Substrate and Solvent Influence on the Photochemical C-H Bond Activation Reactivity of (HBPz'(3))Rh(CO)(2) (Pz' = 3,5-Dimethylpyrazolyl)

The photochemically-induced intermolecular C-H bond activation reaction of (HBPz'(3))Rh(CO)(2) (Pz' = 3,5-dimethylpyrazolyl) has been investigated in various hydrocarbon solutions at 293 K following excitation at 366 and 458 nm. UV-visible and FTIR spectra recorded throughout photolysis illustrate that the dicarbonyl complex can be converted readily to the corresponding (HBPz'(3))Rh(CO)(R)H derivatives at each of the excitation wavelengths. The photochemistry proceeds without interference from secondary photoprocesses or thermal reactions and the reactivity has been measured quantitatively with the determination of absolute quantum efficiencies for intermolecular C-H bond activation (phi(CH)). These measurements indicate that the C-H activation reaction proceeds very efficiently (phi(CH) = 0.13-0.32) on excitation at 366 nm but is much less effective (phi(CH) = 0.0059-0.011) on photolysis at 458 nm for each of the hydrocarbon substrates. The observed dependence of phi(CH) on irradiation wavelength is consistent with different reactivities from two rapidly dissociating low-energy ligand field (LF) excited states and the generation of monocarbonyl (HBPz'(3))Rh(CO) and ligand-dechelated (eta(2)-HBPz'(3))Rh(CO)(2) intermediates upon UV and visible excitation, respectively. The former species is attributed to be responsible for the unusually efficient C-H bond activation, whereas it is suggested that the latter complex effectively lowers the quantum efficiency by undergoing a facile eta(2)-->eta(3) ligand rechelation process. Significantly, the photoefficiencies are found to be unaffected on increasing the dissolved CO concentration, illustrating that the monocarbonyl reaction intermediate is extremely short-lived and is solvated before CO is able to coordinate. Additionally, the lack of a [CO] dependence on phi(CH) indicates that this solvated intermediate is not subject to a competitive back-reaction with CO prior to the C-H activation step, illustrating that the quantum efficiencies in (HBPz'(3))Rh(CO)(2) appear to be solely determined by the branching ratio between the dissociative and nondissociative routes. At any particular excitation wavelength the photoefficiencies are observed to be similar across the series of alkanes but are significantly reduced for the aromatic solvents, even though the aryl hydrido photoproducts are found to be more thermodynamically stable. These phi(CH) differences are also rationalized in terms of photophysical effects on the upper LF level and are related to variations in the nonradiative relaxation rates for the excited (HBPz'(3))Rh(CO)(2) complex in the hydrocarbon solutions.     

Applications of Crank-Nicolson method with ADI in laser transformation hardening

A two-dimensional numerical solution for pulsed laser transformation hardening is developed using the finite difference method (FDM). The FDM has been developed using Crank-Nicolson scheme which solved by using alternating-direction implicit method. If this present model was compared to the analytical solution, then the Crank-Nicolson scheme showed better results in terms of accuracy, consistency, stability, convergence, and performance than to the explicit scheme. The longer heating duration, higher laser beam intensity, and greater number of pulse had influences on increasing the maximum temperature. The repetitive heating had influences on extending the heat duration and increasing the initial temperature of domain. The shorter cooling duration in repetitive pulse produced higher maximum temperature. The thinner material’s thickness increased the cooling rate, which finally increased the possibility of austenite to transform into martensite phase. In addition, it was also found that the higher maximum temperature always reduced the cooling rate value when temperature cools down toward to the starting temperature of martensite formation. It reduced the possibility of martensite formation. It was also seen that the heat was conducted more effective to the axial direction than to the radial direction.     

Tunning of Templated CuWO4 Nanorods Arrays Thickness to Improve Photoanode Water Splitting

The fabrication of the photoanode of the n-type CuWO₄ nanorod arrays was successfully carried out through electrochemical deposition using anodic aluminum oxide (AAO) control templates and for the first time produced distinct gaps between the nanorod arrays. The effectiveness and efficiency of the resulting deposition was shown by the performance of the photoelectrochemical (PEC) procedure with a current density of 1.02 mA cm⁻² with irradiation using standard AM 1.5G solar simulator and electron changed radiation of 0.72% with a bias potential of 0.71 V (vs. Ag/AgCl). The gap between each nanorod indicated an optimization of the electrolyte penetration on the interface, which resulted in the expansion of the current density as much as 0.5 × 10²⁴ cm⁻³ with a flat band potential of 0.14 V vs. Ag/AgCl and also a peak quantum efficiency of wavelength 410 nm. Thus, also indicating the gaps between the nanorod arrays is a promising structure to optimize the performance of the PEC water splitting procedure as a sustainable energy source.     

Influence of Dye Content on the Conduction Band Edge of Titania in the Steam‐treated Dye‐dispersing Titania Electrodes

The titania and dye‐dispersing titania electrodes were prepared by a nitric acid‐catalyzed sol‐gel process. The dye‐dispersing titania contains the dye molecules dispersed on the surface of the individual nanosized titania particles. The photo‐cyclic voltammetry (Photo‐CV) and photoelectric measurements of the dye‐dispersing titania electrodes were conducted to clarify the factors changing the conduction band edge of the titania and the open‐circuit voltage (V_oc) of the electrodes. The remaining nitrate ions caused a negative shift of conduction band edge of the titania of the dye‐dispersing titania. The conduction band edge of the titania was shifted in a negative direction in the electrode containing a greater amount of the dye. These results are due to the adsorption of nitrate ions and the dye‐titania complex formation on the titania particle surface. The effect of the dye‐titania complex formation on the shift in the titania conduction band edge was greater than that of the adsorption of nitrate ions due to strong interaction between the dye and titania through the carboxylate and quinone‐like groups of the dye. The shift in the titania conduction band edge corresponded to the change in the V_oc value.     

Unusual change in molecular weight of polyhydroxyalkanoate (PHA) during cultivation of PHA-accumulating Escherichia coli

This study aimed to investigate the factors affecting molecular weight of poly[(R)-3-hydroxybutyrate] [P(3HB)] when polyhydroxyalkanoate (PHA) synthase (PhaRC_Bsp) from Bacillus sp. INT005 was used for P(3HB) synthesis in Escherichia coli JM109. It was found that the molecular weight of P(3HB) decreased with time in mid- and late-phase of culture and was strongly affected by culture temperature. At 37 °C culture temperature, the molecular weight of P(3HB) rapidly decreased from 4.4 × 10⁵ to 4.8 × 10⁴ with culture time, whereas it was almost unchanged at 25 °C. Kinetic analysis suggested that the decrease in molecular weight of P(3HB) was due to random scission of the polymer chain. The decrease in molecular weight of P(3HB) was not observed when PHA synthases other than PhaRC_Bsp were expressed. This study sheds light on the unique behaviour in molecular weight change of P(3HB) that is synthesized by E. coli expressing PhaRC_Bsp.     

Polarization dependence of an edge filter based on singlemode–multimode–singlemode fibre

The polarization dependent loss (PDL) of a singlemode–multimode–singlemode (SMS) fibre structure used as an edge filter is presented. Minor errors in the fabrication process for the SMS fibre structure can introduce SMS fibre core offsets. The PDL due to lateral and rotational core offsets is investigated numerically and experimentally. It is shown that small core offsets are necessary to achieve low PDL for an SMS fibre based edge filter. It is also demonstrated that when lateral core offsets are unavoidable, the PDL of a SMS edge filter can still be minimized by introducing a rotational core offset of 90^°.     

Faceted Branched Nickel Nanoparticles with Tunable Branch Length for High‐Activity Electrocatalytic Oxidation of Biomass

Controlling the formation of nanosized branched nanoparticles with high uniformity is one of the major challenges in synthesizing nanocatalysts with improved activity and stability. Using a cubic‐core hexagonal‐branch mechanism to form highly monodisperse branched nanoparticles, we vary the length of the nickel branches. Lengthening the nickel branches, with their high coverage of active facets, is shown to improve activity for electrocatalytic oxidation of 5‐hydroxymethylfurfural (HMF), as an example for biomass conversion.