Pure CuBi2O4 Photoelectrodes with Increased Stability by Rapid Thermal Processing of Bi2O3/CuO Grown by Pulsed Laser Deposition

A new method for enhancing the charge separation and photo‐electrochemical stability of CuBi₂O₄ photoelectrodes by sequentially depositing Bi₂O₃ and CuO layers on fluorine‐doped tin oxide substrates with pulsed laser deposition (PLD), followed by rapid thermal processing (RTP), resulting in phase‐pure, highly crystalline films after 10 min at 650 °C, is reported. Conventional furnace annealing of similar films for 72 h at 500 °C do not result in phase‐pure CuBi₂O₄. The combined PLD and RTP approach allow excellent control of the Bi:Cu stoichiometry and results in photoelectrodes with superior electronic properties compared to photoelectrodes fabricated through spray pyrolysis. The low photocurrents of the CuBi₂O₄ photocathodes fabricated through PLD/RTP in this study are primarily attributed to their low specific surface area, lack of CuO impurities, and limited, slow charge transport in the undoped films. Bare (without protection layers) CuBi₂O₄ photoelectrodes made with PLD/RTP shows a photocurrent decrease of only 26% after 5 h, which represents the highest stability reported to date for this material. The PLD/RTP fabrication approach offers new possibilities of fabricating complex metal oxides photoelectrodes with a high degree of crystallinity and good electronic properties at higher temperatures than the thermal stability of glass‐based transparent conductive substrates would allow.     

Novel nanorod Ti0·7Ir0·3O2 prepared by facile hydrothermal process: A promising non-carbon support for Pt in PEMFCs

Late transition metal doped TiO₂ has been exploited for generating efficient catalyst support by enhancing electrical conductivity and modifying properties of TiO₂. The Ti_0·7Ir_0·3O₂ nanorod (NRs), a novel catalyst support for Pt nanoparticles, was prepared for the first time via single-step hydrothermal process at low temperature using IrCl₃·3H₂O and TiCl₄ as starting materials. We found that the Ti_0·7Ir_0·3O₂ NRs with 70–80 nm in length and 25–30 nm in width is successful prepared at 210 °C for 12 h without utilizing surfactants or stabilizers. In addition, the Ti_0·7Ir_0·3O₂ NRs was presented principally as a single-phase solid with the TiO₂ is in the rutile form with high crystallinity without using further treatment after synthesis. More importantly, we found that the Ti_0·7Ir_0·3O₂ NRs possesses high electrical conductivity (0.028 S cm⁻¹) dealing the intrinsically non-conducted drawback of TiO₂. The Pt nanoparticles were then deposited on the support of Ti_0·7Ir_0·3O₂ NRs via chemical reduction method. The properties of 20 wt % Pt/Ti_0·7Ir_0·3O₂ NRs electrocatalyst were characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), the cyclic voltammetry (CV). The uniformly distributed small Pt nanoparticles (3–4 nm diameter) were well adhered to the Ti_0·7Ir_0·3O₂ NRs. The electrochemically active surface area (ECSA) of 20 wt % Pt/Ti_0·7Ir_0·3O₂ NRs was higher than that of the commercial 20 wt % Pt/C (E-TEK) due to the small size and good dispersion of Pt nanoparticles on the surface of Ti_0·7Ir_0·3O₂ NRs. Moreover, the ECSA value of the Pt/Ti_0·7Ir_0·3O₂ NRs retained up to 88% after 2000 cycles of cyclic voltammetry, suggesting the high stability of catalyst resulted from strong metal support interaction (SMSI) of Titania-based materials with the noble metals. More importantly, the onset potential of Pt/Ti_0·7Ir_0·3O₂ NRs catalyst towards oxygen reduction reaction is more positive (∼80 mV) compared to commercial Pt/C, indicating the high catalytic activity of the Pt/Ti_0·7Ir_0·3O₂ NRs catalyst. The results of this research suggested that novel Ti_0·7Ir_0·3O₂ NRs could be applied as promising robust non-carbon support for Pt. This research also creates a preliminary step for investigating systematically promising Iridium doped Titania materials.     

Optimizing the Optoelectronic Properties of Face-On Oriented Poly(3,4-Ethylenedioxythiophene) via Water-Assisted Oxidative Chemical Vapor Deposition

Engineering the texture and nanostructure to improve the electrical conductivity of semicrystalline conjugated polymers must address the rate-limiting step for charge carrier transport. In highly face-on orientation, the charge transport between chains within a crystallite becomes rate-limiting, which is highly sensitive to the π–π stacking distance and interchain charge transfer integral. Here, face-on oriented semicrystalline poly(3,4-ethylenedioxythiophene) (PEDOT) thin films are grown via water-assisted (W-A) oxidative chemical vapor deposition (oCVD). Combining W-A with the volatile oxidant, antimony pentachloride, yields an optimized electrical conductivity of 7520  ±  240 S cm⁻¹, a record for PEDOT thin films. Systematic control of π–π stacking distance from 3.50 Å down to 3.43 Å yields an electrical conductivity enhancement of ≈ 1140%. The highest electrical conductivity also corresponds to minimum in Urbach energy of 205 meV, indicating superior morphological order. The figure of merit for transparent conductors, σ_dc/σ_op, reaches a maximum value of 94, which is 1.9 × and 6.7 × higher than oCVD PEDOT grown without W-A and utilizing vanadium oxytrichloride and iron chloride oxidizing agents, respectively. The W-A oCVD is single-step all-dry process and provides conformal coverage, allowing direct growth on mechanical flexible, rough, and structured surfaces without the need for complex and costly transfer steps.     

A comparative study of direct and indirect evaluation of piezoelectric properties of electrophoreticaly deposited (Ba,Ca) (Zr,Ti)O3 lead-free piezoceramics

The development and optimisation of piezoceramics are targeted usually to enhance their piezoelectric properties evaluated by both the direct or indirect measurement methods. The presented work aims to elaborate on the correlation of one direct (Berlincourt) and two indirect (convert and field-dependent) piezoelectric measurement methods on various material states. The role of the ceramic powder treatment by ball milling and electrophoretic deposition (EPD) technique on the determined electric properties as well as basic physical and mechanical properties of (Ba_0.85Ca_0.15) (Zr_0.1Ti_0.9)O₃ ceramics (BCZT) was investigated. It was found that the EPD technologically supported by milling allows obtaining thick and dense deposits (>2 mm). After sintering, the BCZT ceramics with a relative density of >95%, hardness in the range of 2.3–2.9 GPa and piezoelectric coefficients of d₃₃* = 940 pm/V, d_33(E=0) = 427 pm/V and d₃₃ = 364 pC/N can be achieved. Reported results also suggest that indirect (field-dependent) and direct (Berlincourt) measurements of the piezoelectric coefficients can be comparable at optimal poling conditions.     

Structural transformation in Mn-substituted Sr2Bi2Ta2TiO12 Aurivillius phase synthesized by hydrothermal method: A comparative study and dielectric properties

In this study, a hydrothermal method was applied to synthesize the three-layer Aurivillius phase Sr₂Bi₂Ta₂TiO₁₂ (SBTTO) and Mn-substituted Sr_1·5Bi_2·5Ta₂Ti_0·5Mn_0·5O₁₂ (SBTTMO), with the use of NaOH as a mineralizer. The crystal structure, morphology, dielectric properties, and the correlation between the structural transformation and dielectric properties were investigated. The XRD data reveal that the SBTTO sample adopts a tetragonal crystal structure with the I4/mmm space group and is then transformed into an orthorhombic structure with the B2cb space group for SBTTMO. The morphology of both samples was observed by SEM, which showed anisotropic plate-like grains. With the Mn substitution, the ferroelectric transition temperature (T_c) significantly increases as the influence of the 6s² lone pair of Bi³⁺ increases, and this in turn further induces the relaxor-ferroelectric behavior. Consequently, the increase in T_c confirms the structural transformation from the paraelectric-tetragonal to the ferroelectric-orthorhombic phase.     

Effect of hydrothermal aging on dental multilayered zirconia for monolithic restorations: An in vitro study

The aim of this in vitro study was to investigate the changes in mechanical, optical, and surface properties of multilayered zirconia during hydrothermal aging.One conventional block (Katana Zirconia HT) and three multilayered blocks (Katana Zirconia ML, STML, and UTML) of monolithic zirconia were examined. Bar-shaped specimens were autoclaved at 134°C and 0.2MPa for 0, 5, and 10 h. The Young's modulus, three-point flexural strength, and nanoindentation hardness were measured to evaluate the mechanical properties. The surface roughness, phase distribution, surface microstructure, and elemental composition were measured to analyze the surface properties. The contrast ratio and total transmittance were measured via spectrophotometry to evaluate the optical properties. Statistical differences were analyzed using appropriate ANOVA, Tukey HSD post hoc tests, and independent and paired sample t-tests (α = .05).The monoclinic phase increased gradually after hydrothermal aging. The yttrium and zirconium concentrations decreased, and the oxygen concentration and the surface roughness increased in all specimens (P<.05) after the aging process. All specimens showed significant grain push-out and microcracks. The total transmittance increased, and the contrast ratio and Young's modulus decreased in all specimens (P<.05) after the aging process. The nanoindentation hardness and three-point flexural strength exhibited a decreasing tendency after the aging process. However, there were no statistical differences (P>.05) between the materials. Significant interactions between material grades and hydrothermal aging were found for all the properties studied (P<.001).Microstructural alterations and significant phase transformations were detected on the surface of the multilayered zirconia after hydrothermal aging. The hydrothermal aging led to increased surface roughness, opaqueness, and elasticity of multilayered zirconia. The optical, mechanical, and surface properties of multilayered zirconia were influenced by the grade of the material after hydrothermal aging. Careful consideration of the grade of materials is necessary for the appropriate selection of multilayered zirconia ceramics for monolithic restorations.     

Diluted chemical bath deposition of CdZnS as prospective buffer layer in CIGS solar cell

In this study, dilute chemical bath deposition technique has been used to deposit CdZnS thin films on soda-lime glass substrates. The structural, morphological, optoelectronic properties of as-grown films have been investigated as a function of different Zn²⁺ precursor concentrations. The X-ray diffractogram of CdS thin-film reveals a peak corresponding to (002) plane with wurtzite structure, and the peak shift has been observed with the increase of the Zn²⁺ concentration upon formation of CdZnS thin film. From morphological studies, it has been revealed that the diluted chemical bath deposition technique provides homogeneous distribution of film on the substrate even at a lower concentration of Zn²⁺. Optical characterization has shown that the transparency of the film is influenced by Zn²⁺ concentration and when the Zn²⁺ concentration is varied from 0 M to 0.0256 M, bandgap values of resulting films range from 2.42 eV to 3.90 eV while. Furthermore, electrical properties have shown that with increasing zinc concentration the resistivity of the film increases. Finally, numerical simulation validates and suggests that CdZnS buffer layer with composition of 0.0032 M Zn²⁺ concentration would be a promising candidate in CIGS solar cell.     

Effect of carbon nanotubes grown temperature on the fracture behavior of carbon fiber reinforced magnesium matrix composites: Interlaminar shear strength and tensile strength

The design of an interfacial structure is particularly important for load transfer in composites. In this paper, different amounts of carbon nanotubes (CNTs) were grafted onto the carbon fiber (CF) surface by adjusting grown temperature using injection chemical vapor deposition (ICVD). The prepared CF preform grafted with CNTs (CNTs-CF) were used to reinforce magnesium alloy by squeeze casting process. The microstructures were analyzed by means of optical microscope (OM) and scanning electron microscope (SEM), and the interlaminar shear strength (ILSS) and tensile strength of the composites were determined by double-notch shear test and tensile test. The results indicated that moderate ILSS was more conducive to improving the tensile properties of carbon fiber reinforced magnesium matrix (C_f/Mg) composites. Compared with C_f/Mg, the tensile strength of composite with CNTs increased by about 80%. For C_f/Mg composites grafted with CNTs, CNTs had the effects of delaying crack propagation and increasing energy consumption by the pull-out and bridging mechanism, which were the main reasons for improving the strength. The analysis of shear fracture surface showed that the crack propagation path can be optimized by adjusting the amounts of grafted CNTs. The presence of CNTs affects the stress distribution and consequently the crack initiation as well as the crack propagation.     

Symmetry Breaking in Monometallic Nanocrystals toward Broadband and Direct Electron Transfer Enhanced Plasmonic Photocatalysis

Metallic nanocrystals manifest themselves as fascinating light absorbers for applications in plasmon-enhanced photocatalysis and solar energy harvesting. The essential challenges lie in harvesting the full-spectrum solar light and harnessing the plasmon-induced hot carriers at the metal–acceptor interface. To this end, a cooperative overpotential and underpotential deposition strategy is proposed to mitigate both the challenges. Specifically, by utilizing both ionic additive and thiol passivator to introduce symmetry-breaking growth over gold icosahedral nanocrystals, the microscopic origin can be attributed to the site-specific nucleation of stacking faults and dislocations. By adopting asymmetric crystal shape and unique surface facets, such nanocrystals attain high activity toward photocatalytic ammonia borane hydrolysis, arising from combined broadband plasmonic properties and enhanced direct transfer of hot electrons across the metal–adsorbate interface.     

Fabrication of abrasion-resistant micro-nano hierarchical structure on glass surface by a hydrothermal corrosion method

When applying an additional coating method to fabricate micro-nano hierarchical structure required for superhydrophobic function on glass surface, the hierarchical structure does generally not have good abrasion resistance, due to the weak adhesion between coating and glass surface. However, glass itself is a material with good abrasion resistance. A micro-nano hierarchical structure with honeycomb-shaped micro-armor protection on glass surface by a two-step hydrothermal corrosion method has been constructed: the first step of hydrothermal corrosion in water to construct micro-armor structure, and the second step of hydrothermal corrosion in sodium citrate aqueous solution to fabricate micro-nano hierarchical structure. The advantages of this new method are: the treatment process is simple, and there is no need to apply additional coatings. The micro-nano hierarchical structure constructed on glass surface by this method has a great abrasion resistance. After 1,000 cycles of abrasion under harsh conditions, the nano-structure on glass surface can still be remained intact. It provides a new method for fabricating abrasion-resistant micro-nano hierarchical structure on glass surface, as well as a new approach to the preparation of abrasion-resistant superhydrophobic glass.