Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Gap modulation in MCu[Q1−xQ′x]F (M=Ba, Sr; Q, Q′=S, Se, Te) and related materials

BaCuQF (Q=S, Se, Te) materials exhibit band gaps that allow transmission of much of the visible spectrum. BaCuSF is transparent in thin-film form with a band gap of 3.1 eV. Band gap estimates for powders of the solid solution series BaCuS_1−xSe_xF were obtained from wavelength-dependent diffuse-reflectance measurements using an integrating sphere. The band gap can be tuned by the substitution of Se for S to 2.9 eV for BaCuSeF. The decrease scales almost linearly with the increase in the volume of the tetragonal unit cell, which is determined primarily by the expansion of the a lattice parameter; the overall volume increase is 7.0% from x=0 to 1. Further reduction of the band gap is observed in BaCuSe_1−xTe_xF solid solutions, where a unit cell volume increase of 5.5% produces a band gap of 2.7 eV in BaCuSe_0.5Te_0.5F. Powders and films of BaCuSF exhibit strong red luminescence under ultraviolet excitation, which is suppressed by K doping. Additional tuning of band gap and electrical properties (the materials are p-type conductors) can be achieved by replacing Ba with Sr.     

异质谷间转移电子器件的计算机模拟

使用弛豫时间近似求出了描述两能谷间电子交换的方程。在此基础上建立了双能谷电子的连续性方程和油松方程。对具体的ＧａＡｓ／ＡｌｘＧａ１－ｘＡｓ异质谷间转移电子器件结构求解了这些方程组，得到了直流工作时器件内的电场分布、双能谷中载流子的布居以及两个能谷的电流分布。这些结果正好和常规Ｇｕｎｎ器件相反，说明了两种器件的不同工作机理。最后通过对低Ａｌ组份势垒结构的计算说明了Ｘ谷电子注入对器件工作的重要作用。     

短周期超晶格AlP／GaP能带结构的转变及其带间的光跃迁

介绍了间接跃迁的半导体ＡｌＰ与ＧａＰ形成的超晶格，由于零折叠效应，实现了能带由间接带隙向直接带隙的转变，从而增加了带间的光跃迁几率，并推导了该几率的表达式。     

The mechanics of compressive kinking in unidirectional fiber reinforced ductile matrix composites

Three distinct stages of kink band formation and propagation exist in ductile matrix composites subjected to compressive loading. These stages are called incipient kinking, transient kinking and kink band broadening. Each stage involves a different deformation mode. The mechanics governing each stage are discussed. Incipient kinking, where the peak load is attained, and kink band broadening, where the load attains a steady-state, are important in structural design. Two design philosophies are presented. References to pertinent literature are made throughout.     

省煤器管开裂原因分析

对省煤器开裂管进行了化学成分及宏、微观分析。分析结果表明，在高温高压条件下，在其焊缝溶合区出现粗大的魏氏组织，管材中的珠光体组织产生了不同程度的球化，而母材组织又存在严重的带状组织。在过热条件下熔合区极易出现裂纹，并由此快速扩展，造成省煤器管开裂。     

Electrical and optical properties of fluorine-doped CdO films deposited by ultrasonic spray pyrolysis

The CdO:F samples have been deposited onto microscope glass substrates at 250 °C by ultrasonic spray pyrolysis method. With the incorporation of fluorine into CdO, the direct optical transition has shifted towards the shorter wavelengths, and the transparency of the material has increased at a given wavelength above the fundamental absorption edge. The shift in the absorption edge is explained by means of the Moss–Burstein effect, which is also supported with the results of the current–voltage characteristics. Here, a correlation has been established between the band broadening and the increase in conductivity due to the increase in carrier density.     

Chemical compositions and optical properties of HfOxNy thin films at different substrate temperatures

High-k HfO_xN_y thin films have been grown by radio frequency (rf) reactive sputtering of metal Hf target in N₂/Ar/O₂ ambient at different substrate temperatures. The chemical compositions of the films have been investigated as a function of substrate temperature by X-ray photoelectron spectroscopy (XPS). XPS measurements showed that nitrogen concentration increases with an increase in substrate temperature. Room-temperature spectroscopic ellipsometry (SE) with photon energy 0.75–6.5 eV was used to investigate the optical properties of the films. SE results demonstrated that refractive index n increases with an increase in substrate temperature. Based on TL parameters which were obtained from the best fit results used in a simulation of the measured spectra, meanwhile, we conclude that the energy band gap (E_g) decreases with an increase in substrate temperature.     

SiH4激光等离子体内H谱线的线型研究

本文利用OMA-Ⅲ系统测量了脉冲TEA CO_2激光诱发的SiH_4等离子体发光谱内H巴耳末系的H_α、H_β和H_γ线的线型及线宽。通过理论及实验分析,认为这些谱线的主要加宽机制为Stark加宽。由实验线型和理论线型的拟合得到等离子体的电子温度T≈40000K和电子密度N≈10~(17)cm~(-3)。     

Effects of calcination temperature on phase and microstructure evolution of BaTi4O9 powders

Calcining of the mixture of BaCO₃ and TiO₂ with a ratio 1:4 at different temperatures was carried out to synthesize BaTi₄O₉ powders. Phase evolution of the samples was studied using the differential thermal analysis (DTA) and X-ray diffractometry (XRD). Both techniques confirmed that the formation of BaTi₄O₉ started around 1000 °C. The XRD peaks showed that BaTi₄O₉ was most pronounced at 1250 °C. X-ray line broadening methods were employed to study the variation of particle size and microstrain of the BaTi₄O₉ powders. The Voigt function in a single line and the pseudo-Voigt function in the variance methods were used in our case. We found that both functions resulted in the same trends, i.e., the particle size increased with the temperature with the biggest size of 180 and 160 nm, whilst the microstrain yielded the opposite trend with the lowest values of 6.2 × 10^–3 and 1.1 × 10^–3. The scanning electron microscopy (SEM) study revealed the size of the large particles formed, due to agglomeration, to be about 0.5–1.9 μm. Furthermore, it was shown that irregular shapes of BaTi₄O₉ powders necked to each other appeared at 1000 °C and grew into ellipse and rod shapes at 1250 °C. Electronic Publication