A one‐dimensional manganese(III)–porphyrin coordination polymer: crystal structure and photophysical properties

A novel manganese(III)–porphyrin complex, namely, catena‐poly[[chloridomanganese(III)]‐μ₂‐5,10,15,20‐tetrakis(pyridin‐3‐yl)‐21H,23H‐porphinato(2?)‐κ⁵N²¹,N²²,N²³,N²⁴:N⁵], [MnCl(C₄₀H₂₄N₈)]_n, 1 , was prepared by the hydrothermal reaction of manganese chloride with 5,10,15,20‐tetrakis(pyridin‐3‐yl)‐21H,23H‐porphine. The crystal structure was determined by single‐crystal X‐ray diffraction. The porphyrin macrocycle exhibits a saddle‐like distortion geometry. The Mn^III atom has a six‐coordination geometry. Each porphyrin unit links to two neighbouring units to yield a one‐dimensional coordination polymer. These chains are further interlinked by hydrogen bonds to form a two‐dimensional network. The complex shows red photoluminescence emission bands in ethanol solution, which can be attributed to ligand‐to‐ligand charge transfer (LLCT) accompanied by partial metal‐to‐ligand charge transfer (MLCT), as revealed by TDDFT calculations.     

Dipole‐Induced Band‐Gap Reduction in an Inorganic Cage

Metal‐doped polyoxotitanium cages are a developing class of inorganic compounds which can be regarded as nano‐ and sub‐nano sized molecular relatives of metal‐doped titania nanoparticles. These species can serve as models for the ways in which dopant metal ions can be incorporated into metal‐doped titania (TiO₂), a technologically important class of photocatalytic materials with broad applications in devices and pollution control. In this study a series of cobalt(II)‐containing cages in the size range ca. 0.7–1.3 nm have been synthesized and structurally characterized, allowing a coherent study of the factors affecting the band gaps in well‐defined metal‐doped model systems. Band structure calculations are consistent with experimental UV/Vis measurements of the Ti_xO_y absorption edges in these species and reveal that molecular dipole moment can have a profound effect on the band gap. The observation of a dipole‐induced band‐gap decrease mechanism provides a potentially general design strategy for the formation of low band‐gap inorganic cages.     

Superconducting Double Perovskite Bismuth Oxide Prepared by a Low‐Temperature Hydrothermal Reaction

Perovskite‐type structures (ABO₃) have received significant attention because of their crystallographic aspects and physical properties, but there has been no clear evidence of a superconductor with a double‐perovskite‐type structure, whose different elements occupy A and/or B sites in ordered ways. In this report, hydrothermal synthesis at 220 °C produced a new superconductor with an A‐site‐ordered double perovskite structure, (Na_0.25K_0.45)(Ba_1.00)₃(Bi_1.00)₄O₁₂, with a maximum T_c  of about 27 K.     

自掺杂TiO_2纳米管:液相制备及光催化性能

采用水合肼(N2H4·H2O)作为还原剂,在液相环境中制备了自掺杂TiO2纳米管阵列(NTs)。利用FE-SEM、EDS、XPS、XRD、Raman、UV-Vis/NIR分光光度法以及半导体特性分析系统(Keithley 4200 SCS)分别对样品的形貌,晶体结构,光学特性以及电学性能进行了表征。结果表明:通过这种方法制备的自掺杂TiO2NTs在带隙中引入了大量的氧空位,创造了氧空位能级,从而提高了样品的电导率,有效提高光生电子-空穴对的产生、分离和传输。此外,由于氧空位的作用,使得TiO2NTs的带隙变窄,增强了可见光吸收能力,致使样品具有较高的光催化活性,并通过降解甲基橙溶液对样品的光催化活性进行评估。结果显示当光照150 min后,自掺杂TiO2NTs对甲基橙溶液的降解率达73%,并且这种催化剂便于回收和重复使用。     

Thorough tuning of the aspect ratio of gold nanorods using response surface methodology

In the present work a central composite design based on response surface methodology (RSM) is employed for fine tuning of the aspect ratios of seed-mediated synthesized gold nanorods (GNRs). The relations between the affecting parameters, including ratio of l-ascorbic acid to Au³⁺ ions, concentrations of silver nitrate, CTAB, and CTAB-capped gold seeds, were explored using a RSM model. It is observed that the effect of each parameter on the aspect ratio of developing nanorods highly depends on the value of the other parameters. The concentrations of silver ions, ascorbic acid and seeds are found to have a high contribution in controlling the aspect ratios of NRs. The optimized parameters led to a high yield synthesis of gold nanorods with an ideal aspect ratio ranging from 1 (spherical particle) to 4.9. In addition, corresponding tunable surface Plasmon absorption band has been extended to 880 nm. The resulted nanorods were characterized by UV–visible spectrometry and transmission electron microscopy.     

Effective band gap reduction of titanium oxide semiconductors by codoping from first‐principles calculations

Doping is an efficient approach to narrow the band gap of TiO₂ and enhance its photocatalytic activity. Here, we perform generalized gradient approximation (GGA)+U calculations to narrow the band gap of TiO₂ by codoping of X (F, N) with transition metals (TM = Fe, Co) to extend the absorption edge to longer visible‐light wavelengths. Our results show that all the codoped systems can narrow the band gap significantly, in particular, (F+Fe)‐codoped system could serve as remarkably better photocatalysts with both narrowing of the band gap and relatively smaller formation energies than those of (F+Co) and (N+TM)‐codoped systems. Our results provide useful guidance for codoped TiO₂ efficient for photocatalytic activity. © 2013 Wiley Periodicals, Inc.     

Recent advances in spherical photonic crystals: Generation and applications in optics

Spherical photonic crystals (PCs), generated by assembly of monodisperse colloidal nanospheres in a spherical confined geometry, attract great attention recently owing to their potential applications in the fields of displays, sensors, optoelectronic devices, and others. Compared to their conventional film or bulk counterparts, the optical stop band of the spherical PCs is independent of the rotation under illumination of the surface of a fixed incident angle of the light, broadening their applications. In this paper, we will review recent advances in the field of spherical PCs including design, preparation and potential applications. Various preparation strategies for spherical PCs, including solvent-evaporation induced crystallization method, microfluidic-assisted approach, and others are outlined. Their applications based on the unique optical properties (such as photonic band gaps and structural colors) for sensing and displaying are then presented, followed by the perspective of this emerging field.     

Theoretical studies of the band structure and optoelectronic properties of ZnOxS1−x

In the present article, we have revisited the electronic band gap nature of ZnO_xS_1?x (0 ≤ x ≤ 1) with the recently developed modified Becke and Johnson exchange potential and the calculated band gaps are found consistent with the experimental results. We expect that the band gap bowing parameter obtained in the present work will be close to the experimental one. As the optical properties of ZnO_xS_1?x (0 ≤ x ≤ 1) are very important, therefore different optical parameters like dielectric functions, refractive index and reflectivity are also calculated. The results are illustrated in terms of band structures, band gap energy as a function of oxygen composition, total and partial density of states. © 2012 Wiley Periodicals, Inc.     

Support vector regression with digital band pass filtering for the quantitative analysis of near‐infrared spectra

This paper proposes a novel calibration technique based on combining support vector regression with a digital band pass (DBP) filter for the quantitative analysis of near‐infrared spectra. The efficacy of the proposed method is investigated and validated in the determination of glucose from near‐infrared spectra of a mixture composed of urea, triacetin and glucose. In this paper, the DBP filtering was implemented as a pre‐processing technique in the frequency domain as a Gaussian band pass filter and in the time domain as a Chebyshev filter. The grid‐search optimization method was used to optimize the filter parameters. The results demonstrate that utilization of the optimized DBP filters as a pre‐processing technique improved the performance of the predictive models. Copyright © 2013 John Wiley & Sons, Ltd.