三缺位硅钨酸盐纳米材料的调控形貌的合成及功能化

以三缺位Keggin型硅钨酸盐为前驱体,采用化学沉淀法成功合成出2例新型纳米材料M_3SiW_9(M=Cu.,Co.)。其中,Cu_3SiW_9表现为新颖的纳米晶须形貌,Co_3SiW_9表现为尺寸均一的球形纳米颗粒。经过一系列控制实验证明,通过掺杂不同类型的金属离子可以调控M_3SiW_9的形貌。我们对产生该现象的机理进行了合理推测。此外,使用荧光素钠作为掺杂剂可使Cu_3SiW_9纳米晶须具有优良的光致发光性能,测试表明,多酸并未淬灭荧光素钠的发光,复合材料在510 nm具有明显的发射波长。最后,我们对Cu_3SiW_9纳米晶须负载CdS量子点后的光催化产氢性质进行了研究。结果表明,当Cu_3SiW_9与CdS的质量比为1∶1时,复合材料的产氢效率约为纯CdS量子点的10倍。这也证实多金属氧酸盐的存在可以有效抑制CdS量子点光生电子与空穴的复合,从而大幅提高其光解水产氢的效率。     

不平“钒”的金属元素*

钒是地壳中含量第21丰富元素,是人体必需的微量元素。介绍钒元素的发现、自然分布以及在人体内的循环。重点从化学结构分析钒酸盐磷酸盐的拮抗作用机制,从生化机理阐述钒化合物对激酶与磷酸酶的调节、对RNA和DNA功能的影响、对活性氧作用的影响,从人体健康视角探讨钒对治疗糖尿病和癌症及保护心血管等的潜在药理学作用。     

Topological entropy of continuous self-maps on closed surfaces

The objective of this work is to present sufficient conditions for having positive topological entropy for continuous self-maps defined on a closed surface by using the action of this map on the homological groups of the closed surface.     

Effect of Environment on the Scattering of Electrons by a Junction of Different Topological Materials

The studies of electron transport through a junction of topological materials in the literature so far ignore the coupling of a topological material to its surrounding environment. Here, the dynamics of an open system through a stochastic Hamiltonian are simulated to investigate the influence of the environment on the scattering of electrons by a junction of different topological materials, such as a Dirac–Weyl magnetic junction and a topological insulator. It is found that, although the detrimental effect of the environment is inevitable, the Landauer conductance can be enhanced via adjusting the system–environment coupling strength. This result supplies the possibilty of changing the transport feature of topological materials by modulating the surrounded environment. It is also demonstrated that a non-Hermitian Hamiltonian can be used to replace the stochastic Hamiltonian for this study, when the system and the environment coupling are weak.     

Microstructure and Thermal and Tensile Properties of Poly(vinyl alcohol) Nanocomposite Films Reinforced by Polyacrylamide Grafted Cellulose Nanocrystals

Abstract

Polyacrylamide grafted cellulose nanocrystals (CNC-g-PAM) were incorporated into poly(vinyl alcohol) (PVA) by a solution casting method to fabricate nanocomposite films with enhanced thermal and tensile properties. The microstructure and the thermal and tensile properties of the PVA/CNC-g-PAM nanocomposite films were investigated as a function of CNC-g-PAM content. Infrared spectroscopy corroborated the presence of hydrogen bonds between PVA and the PAM on the surface of the CNC. Polarized optical microscopy and scanning electron microscopy revealed good dispersion of the CNC-g-PAM in the PVA matrix and good interfacial compatibility. Accordingly, the initial degradation temperature of the nanocomposite films was elevated slightly compared to pristine PVA film. The glass transition temperature, melting temperature, and crystallinity of the PVA also varied slightly after the incorporation of the CNC-g-PAM. At both 0% and 50% RH, the nanocomposite films showed an obvious increase of elastic modulus, no apparent change of breaking strength and a drastic reduction of elongation at break with increasing CNC-g-PAM content.     

Multifunctional Sulfur-Hyperdoped Silicon Nanoparticles with Engineered Mid-Infrared Sulfur-Impurity and Free-Carrier Absorption

Si nanoparticles (NPs), which are innovative promising light-harvesting components of thin-film solar cells and key-enabling biocompatible theranostic elements of infrared-laser and radiofrequency hyperthermia-based therapies of cancer cells in tumors and metastases, are significantly advanced in their near/mid-infrared band-to-band and free-carrier absorption via donor sulfur-hyperdoping during high-throughput facile femtosecond-laser ablative production in liquid carbon disulfide. High-resolution transmission electron microscopy and Raman microscopy reveal their mixed nanocrystalline/amorphous structure, enabling the extraordinary sulfur content of a few atomic percents and very minor surface oxidation/carbonization characterized by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. A 200-nm thick layer of the nanoparticles exhibits near−mid-infrared absorbance, comparable to that of the initial 380-micron thick n-doped Si wafer (phosphor-dopant concentration ≈10¹⁵ cm⁻³), with the corresponding extinction coefficient for the hyperdoped NPs being 4–7 orders higher over the broadband spectral range of 1–25 micrometers. Such ultimate, but potentially tunable mid-IR structured, multi-band absorption of various sulfur-impurity clusters and smooth free-carrier absorption are break through advances in mid-infrared (mid-IR) laser and radiofrequency (RF) hyperthermia-based therapies, as envisioned in the RF-heating tests, and in fabrication of higher-efficiency thin-film and bulk photovoltaic devices with ultra-broad (UV−mid-IR) spectral response.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

Controlled synthesis of ZnO nanoparticles from a Zn(II) coordination polymer: Structural characterization,optical properties and photocatalytic activity

A zinc coordination polymer derived from pyridine-2,6-dicarboxylate (PDC), {[Zn₂(PDC)₂]}_n, was successfully prepared via conventional, sonication and microwave-irradiation methods. The composition and characteristics of the obtained coordination polymers (CPs) were investigated by elemental analysis, TGA/DTA, X-ray diffraction and spectroscopic techniques. The so obtained CPs were heat-treated in the air at 600 °C for 2 h to produce ZnO of nanosized particles (NPs). It is of interest to note that the synthesis approach of the precursor greatly affects both the nanoparticle size and the structure of the resulting ZnO NPs. Moreover, the smallest particle size was associated with the sample derived from the ultrasonically prepared precursor. TEM analysis revealed that all samples have sphere-like morphologies. Structural analysis of the prepared ZnO samples was conducted and compared using Rietveld analysis of their PXRD patterns. Optical band gap calculations based on analysis of the UV–vis spectra of ZnO samples using Tauc's power law were achieved. The highest band gap of 3.63 eV was observed for ZnO sample obtained from the ultrasonically prepared precursor. Furthermore, the photocatalytic activity of ZnO NPs for the removal of Eosin Y color was monitored. The highest removal efficiency was recorded for ZnO originated from the ultrasonically synthesized precursor. Enhancement of removal efficiency that reached 98% was attained in only a period of 8 min. Its recycling test showed that it can be reused without structural changes over four cycling experiments.