溶剂热合成纳米材料技术及其进展

较系统地概述了溶剂热法制备纳米材料的技术方法、原理和溶剂选择.详细介绍了该技术的特点和研究进展,认为溶剂热法是一种极有应用前景的纳米材料的制备方法.     

类石墨烯硫族化合物纳米材料及其在能源领域中的应用

2004年以来,以石墨烯为代表的新型二维纳米材料引起了全球范围内的研究热潮,在光电子、生物、能源等领域展现出了巨大的应用潜力。过渡金属硫族化合物因平面内结合力较强、平面外结合力较弱以致可以将其剥离成单个细胞厚度的二维层状纳米材料,且该材料具备类石墨烯物理化学性质而被誉为"无机石墨烯"。关于二维过渡金属硫族化合物纳米材料的研究已有多年,众多研究表明,因其具有独特的结构和特性,在光电器件、催化及能源存储领域有着广阔的应用前景。基于该领域研究的最新进展,综述了二维过渡金属硫族化合物纳米材料在能源领域中的应用,并对目前相关研究领域的发展趋势进行了总结和展望。     

热注入法制备CuIn(Se,S)_2纳米材料的研究进展

介绍了CuIn(Se,S)2纳米材料的晶体结构和性质,以及热注入法的原理和特点。重点论述了近年来国内外采用热注入法制备不同形貌和结构CuIn(Se,S)2纳米材料的研究进展,概括了其反应机理和影响因素。综述了CuIn(Se,S)2纳米材料在太阳能电池、QD-LED及生物标记上的应用。探讨了目前存在的问题及今后的研究方向。     

MSn (M＝ Fe,Cd,Zn)微纳米结构材料的溶剂热合成与表征

以单质硫粉为硫源,乙醇为溶剂,在不添加任何络合剂和表面活性剂的条件下使之与MCln(M=Fe、Cd、Zn,n=2,3)金属盐发生溶剂热反应并成功制备了MS (M=Fe、Cd、Zn,n=1,2)微纳米结构材料.并用XRD、SEM对所得产物进行一系列的表征,研究和讨论了反应温度、反应时间、尤其是溶剂对所得产物的形貌和纯度等...     

Zn(C7H7N2O4)2制备及其吸附脱硫性能研究

经过酯交换、水解两步反应制备了有机配体1,3-二乙酸咪唑.利用溶剂热法以硝酸锌为金属源制备了金属-有机框架材料Zn(C7H7N2O4)2,并对其进行了温度优化、时间优化以及反应物比例优化,采用了X射线衍射(XRD)对其进行了表征分析.同时采用以苯并噻吩为模型化合物,在相同条件下进行吸附脱硫效果评价.实验结果表明:M-2/T-120/t-72显示出最佳的吸附脱硫性能.     

有机溶剂热生长晶体及其应用

介绍了有机溶剂热生长技术在金属碲,硒多聚物合成中的应用,并讨论了这类化俣物的结构特征,及其在制备纳米级半导体薄膜,催化剂载体和离子交换材料方面的应用前景。     

[Mn(en)3]2·Sn2Se4Te2的结构和光吸收性能

按照K2Se:K2Te2:MnCl2@4H2O:SnCl2 2H2O:Se:乙二胺(en)＝3.8:1:2:2:6:270的摩尔比配料,采用溶剂热法使原料混合物在180℃反应7 d,得到黑色块状晶体[Mn(en)3]2@Sn2Se4Te2.属于三斜晶系,空间群为P-1,晶胞参数a＝0.91428(7)nm,b＝1.02781(7)nm,c＝1.15745(8)nm,α＝94.632(2)°,β＝100.944(2)°,γ＝115.918(1)°,V＝0.94382(12)nm3,Z＝1.晶体由[Mn(en)3]2+和(Sn2Se4Te2)4-堆积而成.具有Zintl结构的特征半导体[Mn(en)3]2@Sn2Se4Te2的光学能隙(Eg)为2.2 eV.当温度低于190℃时,[Mn(en)3]2@Sn2Se4Te2晶体是稳定的.详细讨论了这类化合物的组成对晶体结构和光吸收性能的影响.     

Zn_(1-x)Mn_xS稀磁半导体的水热法制备及其性能

以乙二胺为修饰剂,采用水热法合成了不同掺杂比例的Zn_(1-x)Mn_xS(x=0,0.02,0.05,0.07)稀磁半导体材料,并通过XRD、FESEM、HRTEM、XEDS、光致发光光谱(PL)和振动样品磁强计(VSM)对样品的晶体结构、形貌、光学性能和磁学性能进行表征。实验结果表明:本方法制备的所有样品具有结晶良好的纤锌矿结构,没有杂峰出现;样品形貌为一维的纳米棒状,分散性良好;掺杂的Mn2+以替代Zn2+的形式进入到ZnS晶格中,随着Mn掺杂量的增加晶格常数呈现收缩趋势;样品的PL光谱存在明显的紫外发光峰、蓝光发光峰和绿光发光峰,而且峰位发生蓝移;同时一定量的Mn掺杂ZnS纳米晶在室温条件下具有铁磁性。     

一维ZnO纳米材料的溶液法合成及光催化性能的研究现状

溶液法合成一维ZnO纳米材料是目前最常用、最经济的方法。综述了溶液法合成一维ZnO纳米材料的流程、原理以及制备工艺对一维ZnO形貌和结构的影响,并对其光催化性能的研究现状及发展趋势进行了总结和展望,为开展溶液法合成一维ZnO纳米材料及性能研究提供一定的指导。     

Fabrication and Characterization of Modulation-Doped ZnSe/(Zn,Cd)Se (110) Quantum Wells: A New System for Spin Coherence Studies

We describe the growth of modulation-doped ZnSe/(Zn,Cd)Se quantum wells on (110) GaAs substrates. Unlike the well-known protocol for the epitaxy of ZnSe-based quantum structures on (001) GaAs, we find that the fabrication of quantum well structures on (110) GaAs requires significantly different growth conditions and sample architecture. We use magnetotransport measurements to confirm the formation of a two-dimensional electron gas in these samples, and then measure transverse electron spin relaxation times using time-resolved Faraday rotation. In contrast to expectations based upon known spin relaxation mechanisms, we find surprisingly little difference between the spin lifetimes in these (110)-oriented samples in comparison with (100)-oriented control samples.     

Electronic band-edge properties of rock salt PbY and SnY (Y= S, Se, and Te)

The electronic band-edges of lead chalcogenides PbY and tin chalcogenides SnY (where Y = S, Se, and Te) are investigated by the means of a full-potential linearized augmented plane wave (FPLAPW) method and the local density approximation (LDA). All six chalcogenide binaries have similar electronic structures and density-of-states, but there are differences in the symmetry of the band-edge states at and near the Brillouin zone L-point. These differences give the characteristic composition, pressure, and temperature dependences of the energy gap in Pb_1−xSn_xY alloys.We find that: (1) SnY are zero-gap semiconductors E_g = 0 if the spin–orbit (SO) interaction is excluded. The reason for this is that the conduction band (CB) and the valence band (VB) cross along the Q ≡ LW line. (2) Including the SO interaction splits this crossing and creates a direct gap along the Q-line, thus away from the L symmetry point. Hence, the fundamental band gap E_g in SnY is induced by the SO interaction and the energy gap is rather small E_g ≈ 0.2–0.3 eV. At the L-point, the CB state has symmetric and the VB state is antisymmetric thereby the L-point pressure coefficient ∂E_g(L)/∂p is a positive quantity. (3) PbY have a direct band gap at the L-point both when SO coupling is excluded and included. In contrast to SnY, the SO interaction decreases the gap energy in PbY. (4) Including the SO interaction, the LDA yields incorrect symmetries of the band-edge states at the L-point; the CB state has and the VB state has symmetry. However, a small increase of the cell volume corrects this LDA failure, producing an antisymmetric CB state and a symmetric VB state, and thereby also yields the characteristic negative pressure coefficient ∂E_g(L)/∂p in agreement with experimental findings. (5) Although PbY and SnY have different band-edge physics at their respective equilibrium lattice constants, the change of the band-edges with respect to cell volume is qualitatively the same for all six chalcogenides. (6) Finally, in the discussion of the symmetry of the band edges, it is important to clearly state the chosen unit cell origin; a shift by (a/2,0,0) changes the labeling of the irreducible representations.     

Fabrication and Characterization of Modulation-Doped ZnSe/(Zn,Cd)Se (110) Quantum Wells: A New System for Spin Coherence Studies

We describe the growth of modulation-doped ZnSe/(Zn,Cd)Se quantum wells on (110) GaAs substrates. Unlike the well-known protocol for the epitaxy of ZnSe-based quantum structures on (001) GaAs, we find that the fabrication of quantum well structures on (110) GaAs requires significantly different growth conditions and sample architecture. We use magnetotransport measurements to confirm the formation of a two-dimensional electron gas in these samples, and then measure transverse electron spin relaxation times using time-resolved Faraday rotation. In contrast to expectations based upon known spin relaxation mechanisms, we find surprisingly little difference between the spin lifetimes in these (110)-oriented samples in comparison with (100)-oriented control samples.     

Optical and EPR spectroscopy of Zn:Cr:ZnSe and Zn:Fe:ZnSe crystals

Optical and EPR characterization of Cr and Fe doped ZnSe crystals annealed in Zn vapor revealed a strong bleaching of the divalent state of transition metal ions. Photo induced EPR kinetics were studied in 20–80 K temperature range. Analysis of time-dependent data reveals Cr¹⁺ signal rise time decreases with increasing temperature. The non-exponential decay of Cr¹⁺ concentration were analyzed using Auger-type recombination process. The photoluminescence quantum yield of Cr²⁺ ions at ⁵E(D) → ⁵T₂(D) mid-IR transition excited via chromium ionization process was measured to be close to 100%.     

A voltammetric and nanogravimetric study of ZnSe electrodeposition from an acid bath containing Zn(II) and Se(IV)

The negative potential sweep of a polycrystalline Au electrode in a solution containing 5 × 10^− 4 mol L^− 1 SeO₂, 0.2 mol L^− 1 Zn(ClO₄)₂ and 0.5 mol L^− 1 HClO₄ was analyzed at 0.05 V s^− 1. The simultaneously collected voltammetric and nanogravimetric responses allowed to analyze the several electrochemical processes occurring in the studied range of potential, finishing with the formation of a thin film of ZnSe. The association of results obtained using both techniques was applied to identify the species involved in the AuO reduction as (AuO)₂H₂SeO₃, which was desorbed during the oxide reduction with a mass variation much larger than that one observed in the supporting electrolyte. Initially, the Se(IV) reduction results in Se_ads coverage, followed by a further reduction to H₂Se, which is a gas and desorbs from the electrode surface. Finally, the Zn(II) reduction inhibits the H₂Se formation and generates a thin film of ZnSe, as the final coating. The strong dependence of the nature of reacting compound and the mass as well as the charge variations allowed to postulate a reaction mechanism.     

Generation of white light from co-doped (Cu and Mn) ZnSe QDs

White light generation is achieved by single-step co-doping of copper and manganese into the robust ZnSe quantum dots (QDs) which were synthesised using a wet chemical route. Photoluminescence (PL) emission spectra revealed three peaks related to blue (ZnSe), green (copper related) and orange (manganese related). The PL spectra indicated no surface and/or trap state related emission. Photoluminescence excitation (PLE) measurements confirmed co-doping of copper and manganese in the same QD. PLE spectra recorded with emission wavelength fixed at copper and manganese showed a band edge at the same position, indicating the incorporation of both copper and manganese in the same QD. Time-resolved PL measurements suggest an atomic like nature of Mn and Cu in ZnSe QDs.     

Optical,Thermal, and Mechanical Characterization of Ga2Se3‐Added GLS Glass

Gallium lanthanum sulfide glass (GLS) has been widely studied in the last 40 years for middle‐infrared applications. In this work, the results of the substitution of selenium for sulphur in GLS glass are described. The samples are prepared via melt‐quench method in an argon‐purged atmosphere. A wide range of compositional substitutions are studied to define the glass‐forming region of the modified material. The complete substitution of Ga₂S₃ by Ga₂Se₃ is achieved by involving new higher quenching rate techniques compared to those containing only sulfides. The samples exhibiting glassy characteristics are further characterized. In particular, the optical and thermal properties of the sample are investigated in order to understand the role of selenium in the formation of the glass. The addition of selenium to GLS glass generally results in a lower glass transition temperature and an extended transmission window. Particularly, the IR edge is found to be extended from about 9 µm for GLS glass to about 15 µm for Se‐added GLS glass defined by the 50% transmission point. Furthermore, the addition of selenium does not affect the UV edge dramatically. The role of selenium is hypothesized in the glass formation to explain these changes.     

In-situ synthesis and characterizations of Bi2(O,S)3/Zn(O,S) composites for visible light hexavalent chromium reduction

Heterojunction construction with low band gap materials is an effective way of utilizing UV light active materials under visible light irradiation. Here, we report the synthesis of Bi₂(O,S)₃/Zn(O,S) heterostructure using simple solvothermal method without surfactant. The catalysts were investigated with different characterization techniques. All the composite catalysts showed high light absorption capacity in the whole visible light spectrum. The catalytic activity of the catalysts was evaluated by Cr(VI) reduction. While pure Zn(O,S) catalyst showed no significant Cr(VI) reduction, higher photocatalytic activity than individual components were exhibited after heterojunction construction with Bi₂(O,S)₃. 20-BiZnOS catalyst with Bi/Zn molar percentage of 20% showed the best photocatalytic activity among the composites with 99.5% Cr(VI) reduction within 12 min under visible light irradiation. Heterojunction formation between Bi₂(O,S)₃ and Zn(O,S) nanoparticle, and selective adsorption of Cr(VI) and desorption of Cr(III) on the surface of 20-BiZnOS composite catalyst were ascribed to the enhanced photocatalytic activity of the composite catalyst.