Heteroborospherene nanoclusters as high-performance nonlinear optical materials

Today, the design of new compounds with giant nonlinear optical responses is attracted to many researchers. Inspired by an interesting finding of a new class of heteroborospherenes which were formed by doping four carbon atoms in the B364- nanocluster (C4B32), we suggest the alkali metal-doped C4B32 (M@C4B32, M=Li, Na, and K) nanoclusters as high-performance nonlinear optical materials. Our results show that the alkali metal atoms have a considerable effect on the structural and electronic properties of the C4B32 nanocluster. We found that the doping alkali metal can remarkably decrease the HOMO-LUMO gap and significantly increases the first hyperpolarizability of the C4B32 nanocluster. Also, our results reveal that the first hyperpolarizability of the M@C4B32 nanoclusters can be progressively enhanced by increasing the atomic number of alkali metals. The effect of external electric fields on the nonlinear optical responses of the M@C4B32 has been systematically explored. We found that the first hyperpolarizability of the M@C4B32 compounds can be gradually increased by increasing the imposed external electric field from zero to the critical external electric field along the charge transfer direction (M→C4B32). Accordingly, this work presents an efficient strategy to improve the nonlinear optical responses of the heteroborospherenes.     

Microstructure evolution of room-temperature-sputtered ITO films suitable for silicon heterojunction solar cells

Thickness influence on structural, optical and electrical properties of sputtered indium tin oxide (ITO) with thickness ranging from 60 up to 430 nm films has been studied. At the increase of the film thickness crystallinity degree and grain size increased, whereas tensile structural distortion as well as resistivity decreased. It was observed that a microstructure evolution takes place: the initial amorphous layer evolved in polycrystalline phase, with a grain–subgrain surface morphology. Carrier concentration increased at the increase of the film thickness and a general relationship between electrical characteristics and structural distortion has been found. In thinner films larger tensile distortion allowed to include larger amount of interstitial O and/or Sn atoms in the lattice. An appreciable impact of the thickness was also observed on electro-optical properties in terms of changes in energy gap, resistivity and optical absorption. Silicon heterojunction solar cells have been produced and J_sc as high as 33.0 mA/cm² has been obtained.     

Nanostructured BiVO4 Derived from Bi-MOF for Enhanced Visible-light Photodegradation

BiVO4,a promising visible-light responding photocatalyst,has aroused extensive research interest because of inexpensiveness and excellent chemical stability.However,its main drawback is the poor photoinduced charge-transfer dynamics.Building nanostructures is an effective way to tackle this problem.Herein,we put forward a new method to prepare nanostructured BiVO4 from Bi-based metal-organic frameworks[Bi-MOF(CAU-17)]precursor.The as-prepared material has a rod-like morphology inherited from the Bi-MOF sacrificial template and consists of small nanoparticle as building blocks.Compared with its counterparts prepared by conventional methods,MOF-derived nanostructured BiVO4 shows better light absorption ability,narrower bandgap,and improved electrical conductivity as well as reduced recombination.Consequently,BiVO4 nanostructure demonstrates high photocatalytic activity under visible light towards the degradation of methylene blue.Methylene blue can be degraded up to 90%within 30 min with a reaction rate constant of 0.058 min-1.Moreover,the cycling stability of the catalyst is excellent to withstand unchanged degradation efficiency for at least 5 cycles.     

Dimensional scaling of flame propagation in discrete particulate clouds

The critical dimension necessary for a flame to propagate in suspensions of fuel particles in oxidiser is studied analytically and numerically. Two types of models are considered: First, a continuum model, wherein the individual particulate sources are not resolved and the heat release is assumed spatially uniform, is solved via conventional finite difference techniques. Second, a discrete source model, wherein the heat diffusion from individual sources is modelled via superposition of the Green's function of each source, is employed to examine the influence of the random, discrete nature of the media. Heat transfer to cold, isothermal walls and to a layer of inert gas surrounding the reactive medium are considered as the loss mechanisms. Both cylindrical and rectangular (slab) geometries of the reactive medium are considered, and the flame speed is measured as a function of the diameter and thickness of the domains, respectively. In the continuum model with inert gas confinement, a universal scaling of critical diameter to critical thickness near 2:1 is found. In the discrete source model, as the time scale of heat release of the sources is made small compared to the interparticle diffusion time, the geometric scaling between cylinders and slabs exhibits values greater than 2:1. The ability of the flame in the discrete regime to propagate in thinner slabs than predicted by continuum scaling is attributed to the flame being able to exploit local fluctuations in concentration across the slab to sustain propagation. As the heat release time of the sources is increased, the discrete source model reverts back to results consistent with the continuum model. Implications of these results for experiments are discussed.     

Thin film photocatalysis for environmental remediation: A status review

This review accounts, various metal oxide and metal sulfide thin films available for photodegradation of several organic compounds. Due to difficulties in recycling and to avoid rigorous recollection of powder catalysts, the thin film catalyst are gaining rapid attention for photocatalytic applications. The semiconducting thin films are growing as promising photocatalyst for water treatment. This review focuses mainly on the photocatalytic activity of metal oxide thin films in terms of its stability, charge transport and absorption properties. Thin film photocatalyst provides the increased efficiency and cost reduction of device. Furthermore, this review summarizes some key factors regarding the enhancement in photocatalytic performance of thin films.     

自动石墨消解–电感耦合等离子体质谱法同时测定左氧氟沙星胶囊中7种金属元素

建立自动石墨消解-电感耦合等离子体质谱法(ICP-MS)同时测定左氧氟沙星胶囊中铅、铬、砷、镉、锡、铝、铁7种金属元素含量的方法。以HNO3-H2O2()体积比为1∶1为消解体系,采用自动石墨消解法消解左氧氟沙星胶囊样品,消解液除酸后,用5%硝酸溶液定容至50 mL,采用电感耦合等离子体质谱法对消解液进行测定,以内标法定量。铅、铬、砷、镉、锡、铝、铁的质量浓度在0.05~20.0μg/mL范围内与质谱响应值成良好的线性关系,相关系数均大于0.998,方法检出限为0.119~1.323μg/kg。样品加标回收率为91.2%~105.5%,测定结果的相对标准偏差为1.67%~3.46%(n=6)。该方法样品前处理简单,检出限低,测定结果准确,适用于左氧氟沙星胶囊等沙星类抗生素中多种金属元素残留的测定。     

Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms

The interplay between the self-assembly and surface chemistry of 2,3,6,7,10,11-hexaaminotriphenylene (HATP) on Cu(111) was complementarily studied by high-resolution scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) under ultra-high vacuum conditions. To shed light on the competitive metal coordination, comparative experiments were carried out on pristine and nickel-covered Cu(111). Directly after room-temperature deposition of HATP onto pristine Cu(111), self-assembled aggregates were observed by STM, and XPS results indicated still protonated amino groups. Annealing up to 200 °C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both the N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically diverse π–d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal–organic trimer, in which three HATP molecules were coordinated by Cu₃ clusters, as corroborated by the accompanying density functional theory (DFT) simulations. Additional deposition of more reactive nickel atoms resulted in both chemical and structural changes with deprotonation and formation of bis(diimino)–Ni bonded networks already at room temperature. Even though fused hexagonal metal-coordinated pores were observed, extended honeycomb networks remained elusive, as tentatively explained by the restricted reversibility of these metal–organic bonds.     

Redox-Guest-Induced Multimode Photoluminescence Switch for Sequential Logic Gates in a Photoactive Coordination Cage

Molecular or supramolecular level photoluminescence (PL) modulation combining chemical and photonic input/output signals together in an integrated system can provide potential high-density data memorizing and process functions intended for miniaturized devices and machines. Herein, a PL-responsive supramolecular coordination cage has been demonstrated for complex interactions with redox-active guests. PL signals of the cage can be switched and modulated by adding or retracting Fc derivatives or converting TTF into different oxidation states through chemical or photochemical pathways. As a result, reversible or stepwise PL responses are displayed by these host–guest systems because of the occurrence of photoinduced electron-transfer (PET) or fluorescence resonance energy transfer (FREnT) processes, providing unique nanodevice models bearing off/on logic gates or memristor-like sequential memory and Boolean operation functions.     

Molecular Encapsulation of Trimeric Chromium Carboxylate Clusters in Metal–Organic Frameworks and Propylene Sorption

Oxo-bridged trimeric chromium acetate clusters [Cr₃O(OOCCH₃)₆(H₂O)₃]NO₃ have been encapsulated for the first time in the mesoporous cages of the chromium terephthalate MIL-101(Cr). The isolated clusters in MIL-101(Cr) have increased affinity towards propylene compared to propane, due to generation of a new kind of pocket-based propylene-binding site, as supported by DFT calculations.