carbon and Mo_6S_8 for cathode and anode, respectively. Impedance measurement reveals that introduced G4 increases the activation energy of the anode; however, decreases the activation energy for anion intercalation into the carbon cathode. This decreases the activation energy resulted from the G4 molecule strongly solvated to Li^+ resulting in weakening anion trapped in “contact ion pair” in concentrated aqueous electrolyte. So, hybrid G4-aqueous electrolyte is useful for better electrochemical intercalation of anion. In addition, this hybrid electrolyte is highly stable by formation of stable solid electrode–electrolyte interphase on Mo_6S_8 anode and discharge capacity of 37 mAh g^<−1>, and 72% retained capacity after 500 cycles with a high average coulombic efficiency of 93% is achieved.

CiNii Research

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Small Methods  

The amount of support salt in electrolytes determines the capacity of a dual-ion battery (DIB), and highly concentrated electrolytes are required for developing the high energy density DIB. In this study, hybrid aqueous tetraglyme (G4) electrolyte is investigated to develop high energy density aqueous DIB that is composed of carbon and Mo6S8 for cathode and anode, respectively. Impedance measurement reveals that introduced G4 increases the activation energy of the anode; however, decreases the activation energy for anion intercalation into the carbon cathode. This decreases the activation energy resulted from the G4 molecule strongly solvated to Li+ resulting in weakening anion trapped in "contact ion pair" in concentrated aqueous electrolyte. So, hybrid G4-aqueous electrolyte is useful for better electrochemical intercalation of anion. In addition, this hybrid electrolyte is highly stable by formation of stable solid electrode-electrolyte interphase on Mo6S8 anode and discharge capacity of 37 mAh g(-1), and 72% retained capacity after 500 cycles with a high average coulombic efficiency of 93% is achieved.

DOI： 10.1002/smtd.202300249

Web of Science

Scopus

PubMed

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of Physical Chemistry C  

A rechargeable Zn-air battery is expected as a large capacity battery alternative to the Li ion battery; however, short cycle life is the current issue. In this study, it was found that the addition of 3,3-diaminodipropylamine was effective for preventing the formation of a Zn dendrite in the anode resulting in a long cycle life with more than 300 cycles and a discharge capacity larger than 700 mAh/g (>85% Zn used for discharge) when Ni0.8Fe0.2Co2O4 and 8 M KOH-H2O were used for the air electrode and electrolyte, respectively. The increased cycle stability could be assigned to the change in the solvated structure of Zn2+ in the electrolyte by the strong interaction between 3,3-diaminodipropylamine and solvated water, which is suggested by Raman and Fourier transform infrared spectroscopic analyses. Ab initio molecular dynamics simulations suggest that the amine is strongly interacted with OH of solvated water molecules and changes the coordination number of Zn2+, and as result, the size of the solvated Zn2+ cluster was increased, resulting in enhanced Zn2+ mobility in the electrolyte for the uniform deposition of Zn on the anode during charge by increased mobility.

DOI： 10.1021/acs.jpcc.2c08682

Web of Science

Scopus

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Applied Catalysis A: General  

Photobiocatalytic system has been developing as a promising approach for H2 production. Herein, the rational characteristics of biocatalysts and the role of individual components affecting the efficiency of the system were investigated. Photocatalytic studies showed that tris (2-amino-2-hydroxymethyl-1,3-propanediol) was an ideal electron donor for viologen reduction by TiO2. Biocatalytic reaction revealed that cell permeability, the redox potential of electron mediators and the cell envelope were crucial to the activity of whole-cell biocatalysts. In photobiocatalytic system, recombinant Escherichia coli with a turnover frequency of 39.43 +/- 3.77 s-1 based on [FeFe]-hydrogenase activity was a more rational biocatalyst than Anabaena variabilis. A comprehensive study found that the presence of TiO2, light and biocatalysts strongly enhanced H2 production, whereas Tris and MV2+ had less influence. A maximum rate was found at 16.73 +/- 1.03 mu mol/min with a solar-to-H2 conversion of 1.58 +/- 0.10 %. Understanding the role of each component will guide the development of high-efficient photobiocatalysis.

DOI： 10.1016/j.apcata.2022.119019

Web of Science

Scopus

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Applied Physics A: Materials Science and Processing  

Squaraine dyes are organic dyes having strong and narrow absorption properties in the near-infrared region that are widely used in photovoltaic and biomedical applications. In this work, squaraine dye (SA1) was synthesized as a dye sensitizer for a dye-sensitized photocatalytic system, which was composed of SA1 and Pt-loaded TiO2 powder photocatalyst (SA1/Pt-TiO2). The SA1/Pt-TiO2 system exhibited a good hydrogen production performance within 150 h and an apparent quantum yield of 1.4% under 800 nm monochromatic light irradiation. However, during the photocatalytic reaction, the photocatalytic activity of SA1/Pt-TiO2 decreased due to photodecomposition. Ultraviolet-visible absorption spectroscopy, H-1 nuclear magnetic resonance spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry measurements were performed to investigate the mechanism of the decomposition of the squaraine moiety of SA1, the decomposition process, and the structure of the decomposed material. The results show that even without the Pt-loaded TiO2 powder photocatalyst, SA1 undergoes photodissociation, which cleaves the bond between the indoline moiety and the square acid.

DOI： 10.1007/s00339-022-06281-7

Web of Science

Scopus

researchmap

DOI： 10.1111/ncn3.12681

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the Electrochemical Society  

Water-acetonitrile (AN) hybrid electrolyte with high concentration of bis(trifluoromethanesulfonyl) imide (LiTFSI) and Lithium bis(fluorosulfonyl) imide (LiFSI) (LiTFSI-LiFSI=3:1, molar ratio) supporting salts are studied for the high potential and large capacity rechargeable dual-ion battery. Water-acetonitrile hybrid electrolyte (WA) shows a wide electrochemical stability window of 3.1 V in 20 m aqueous electrolyte and 3.6 V in 20 m 9LiFSI-1LiTFSI in water: AN=1:3 molar ratio electrolyte. In particular, high oxidation potential, which can be assigned to the strong solvated ionic cluster formed between AN, water and LiTFSI-LiFSI supporting salts. The dual-ion battery is assembled using the graphitic carbon (KS6) and the activated carbon (AC) as cathode and anode, respectively, and 20 m LiTFSI-LiFSI in hybrid AN-water as electrolyte. It is found that the reasonably large capacity, coulombic efficiency and cycle stability were achieved. The KS6/AC cell shows 86 mAh g(-1) at the initial cycle and 50 mAh g(-1) at 100th cycle in a voltage range of 0-3.25 V, and the average coulombic efficiency of 85% is sustained over 200 cycles. The solvated structure of water to Li+ is strengthened by addition of AN from ATR-IR and NMR spectrums analysis and this change in the solvated structure is the main reason for the increased performance of the aqueous dual-ion battery.

DOI： 10.1149/1945-7111/acaad1

Web of Science

Scopus

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ChemSusChem  

The solvated structure of a highly concentrated hybrid tetraglyme (G4)-water electrolyte was studied for an increasing cycle stability and performance of a KS6 used dual-ion battery. Hybrid solvent of G4 and water with a weight ratio of 2 to 8 was able to dissolve 9LiFSI-1LiTFSI supporting salts up to 37 mol kg(-1) (37 mol kg(-1) G2W8). In spite of such high concentration of supporting salts, reasonable charge and discharge performance of dual-ion battery (discharge capacity of approximate to 40 mAh g(-1) and coulombic efficiency of 90 %) were exhibited over 300 cycles. This was attributed to the decreased hydrogen evolution reaction (HER) potential to -1.05 V vs. Ag/AgCl by addition of G4. From Fourier-transform infrared, nuclear magnetic resonance, and Raman spectroscopies, G4 molecules were more strongly coordinated to Li+ to form ion pairs of [Li(G4)(x)(H2O)(y)](+) complex in hybrid G4-water electrolyte. Co-intercalation of bis(trifluoromethanesulfonyl)imide (TFSI-) and bis(fluorosulfonyl)imide (FSI-) into graphitic carbon KS6 cathode was confirmed in hybrid aqueous electrolyte.

DOI： 10.1002/cssc.202201805

Web of Science

Scopus

PubMed

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Engineering Journal  

CO(2 )photoreduction on photocatalysts is a nature-friendly solution to decrease the CO2 amount, but the method still has low efficiency because of difficult separation and easy recombination of charge carriers in available catalysts. In this study, a high-entropy oxynitride was introduced as an active photocatalyst for photoreduction. The material had a chemical composition of TiZrNbHfTaO6N3 and was produced by a high-pressure torsion method followed by oxidation and nitriding. It showed higher photocatalytic CO2 to CO conversion compared to corresponding high-entropy oxide, benchmark photocatalyst P25 TiO2, and almost all catalysts introduced in the literature. The high activity of this oxynitride, which also showed good chemical stability, was attributed to the large absorbance of light and easy separation of electrons and holes, the low recombination of charge carriers, and the high CO(2 )adsorption on the surface. These findings introduce high-entropy oxynitrides as promising photocatalysts for CO(2 )photoreduction.

DOI： 10.1016/j.cej.2022.137800

Web of Science

Scopus

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Catalysis Science and Technology  

Strained metal oxides are known to exhibit improved activity for redox and photocatalytic reactions. Here, we intentionally introduced tensile strain into rutile-type TiO2 by utilizing the difference in thermal expansion coefficients between TiO2 and Au and applied it as a solid acid catalyst. It was demonstrated that its acid catalytic activity in the acetalization of furfural was enhanced by increasing the degree of the strain introduced.

DOI： 10.1039/d2cy00736c

Web of Science

Scopus

researchmap

記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：公益社団法人 石油学会  

<p>白金担持アルミナ上で，一酸化窒素（NO）を酸化剤としてメタンをシアン化水素（HCN）に変換する際の白金ナノ粒子の粒径効果について検討した。担持量と焼成温度を制御することにより，1.6〜4.1 nmの範囲で様々な平均粒子径のPt触媒を得ることができた。Pt表面サイト量はパルス法によるCO滴定で決定し，触媒活性は同一接触時間下で評価した。Pt の粒子が小さい触媒（1.6〜3.2 nm）では，NO 転化率が粒子径の大きい触媒よりも低いことが分かった。粒子径の大きな触媒（4.1〜4.2 nm）は，10 wt% Pt/Al₂O₃ において 400 ℃で 収率1.3 %（炭素ベース）で高い HCN 選択率（53.5 %）を示した。大きなPt粒子が高い活性を示す理由の一つは，金属と担体の界面で進行するHCNから二酸化炭素とアンモニアへの逐次反応を抑制したためと思われる。Pt L₃端X線吸収微細構造（XAFS）スペクトルから，反応試験後の小粒子触媒はPt–CN種で覆われていることが分かった。一方，大粒子触媒ではPt–COが主な吸着種として観測され，大粒子触媒の方がHCN脱離が容易であることが示唆された。</p>

DOI： 10.1627/jpi.65.184

Web of Science

Scopus

CiNii Research

researchmap

DOI： 10.1016/j.cej.2022.136209

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry - A European Journal  

Novel donor-acceptor dyads containing [2.2]- and [3.3]paracyclophane (PCP) as the bridging moiety were synthesized and used to effectively fabricate dye-sensitized hydrogen production systems. All the prepared compounds had a phenothiazine and a cyanoacrylic acid/pyridinyl acrylonitrile moiety acting as an electron donor and acceptor, respectively. Although cyclic voltammetry measurements showed similar electron-donating properties among all the synthesized dyads, the lowest absorption energy of the [2.2]PCP moiety was lower than that of the [3.3]PCP one; this was due to its shorter distance between benzene rings, which could effectively drive the charge transfer between the donor and acceptor chromophores. Under visible light (>395 nm), a dyad-loaded photocatalyst in a 0.5 M aqueous glycerol solution generated detectable hydrogen gases. The optimal turnover number and photocurrent order exhibited the same trend as the hydrogen production rate since the suggested number of excited photons played a critical role in hydrogen production.

DOI： 10.1002/chem.202200790

Web of Science

Scopus

PubMed

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of Physical Chemistry C  

The modification effect of acene dyes such as 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-PEN) and difuranoan-thracene derivatives on the photocatalytic water splitting activity of Pt-loaded KTa(Zr)O-3 was studied. The surface modification of KTa(Zr)O-3 powder with acene dyes was conducted with an evaporation-to-dryness method using pyridine as a solvent. TIPSPEN is the most effective dye for increasing the hydrogen formation rate on the KTa(Zr)O-3 catalyst, which became larger by 14 times. The fluorescence spectrum of the TIPS-PEN-modified catalyst revealed that the excitation energy of KTa(Zr)O(3 )was transferred to the Pt cocatalyst through the TIPS-PEN moiety. The wavelength dependence of the photocatalytic activity was investigated, and the water splitting activity was improved by irradiating with both ultraviolet and visible light comparing with the case of irradiating with only ultraviolet light. Furthermore, the water splitting reaction did not occur under visible light irradiation, which suggests that a Z-scheme-type water splitting reaction, that is, a two-step photoexcitation mechanism similar to that occuring in plant photosynthesis, proceeded on PtOx/TIPS-PEN/KTa(Zr)O-3.

DOI： 10.1021/acs.jpcc.2c02532

Web of Science

Scopus

researchmap

出版者・発行元：Electrochemical Science Advances  

The addition of 3,3,3-trifluoropropyl acetate (TFPA) to electrolyte in a Li-ion rechargeable battery (LIB) provides a means for increasing the discharge performance at low temperatures as a result of the formation of a superior solid electrolyte interphase (SEI) on the graphite anode. For instance, the addition of 2 wt% TFPA to the electrolyte significantly increased the cycle stability and the discharge capacities at low temperatures (-10°C) even at current rates of 3 C. The SEI films formed on the graphite anodes were characterized by electrochemical and spectroscopic techniques and by computational analysis. Although the formation of LiF on the anode has been recognized, present research revealed that the decomposition of TFPA on the anode surface resulted in the formation of an SEI layer consisting predominantly of organic fluorides. This layer suppressed the decomposition of the electrolyte resulting in a decreased anode impedance and an increase in cycle stability and discharge capacity at low temperatures.

DOI： 10.1002/elsa.202100062

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Applied Catalysis A: General  

Porous boron nitride was synthesized using boric acid with urea and/or hexamethylenetetramine (HMTA) via pyrolysis method. X-ray diffraction and Fourier transform infrared measurements indicated that the synthesized boron nitride has a turbostratic structure with both amino and hydroxyl group on the surface. The synthesis using a mixture of two nitrogen-containing precursors was found to not only significantly increase the porosity, but also improve the surface functionality. X-ray photoelectron spectroscopy and B K-edge and O K-edge X-ray absorption fine structure measurements revealed that the proportion of amino and hydroxyl groups on the surface increased with increasing concentration of HMTA during synthesis. Solid-state 11B nuclear magnetic resonance spectroscopy indicated that all samples contained trigonal B-N, trigonal B-O and tetrahedral B-O sites, and that samples prepared with high concentrations of HMTA had less tetrahedral B-O sites, suppressing the formation of BOx species as byproducts. Solid base catalytic activity was evaluated through Knoevenagel condensation, and the catalytic performance was significantly improved by synthesizing boron nitride catalyst using a mixture of the two nitrogen-containing precursors. The enhancement of the activity was influenced by the development of the pore structure as well as the emergence of functional groups on the surface.

DOI： 10.1016/j.apcata.2022.118635

Web of Science

Scopus

researchmap

DOI： 10.1016/j.apcatb.2021.120896

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20210185

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.202100936

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d1ta03861c

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.ensm.2021.03.029

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1063/5.0041881

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.jpowsour.2021.229543

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.jpowsour.2020.229084

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apcatb.2020.119292

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/cctc.202001435

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/cbic.202000383

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apcata.2020.117843

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1016/j.scriptamat.2020.06.052

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.scriptamat.2020.06.052

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apcatb.2020.118931

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apcatb.2020.118931

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apcata.2020.117743

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apcata.2020.117737

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.mtla.2020.100670

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.jpcc.0c03923

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d0cy00128g

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.mtla.2020.100670

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.3390/catal10050535

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.3390/catal10050535

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d0nr01762k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d0cy00194e

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d0cy00194e

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Oxynitrides are considered as new potential candidates for photocatalysis due to their lower bandgap compared with traditional oxide photocatalysts. However, the formation of native nitrogen monovacancies during the synthesis of oxynitrides reduces their photocatalytic activity due to the vacancy-induced electron/hole recombination. This study shows that a transition from the native nitrogen monovacancies to the nitrogen-based vacancy complexes in a GaN–ZnO oxynitride not only diminishes the recombination but also enhances the photocatalytic hydrogen production. Here, the vacancy complexes are introduced by mechanical straining via the high-pressure torsion (HPT) method and it is shown that the vacancy complexes reduce the bandgap and increase the over-potential for hydrogen production on the conduction band. The current results introduce a simple but effective approach to turn the nitrogen vacancies to favorable defects for photocatalysis.

DOI： 10.1016/j.actamat.2019.12.007

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c9ta11839j

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsaem.9b02197

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.actamat.2019.12.007

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c9ta11839j

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsaem.9b02197

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c9ta11048h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c9ta11048h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.scriptamat.2019.08.011

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/cctc.201901549

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.scriptamat.2019.08.011

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/cctc.201901549

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c9nj02790d

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Solar water splitting to produce hydrogen is a promising solution for global energy issues. One of the main bottlenecks in this technology is the spontaneous fast backward reaction (2H₂ + O₂ → H₂O, ΔG < 0), limiting the solar energy conversion efficiency. How to suppress backward reaction is vitally important but rarely reported. Here we found that single-electron-trapped oxygen vacancy (Vo·) can suppress spontaneous backward reaction in pure water splitting. Taking WO₃·0.33H₂O catalyst as an example, ultrathin WO₃·0.33H₂O {100} facets with large amount of surface Vo· realized a continuous H₂ evolution from pure water splitting with a productivity of 9.9 μmol/g·h without the assistance of any sacrifice agent and noble metal cocatalyst. Quantum chemical calculations revealed that the backward-reaction suppression ability of Vo· is attributed to the high concentration of localized electrons around Vo·, stimulating unidirectional simultaneous water dissociation into H and OH under light irradiation.

DOI： 10.1021/acs.jpclett.9b01032

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.jpclett.9b01032

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsaem.8b02153

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsaem.8b02153

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20180261

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20180261

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c9nj02790d

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.triboint.2018.06.003

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsaem.8b01113

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.triboint.2018.06.003

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsaem.8b01113

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201801774

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201803214

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201803214

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tet.2018.03.072

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.8b03316

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tet.2018.03.072

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Artificial photosynthesis from CO₂ reduction is severely hampered by the kinetically challenging multi-electron reaction process. Oxygen vacancies (Vo) with abundant localized electrons have great potential to overcome this limitation. However, surface Vo usually have low concentrations and are easily oxidized, causing them to lose their activities. For practical application of CO₂ photoreduction, fabricating and enhancing the stability of Vo on semiconductors is indispensable. Here we report the first synthesis of ultrathin WO₃·0.33H₂O nanotubes with a large amount of exposed surface Vo sites, which can realize excellent and stable CO₂ photoreduction to CH₃COOH in pure water under solar light. The selectivity for acetum generation is up to 85%, with an average productivity of about 9.4 μmol g^-1 h^-1. More importantly, Vo in the catalyst are sustainable, and their concentration was not decreased even after 60 h of reaction. Quantum chemical calculations and in situ DRIFT studies revealed that the main reaction pathway might be CO₂ → ^•COOH → (COOH)₂ → CH₃COOH.

DOI： 10.1021/jacs.8b03316

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201801774

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7ra13632c

記述言語：英語  

DOI： 10.1016/j.jphotochemrev.2017.09.001

記述言語：英語  

DOI： 10.1080/14686996.2017.1375376

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.surfcoat.2016.10.054

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.surfcoat.2016.10.054

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apcatb.2017.04.015

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/ajoc.201700088

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/ajoc.201700088

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7se00084g

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apcatb.2017.04.015

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.dyepig.2016.09.043

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.joc.6b02668

記述言語：英語  

DOI： 10.1627/jpi.60.10

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.dyepig.2016.09.043

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.joc.6b02668

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7se00084g

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tet.2016.05.069

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1055/s-0035-1560421

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.3390/catal6030042

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.3390/catal6030042

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1055/s-0035-1560421

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A series of alkylated indigos were synthesized. Alkylated indigos were characterized by NMR, mass spectrometry, absorption spectra, cyclic voltammetry, and density functional theory (DFT) calculations. Propyl and butyl group substituted indigo was most soluble in chloroform and 1,2-dicrolobenzene, and these solubility were 65–89 times increased as compared to the parent indigo. DFT calculations suggested that the presence of the alkyl chains at the 5.5′-position increases the energy of the highest occupied molecular orbital, while reducing the energy of the lowest unoccupied molecular orbital. This theoretical finding was in good agreement with the experimental results. Crystal structures obtained by X-ray diffraction showed one-dimensional pi–pi stacking. Alkylated molecules were converted to leuco structure, and these structures were then converted to the corresponding indigos in the film state. After deposition of the films on TiO₂/FTO substrate, oxidative photocurrents were observed.

DOI： 10.1016/j.tet.2016.05.069

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1149/2.0381607jes

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2015.10.070

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2015.10.070

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.joc.5b01525

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.joc.5b01525

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2015.02.012

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tet.2015.01.056

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2015.02.012

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tet.2015.01.056

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2015.01.093

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2015.01.093

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c5ta04991a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2014.10.151

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jo5020273

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2014.10.151

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Three types of the donor(D)-donor′(D′)-acceptor(A) triads 1-6 with different D-A combinations, carbazole (Cz, D)-[n.n]PCP(D′)-1,8-naphthalimide (NI, A) (1-3), 10H-phenothiazine (PTZ, D)-[n.n]PCP(D′)-NI(A) (4, 5), and 10-methyl-10H-phenothiazine (Me-PTZ, D)-[2.2]PCP-2,1,3-benzothiadiazole (BTD, A) 6, were synthesized for the elucidation of their photophysical properties. The absorption spectra and electrochemical properties indicated that the chromophores (D, D′, and A) do not interact with each other in the ground state. Cz-(CH₂)₃-[2.2]PCP-(CH₂)₃-NI 1 and Cz-(CH₂)₃-[3.3]PCP-(CH₂)₃-NI 2 show an exciplex emission between the PCP and NI moieties in cyclohexane and the intensity of the band is much higher in 2 than in 1, whereas Cz-(CH₂)₂-[2.2]PCP-(CH₂)₂-NI 3 does not show any exciplex emission in cyclohexane. These results indicated that the combination of [3.3]PCP and a trimethylene chain is preferable for the exciplex formation. PTZ-(CH₂)₃-[2.2]PCP-(CH₂)₃-NI 4 shows a broad band at 519 nm in cyclohexane, which is associated with the formation of the exterplex band among the NI, [2.2]PCP, and PTZ moieties, while PTZ-(CH₂)₃-[3.3]PCP-(CH₂)₃-NI 5 does not show the band. Me-PTZ-(CH₂)₂-[2.2]PCP-(CH₂)₂-BTD 6 shows a broad fluorescence band due to both the BTD and PTZ moieties in cyclohexane. In CH₃CN, the fluorescence spectra of 1-6 suggest the presence of a photoinduced charge separation process. The study of the photoinduced charge separation process will be soon reported elsewhere.

DOI： 10.1021/jo5020273

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1107/S1600536814023691

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp5081884

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c4cc05127k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1142/S1088424614500692

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.dyepig.2014.04.043

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1107/S1600536814018388

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c4ta02720e

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c4ta02720e

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1142/S1088424614500692

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tsf.2014.03.010

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1107/S1600536814009362

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tsf.2014.03.010

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2014.01.036

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2014.01.036

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tet.2013.11.072

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tet.2013.11.072

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp5081884

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1107/S1600536814009362

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1107/S1600536814018388

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1107/S1600536814023691

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Novel organic dyes that consist of either a benzo[1,2-b:4,5-b′] dithiophene or a benzo[1,2-b:4,5-b′]difuran core exhibited remarkable solar-to-energy conversion efficiency in dye-sensitized solar cells. The planar geometry of bridge moiety and its bulky substituents helped the dyes to form a high quality monolayer on the surface of titanium oxide. A typical device displayed photon-to-current conversion efficiency 60% in the region of 380-575 nm, a short-circuit photocurrent density 13.45 mA cm
^-2
, an open-circuit photovoltage 0.72 V, and a fill factor 0.63, corresponding to an overall conversion efficiency 6.12%. In a test of using deoxycholic acid as a co-absorbent, an improvement of quantum efficiencies 8.37% was observed for certain compounds. However, for others the quantum efficiency decreased in 6.60-7.91%. The latter result indicated that the quality of some films cannot be further improved by the addition of deoxycholic acid. The photophysical properties were analyzed with the aid of TDDFT.

DOI： 10.1016/j.dyepig.2014.04.043

記述言語：英語  

DOI： 10.1021/ar400002y

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c3cc00278k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2012.11.126

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2012.11.126

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.201200834

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.201200834

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c2jm35556f

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c2jm35556f

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c2jm31134h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/NCHEM.1381

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/nchem.1381

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c2cc31754k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2012.02.060

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2012.02.060

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.201100777

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.201100777

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c2jm13961h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c1cc16248a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

We have synthesized p-conjugated acceptor-type molecules 3a-d containing a cyanomethylene unit as the electron acceptor site and a 4,5-diazafluorene ligand for metal complexation. In the crystal, the planar 3a molecules stack along the b axis in the head-to-tail fashion. Compound 3a shows distinctive electrochromism and its three differently colored redox states (dianion (3 ^2-), anion radical (3^.-), neutral (3)) exhibit remarkable stability.

DOI： 10.1016/j.tetlet.2011.08.164

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2011.08.164

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2011.07.060

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2011.07.060

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c1jm11834j

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2011.04.087

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2011.04.087

記述言語：英語   掲載種別：研究論文（学術雑誌）  

In the present study, delocalization of a positive charge in π-stacked multi-benzene rings in multilayered para-and meta-cyclophanes, in which benzene rings are connected by propyl chains to form a chromophore array with the face-to-face structure, was investigated by means of transient absorption spectroscopy during the pulse radiolysis using dichloroethane as a solvent. The local excitation and charge resonance (CR) bands were successfully observed. It was revealed that the CR band shifted to the longer wavelength side with the number of the benzene rings. The stabilization energy estimated from the peak position of the CR band showed the efficient charge delocalization over the cyclophanes. Furthermore, the CR bands showed the slight spectral change attributable to the change in distribution of the conformers. The substantially long lifetime of the CR band can be explained on the basis of the smaller charge distribution on the outer layers of the multilayered cyclophanes.

DOI： 10.1021/jp110916m

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp110916m

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20100085

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20100085

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jo100688m

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jo100688m

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2009.01.051

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2009.01.051

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1055/s-0028-1083633

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1055/s-0028-1083633

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jo801441h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jo801441h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jo8013484

記述言語：英語  

DOI： 10.1021/jo8013484

記述言語：英語   掲載種別：研究論文（学術雑誌）  

(Figure Presented) The synthesis of three- and four-layered [3.3]paracyclophanes ([3.3]PCPs) 3-5 has been accomplished by utilizing the (p-ethylbenzenesulfonyl)methyl isocyanide (EbsMIC) method. The structures of the three- to four-layered [3.3]PCPs 3-5 and their diones 8, 10, and 11 have been elucidated based on the ¹H NMR spectra and finally by X-ray structural analysis. In the three-layered [3.3]PCP-dione 8, the trimethylene bridges of the [3.3]PCP unit assume a chair conformation similar to that of 2, while the [3.3]PCP-2,11-dione unit assumes a boat conformation different from that of [3.3]PCP-dione 1 with a chair conformation. On the other hand, the two [3.3]PCP units in three-layered [3.3]PCP 3 both assume a boat conformation. In the four-layered [3.3]PCP-dione 10, the two outer [3.3]PCP units assume a boat conformation while the inner dione unit has a chair conformation. The trimethylene bridges in the four-layered [3.3]PCP 4 are highly disordered even at -150°C. All the outer benzene rings are distorted into a boat form while the inner ones are distorted into a twist form. In the electronic spectra, bathochromic shift and hyperchromic effect are observed, but the magnitude decreases with an increase in the number of layers and the spectra become structureless. In the charge-transfer (CT) bands of the three- to four-layered [3.3]PCPs 3-5 with tetracyanoethylene (TCNE), two absorption maxima (λ_max) are observed. The effect of an increase in the layers becomes significant, and the changes in the longest wavelength λ_max values from two to three and three to four are ca. 60 and 50 nm, respectively. By comparison of the stereoisomeric four-layered [3.3]PCPs 4 (meso) and 5 (racemic), the helical arrangement of the trimethylene bridges of 5 shows a more efficient transannular π-electronic interaction. In the three- to four-layered [3.3]PCP-diones, a magnitude of the CT interaction almost comparable to that of [3.3]PCP 2 was observed, and this indicates that the -CH₂COCH₂- bridges inhibit the CT interaction and that this tendency is supported by the calculated HOMO energy levels and observed oxidation potentials. Three- and four-layered [3.3]PCPs 3-5 show reversible redox processes, and 4 and 5 show an electron-donating ability almost comparable to that of [3₆]CP. Very good correlation between the λλ_max of the CT bands with TCNE and the oxidation potentials is observed.

DOI： 10.1021/jo8003309

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jo8003309

記述言語：英語   掲載種別：研究論文（学術雑誌）  

(Figure Presented) The synthesis of a series of three- to six-layered [3.3]metacyclophanes ([3.3]MCPs) 3-6 has been successfully accomplished by the (p-tolylsulfonyl)methyl isocyanide (TosMIC) method as a critical coupling reaction. Their important synthetic intermediates are the two- and three-layered bis(bromomethyl) compounds 11, 17, 21, and tetrakis(bromomethyl) compounds 25 and 28. The structures of the three- to six-layered [3.3]MCPs (3-6) as well as three- to six-layered [3.3]MCP-di- (22-24) and tetraones (26, 27, and 29) as the synthetic intermediates have been elucidated based on the ¹H NMR data and X-ray structural analysis. These multilayered cyclophanes are constructed with two different geometries, syn[3.3]MCP and anti-[3.3]MCP-2,11- dione. In principle, their geometries are maintained in the multilayered [3.3]MCPs, but deformation of the dihedral angle of the two benzene rings of the syn-[3.3]MCP moiety is generally observed. In the four-layered MCP 4, the central [3.3]MCP moiety takes an anti geometry. These data indicate the structural flexibility of the [3.3]MCP moiety. In the electronic spectra, rather simple and structureless absorption curves are observed, and the most significant spectral change is observed for the two to three layers and becomes less effective even if it is more layered. In the charge-transfer (CT) bands of the multilayered [3.3]MCPs with tetracyanoethylene (TCNE), the λ_maxmax gradually shifts to the longer wavelength region, but the extent of the shift is much smaller as the number of layers increases. In the multilayered [3.3]MCP-di- and tetraones, the anti-[3.3]MCP-dione moiety works as an insulator. Therefore, the CT interaction of the four- and five-layered [3.3]MCPs with one anti-[3.3]MCP-dione moiety (23 and 24) shows the almost comparable magnitude of the interaction with the two- and three-layered [3.3]MCPs (2 and 3), respectively. The tetraones of the three and four-layered MCPs (29 and 26) do not show CT interactions except for the six-layered MCP 27.

DOI： 10.1021/jo062220m

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jo062220m

記述言語：英語   掲載種別：研究論文（学術雑誌）  

開催年月日： 2023年6月

記述言語：英語  

国名：日本国  

開催年月日： 2023年6月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：July 11, 2022, Hiroshima   国名：日本国  

開催年月日： 2023年6月

記述言語：英語   会議種別：口頭発表（招待・特別）  

開催地：July 22-23,2022, Minamiaso, Kumamoto.   国名：日本国  

開催年月日： 2022年7月

記述言語：英語   会議種別：口頭発表（招待・特別）  

開催地：Minamiaso, Kumamoto.   国名：日本国  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

国名：台湾  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：口頭発表（一般）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

国名：日本国  

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

国名：フランス共和国  

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

国名：台湾  

種別：査読等 

外国語雑誌　査読論文数：27

日本語雑誌　査読論文数：0

国際会議録　査読論文数：0

国内会議録　査読論文数：0

種別：学会・研究会等 

種別：査読等 

外国語雑誌　査読論文数：20

日本語雑誌　査読論文数：0

国際会議録　査読論文数：0

国内会議録　査読論文数：0

種別：大会・シンポジウム等 

種別：大会・シンポジウム等 

種別：査読等 

外国語雑誌　査読論文数：21

日本語雑誌　査読論文数：0

国際会議録　査読論文数：0

国内会議録　査読論文数：0

種別：査読等 

外国語雑誌　査読論文数：10

日本語雑誌　査読論文数：0

国際会議録　査読論文数：0

国内会議録　査読論文数：0

種別：査読等 

外国語雑誌　査読論文数：9

日本語雑誌　査読論文数：0

国際会議録　査読論文数：0

国内会議録　査読論文数：0

種別：大会・シンポジウム等 

種別：査読等 

外国語雑誌　査読論文数：12

日本語雑誌　査読論文数：0

国際会議録　査読論文数：0

国内会議録　査読論文数：0

種別：査読等 

外国語雑誌　査読論文数：2

日本語雑誌　査読論文数：0

国際会議録　査読論文数：0

国内会議録　査読論文数：0