Lattice Distortion in Hollow Multi-Shelled Structures for Efficient Visible-Light CO2 Reduction with a SnS2/SnO2 Junction

Precise control of the micro-/nanostructures of nanomaterials, such as hollow multi-shelled structures (HoMSs), has shown its great advantages in various applications. Now, the crystal structure of building blocks of HoMSs are controlled by introducing the lattice distortion in HoMSs, for the first time. The lattice distortion located at the nanoscale interface of SnS₂/SnO₂ can provide additional active sites, which not only provide the catalytic activity under visible light but also improve the separation of photoexcited electron–hole pairs. Combined with the efficient light utilization, the natural advantage of HoMSs, a record catalytic activity was achieved in solid–gas system for CO₂ reduction, with an excellent stability and 100 % CO selectivity without using any sensitizers or noble metals.     

Rare-earth Metal Borosilicides R9Si15–xB3 (R = Tb,Yb): New Ordered Structures Derived from the AlB2 Structure Type

Two novel ternary borosilicides R₉Si_15–xB₃ (R = Tb, x = 1.80, R = Yb, x = 1.17) were synthesized from the initial elements using tin flux method. Their crystal structures were determined by means of X-ray single crystal diffraction. Both refer to space group R32, Z = 1: a = 6.668(2) Å, c = 12.405(4) Å [R₁ = 0.027, wR₂ = 0.031 for 1832 reflections with I_o > 2σ (I_o)] for Tb₉Si_15–xB₃, and a = 6.5796(3) Å, c = 12.2599(5) Å [R_F = 0.052, wR = 0.090 for 1369 reflections with I_o > 2σ (I_o)] for Yb₉Si_15–xB₃. The structures represent a new structure type, derived from that of AlB₂, with ordering in the metalloid sublattice resulting in distorted [Si₅B] hexagons. The presence or absence of boron in this ordered structure is discussed on the basis of difference Fourier syntheses, interatomic distances, structural analysis, and theoretical calculations in relation with the parent structures of the binaries AlB₂ and Yb₃Si₅ (Th₃Pd₅ type of structure). Theoretical calculations show substantial covalent interactions between the metal and nonmetal elements. The small percentage of silicon atoms, which are missing in these nonstoichiometric compounds, probably allows strengthening boron-metal and boron-silicon bonding.     

Insights into the interactions between DNA and an infinite clamp-like copper (II) complex

Transition Metal Chemistry - A Cu(II) complex [Cu2(phen)2(NAB)2(HO)]n (phen?=?1, 10-phenanthroline and NABH?=?p-N, N-(2-hydroxyethyl)amino benzoic acid) was synthesized, and...     

Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering

Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively studied and can be tuned by modifying the substituents on the pyridine ligands. On the other hand, ligand modifications that enable substrate binding to control reaction selectivity remain rare. Given the exquisite control that enzymes exert over electron and energy transfer processes in nature, we envisioned that artificial metalloenzymes (ArMs) created by incorporating Ru(ii) polypyridyl complexes into a suitable protein scaffold could provide a means to control photocatalyst properties. This study describes approaches to create covalent and non-covalent ArMs from a variety of Ru(ii) polypyridyl cofactors and a prolyl oligopeptidase scaffold. A panel of ArMs with enhanced photophysical properties were engineered, and the nature of the scaffold/cofactor interactions in these systems was investigated. These ArMs provided higher yields and rates than Ru(Bpy)₃²⁺ for the reductive cyclization of dienones and the [2 + 2] photocycloaddition between C-cinnamoyl imidazole and 4-methoxystyrene, suggesting that protein scaffolds could provide a means to improve the efficiency of visible light photocatalysts.

Artificial metalloenzyme visible light photocatalysts possess enhanced optical properties and are competent towards single electron and energy transfer organic transformations.     

A conditional symmetric memristive system with amplitude and frequency control

By introducing a memristor into a chaotic system with a single non-quadratic term and substituting an absolute value function for conditional symmetry, a unique chaotic system is constructed. Firstly, the system shares a special structure of symmetry and conditional symmetry. Secondly, the amplitude and frequency of the system variables can be rescaled by the applied memristor. Interestingly it gives a new case of attractor control namely partial amplitude control and global frequency control. At last, as a new regime of extreme multistability, the memristive system shows relatively simple bifurcation according to the initial condition. This new class of chaotic system has never been reported to the best of our knowledge.

     

苄嘧磺隆印迹聚合物的波谱分析及吸附性能研究

以苄嘧磺隆为模板分子, α-甲基丙烯酸为功能单体, 三甲氧基丙烷三甲基丙烯酸酯为交联剂, 二氯甲烷为致孔剂, 在20 ℃温度下, 采用紫外引发沉淀聚合方法制备了苄嘧磺隆分子印迹聚合物. 紫外光谱和核磁共振氢谱实验提示了聚合前模板分子与功能单体之间的相互作用主要是分子间氢键, 分子间氢键相互作用能和双氢键的键距由Hyperchem 7.0和Gaussian 03W软件分别计算为: －28.6163 kJ/mol和0.179～0.181 nm. 制备的印迹聚合物在高效液相色谱和吸附动力学实验中都表现出对模板分子有较强的吸附作用.     

Giant lamb shift in photonic crystals

We obtain a general result for the Lamb shift of excited states of multilevel atoms in inhomogeneous electromagnetic structures and apply it to study atomic hydrogen in inverse-opal photonic crystals. We find that the photonic-crystal environment can lead to very large values of the Lamb shift, as compared to the case of vacuum. We also suggest that the position-dependent Lamb shift should extend from a single level to a miniband for an assembly of atoms with random distribution in space, similar to the velocity-dependent Doppler effect in atomic/molecular gases.     

Long-lasting near-infrared persistent luminescence from β-Ga2O3:Cr nanowire assemblies

Near-infrared (NIR) persistent luminescent β-Ga₂O₃:Cr³⁺ nanowire assemblies were synthesized by a hydrothermal process followed by calcination. The phosphor exhibits more than 4 h afterglow in the wavelength range of 650-850 nm after ceasing the ultraviolet light (280-360 nm) irradiation. The trap structure and persistent luminescence mechanism were revealed by thermoluminescence measurement. The β-Ga₂O₃:Cr³⁺ nanowire assemblies may find applications as identification taggants in security and optical probes in bio-imaging.     

Electronic band structure of a type-II ’W’ quantum well calculated by an eight-band k·p model

In this paper, we present an investigation of type-II 'W' quantum wells for the InAs/Ga_1-xIn_xSb/AlSb family, where 'W' denotes the conduction profile of the material. We focus our attention on using the eight-band k?p model to calculate the band structures within the framework of finite element method. For the sake of clarity, the simulation in this paper is simplified and based on only one period---AlSb/InAs/Ga_1-xIn_xSb/InAs/AlSb. The obtained numerical results include the energy levels and wavefunctions of carriers. We discuss the variations of the electronic properties by changing several important parameters, such as the thickness of either InAs or Ga_1-xIn_xSb layer and the alloy composition in Ga_1-xIn_xSb separately. In the last part, in order to compare the eight-band k?p model, we recalculate the conduction bands of the 'W' structure using the one-band k?p model and then discuss the difference between the two results, showing that conduction bands are strongly coupled with valence bands in the narrow band gap structure. The in-plane energy dispersions, which illustrate the suppression of the Auger recombination process, are also obtained.