二维过渡金属硫族化合物缺陷工程

二维过渡金属硫族化合物(two-dimensional transition metal dichalcogenides,TMDs)具有厚度在原子级别、禁带宽度随层数在1～2 eV内变化、高载流子迁移率(如MoS₂载流子迁移率达到了200 cm²·V^-1·s^-1)等特点,在光学、电学等领域具有广泛应用。TMDs的超薄特性使此类材料与块体材料相比,更容易受到缺陷调控的影响,改变材料原有性能。在本综述中,首先介绍了TMDs的晶体结构和相结构,并根据维度特征对缺陷的类型进行了分类;接着从缺陷的抑制和修复,以及缺陷的制造两方面出发,总结了缺陷调控TMDs材料性能的最新研究进展;在此基础上,介绍了缺陷工程在电学、光学、磁学、电催化等领域的具体应用;最后,本综述讨论了缺陷工程在应用过程中面临的实际问题,并对其未来的研究及发展方向进行了展望。     

固态TiO2纳米太阳电池研究进展

本文介绍了固态TiO2纳米太阳电池的结构和工作有理，对近年来全固态纳米太阳电池，纳米TiO2膜、染料敏化剂的研究进展进行了综述。     

Self-assembly and photoelectric properties of cerium complexes with 3,4,9,10-perylenetetracarboxylic acid on nanocrystalline TiO_2 films

Self-assembled (SA) films (PMP, M = Ce3+ or Ce4+) of 3,4,9,10-perylenetetracarboxylic acid (PTA) on nanocrystalline TiO2 films with Ce3+ or Ce4+ as a bridge were fabricated and characterized with UV-Vis, IR, and XPS synchrotron radiation photoelectron spectroscopy (SRPES) which gave the HOMO energy levels for the SA films. It was shown that thin-layer sandwich-type solar cells based on these SA films possess good properties for photoelectric conversion. While PTA-loaded TiO2 electrode (P) generated 26.9% of incident monochromatic photon-to-electron conversion efficiency (IPCE), PMP-sensitized Ti02 electrodes yielded 55.8% and 39.1% for Ce4+ and Ce3+ respectively. PMP films can be considered as a kind of complexes whose HOMO energy levels were proved to be higher than that of film P, which is one of the major reasons for the increase in IPCE from film P to film PMP.     

Preparation and characterization of nanocrystalline ZnO by direct precipitation method

Nanocrystalline ZnO was prepared with ZnCl₂·2H₂O and (NH₄)₂CO₃ as raw materials by direct precipitation method. The precursor was proved to be [Zn₅(OH)₆(CO₃)₂] by TG-DTG-DTA and IR analysis. This precursor was calcined at 300°C for 1, 2 and 3 hours respectively, and then the nanocrystalline ZnO of different grain size were obtained. The nanocrystalline ZnO was characterized using X-ray diffraction (XRD), TEM and Brunner-Emmett-Teller method (BET). Experimental results for nanocrystalline ZnO showed that the minimum size was about 8nm, the maximum was about 15 nm and the mean grain size was 12 nm, the surface area was 80.56 m²/g and the purity was 99.9% when the precursor was calcined at 300°C for 2 h. __________ Translated from Journal of Inner Mongolia Normal University (Natural Science Edition), 2006, 35(1) (in Chinese)     

Biocidal activity of nanocrystalline silver powders and particles

While the activity of the SMAD powders is lower than that of pure silver nitrate, it has the ability to kill bacteria very effectively and over long periods of time.     

燃烧合成法制备稀土氧化物纳米粉

本文采用硝酸盐 甘氨酸体系合成Ｙ2 Ｏ3、ＣｅＯ2 、Ｎｄ2 Ｏ3、Ｐｒ6 Ｏ11、Ｓｍ2 Ｏ3纳米粉 ,并研究了后三者在潮湿空气中的化学稳定性。其ＩＲ谱随着颗粒尺寸的减少 ,Ｙ Ｏ振动峰发生红移 ,同时谱峰强烈展宽[1,2 ] 。1　仪器及实验ＲｉｇａｋｕＤ/ｍａｘγＡ转靶衍射仪 ,ＨｉｔａｃｈｉＨ 80 0ＴＥＭＳＸ 1 70ＦＴＩＲ光谱仪 ,ＲｉｇａｋｕＰＴＣ 1 0ＡＴＧ ＤＲＡ分析仪。制备时所用前驱物均为水合稀土硝酸盐 ,其中Ｃｅ(ＮＯ3) 3·6Ｈ2 Ｏ为分析纯商用试剂 (纯度为99 99% ) ,其他水合稀土硝酸盐则参照文献[3,4 ] 分别由高纯稀土氧化物…     

Preparation of nanocrystalline anatase TiO2 using basic sol-gel method

Nanocrystalline titanium dioxide particles with anatase structure and high thermal stability have been synthesized using the basic sol-gel method. The particle size and morphology were refined under hydrothermal conditions in the presence of different concentrations of tetramethylammonium hydroxide (TMAH) at 210°C and 230°C. XRD and TEM analysis showed that the TiO₂ particles obtained were homogeneous and monodispersive at low contents of TMAH. All intense peaks, clearly observed in the XRD patterns, were assigned to the anatase phase and no rutile phase was observed. At high contents of TMAH, nanoscale small (10–30 nm) and larger (>100 nm) TiO₂ particles were one-pot synthesized. The nanocrystalline TiO₂ particles synthesized by this method have good thermal stability. With the sintering temperature of up to 650°C, all the XRD peaks maintained good agreement with the anatase reference data.     

Electrochemical behavior of nitrogenated nanocrystalline diamond electrodes

Nitrogenated nanocrystalline diamond films with controlled conductivity are deposited from microwave plasma in CH₄-Ar-H₂-N₂ gas mixtures. They are characterized using atomic force microscopy, Raman spectroscopy, and electrophysical measurements. Their electrochemical properties are studied by cyclic voltammetry and electrochemical impedance spectroscopy. Kinetic parameters of reactions in [Fe(CN)₆]^3-/4- redox system are determined. The character of electrode behavior is controlled by the degree on nitrogenation. With the increasing of the nitrogen content in the reaction gas mixture (from 0 to 25%), the potential window somewhat narrows, the background current increases, the reversibility of reactions in the [Fe(CN)₆]^3-/4- redox system increases. By and large, the transition occurs from the electrochemical behavior of a “poor conductor” to that of a metal-like electrode.     

Study on the coating of nano-scale SiO<Subscript>2</Subscript> film on the surface of nanocrystalline Mg-Al layered double hydroxides

Since the layered double hydroxides (abbreviatedas LDHs) were firstly reported to be used as precur-sors of new catalytic materials by S. Miyata[1] in 1971,their preparations, ion-exchanges with the balancinginterlayer anions, structure characteristics an…     

New copper and silver trimethylsilylchalcogenolates

The synthesis and characterization of the copper and silver trimethylsilylchalcogenolates (EtPh2P)3MESiMe3 and (Et2PhP)3MESiMe3 (M = CuI, AgI) are reported. These chalcogenolate complexes can be prepared in high yield; however, they are thermally unstable. Low-temperature single-crystal X-ray analysis of (EtPh2P)3CuSSiMe3 (1b) and (Et2PhP)3CuSeSiMe3 (2a) confirms the terminal coordination of the chalcogen ligand and the tetrahedral coordination about the metal. Protonolysis of 2a with EtOH yields the terminal selenol complex (Et2PhP)3CuSeH (6). Reaction of 1b with EtPh2P-solubilized AgOAc yields the heterometallic cluster [Cu9Ag3S6(PEtPh2)8] (7) in good yield.     

Dopants in nanocrystalline tin dioxide

The review surveys studies aimed at constructing new materials for gas sensors based on nanocrystalline tin dioxide. The influence of doping with various impurities (Pt, Pd, Ru, Rh, Cu, Ni, or Fe) on the composition, microstructure, and electrophysical and sensor properties of nanocrystalline SnO₂ was discussed. The conditions for the preparation of powders and thick and thin SnO₂ films by the wet chemical method and aerosol pyrolysis of organometallic compounds are reported. The mechanism of interaction of pure and doped nanocrystalline SnO₂ with a gas phase was analyzed based on the data from Mossbauer, Auger electron, and X-ray photoelectron spectroscopy and the results of in situ Raman spectroscopy, XANES, and conductivity measurements.     

Defect and transport properties of nanocrystalline ceramics and thin films

This paper presents an overview of recent research on the defect and transport properties of nanocrystalline ionic and mixed conducting ceramics and thin films. In the first part, some basic concepts and properties of boundaries are reviewed, including diffusion, segregation, and space charge regions. Experimental data on nanoceramics and thin films made from pure and doped CeO₂, TiO₂, ZrO₂, and CaF₂ are presented and discussed in the second part; opportunities for future work on this topic are outlined. Electronic Publication     

Studies on the interfacial charge transfer processes of nanocrystalline CdSe thin film electrodes by intensity modulated photocurrent spectroscopy

Interfacial charge transfer kinetics of the nanocrystalline CdSe thin film electrodes have been studied in sodium polysulfide solutions by intensity modulated photocurrent spectroscopy (IMPS). The interfacial direct and indirect charge transfer and recombination processes were analyzed in terms of the parameters: normalized steady state photocurrents and surface state lifetimes obtained by measuring the IMPS responses under different applied potentials and different solution concentrations. IMPS responses of polycrystalline CdSe thin film electrodes were also presented for comparison.     

Iridium oxide-based nanocrystalline particles as oxygen evolution electrocatalysts

Iridium-based oxides are highly active as oxygen evolving electrocatalysts in PEM water electrolyzers. In this work XRD reveals that Ir-Sn oxides contain a single rutile phase with lattice parameters between those of pure IrO₂ and SnO₂. Addition of Ru leads to the synthesis of a core-shell type material due to the strong agglomeration of Ru colloids during the preparation procedure. The shell of this material consists of an Ir-Sn-Ru oxide deficient in Ru relative to the bulk. This leads to a decrease in the surface noble metal concentration (as found by XPS), which in turn results in a significant reduction in electrochemically active surface area. Polarization analysis indicates that the addition of Ru can influence the rate-determining step or mechanism by which oxygen is evolved. In a PEM water electrolysis cell, small additions of Sn do not significantly reduce the operating performance, however larger additions cause a performance loss due to a reduction in active surface area and increased ohmic resistance. When a pure IrO₂ anode is used, a cell voltage is 1.61 V at 1 A cm⁻² and 90°C. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 10, pp. 1260–1267. The text was submitted by the authors in English.     

Antibacterial membranes based on chitosan and quaternary ammonium salts modified nanocrystalline cellulose

Etherification of nanocrystalline cellulose (NCC) with three kinds of quaternary ammonium salts epoxypropyltrimethylammonium chloride, N,N‐dimethyl‐N‐dodecyl‐N‐(1,2‐epoxypropyl) ammonium chloride (DMDEPAC), and N,N‐dimethyl‐N‐octadecyl‐N‐(1,2‐epoxypropyl) ammonium chloride (DMOEPAC) was successfully performed via a nucleophilic addition reaction. The synthesized DMDEPAC and DMOEPAC were characterized by nuclear magnetic resonance. The modified NCC particles, NCC epoxypropyltrimethylammonium chloride, NCC‐DMDEPAC, and NCC‐DMOEPAC, were characterized by energy dispersive spectrometer. Nanocomposite films based on chitosan (CS) containing quaternary ammonium salts modified NCC were prepared with nanoparticle loadings of 5.0, 7.5, and 10.0%, respectively. The effect of nanoparticle content on the tensile strength of composite films was studied. The results indicated that the films with 5.0% nanoparticle loading exhibited the biggest increase in tensile strength. Surface morphology, smoothness, and antibacterial properties of composite films containing 5% modified NCC were also studied. CS/NCC‐DMDEPAC‐5.0 and CS/NCC‐DMOEPAC‐5.0 displayed excellent biocidal abilities against both Gram‐positive Staphylococcus aureus (ATCC 6538) and Gram‐negative Escherichia coli O157:H7 (ATCC 43895). The bio‐based nanocomposite films with increased mechanical strength and excellent antibacterial properties show great potential as food packaging materials. Copyright © 2017 John Wiley & Sons, Ltd.     

溴氧化镧的缺陷发光

用高温固相法合成了具有缺陷发光的溴氧化镧基质。对样品进行了X-射线衍射、荧光光谱和热释光谱的测试。荧光光谱分析得出在1000℃合成溴氧化镧基质在350nm到500nm存在两个宽带发射,通过与LaOF、LaOCl的荧光光谱和热释光谱对比,得出溴氧化镧基质的发光归结于溴的缺陷,通过计算发现两种不同类型的缺陷能级分别为0.74eV,0.70eV。     

Adsorption of oxygen on copper and silver

Oxygen adsorption on silver has been studied using field-emission microscopy. It has been shown that adsorption is an activated process which proceeds on rough planes through the stage of formation of adsorption islands, O_ads. Using a semi-empirical interacting bonds method, the heat of oxygen adsorption has been estimated in a dissociative from on the (111), (100) and (201) planes of silver and on the (111) and (100) planes of copper.

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. , _. (111), (100), (201) (111), (100) .

     

Complexes of copper and silver with tetracyanobiimidazole

We have recently reported the synthesis and properties of a remarkable new ligand 4,4′,5,5′-tetracyano-2,2′-biimidazole (H₂Tcbiim).¹ This acidic ligand readily binds metal ions in its dianionic form and appears to act as a strong pi acceptor. Its use as a quadridentáte bridging ligand allows study of metal-metal interactions through a planar conjugated system and extends earlier work by us² and by Hendrickson and coworkers³ on 2,2′-biimidazole. In this communication we report on the reactions of H₂Tcbiim with Ag(I), Cu(I) and Cu(II) salts.