乙醇与水协同修饰Bi2WO6纳米片形貌及改善其光致发光性

通过控制前驱体中乙醇与水的体积比,采用溶剂热法得到不同形貌的Bi2WO6纳米片,探讨了Bi2WO6形貌与光致发光性能之间的关系。Bi2WO6的结晶度、纳米片的棱长以及片层间距随醇水比增大而逐渐提高,当醇水比为1∶1时,Bi2WO6纳米片的棱长、片层间距和比表面积（BET）最大,表现出优异的光致发光性能;而在醇水比大于1∶1时,纳米片的棱长、片层间距和BET随之降低,光致发光性能继而减弱。以上表明醇水比为1∶1时,复配乙醇与水协同修饰Bi2WO6纳米片形貌的效果最佳,BET最大,从而促进其光致发光性能的改善。     

Bi2WO6纳米晶的制备、表征及光催化性能

以硝酸铋、钨酸钠等为原料,利用水热法在150℃下反应24h得到Bi2WO6纳米晶。X射线粉末衍射结果表明,所制备的Bi2WO6属于正交晶系,晶胞参数为a=5.457,b=16.435及c=5.438。XPS结果表明所制造的Bi2WO6纯度较高。研究了分别以水、N,N-二甲基甲酰胺、乙二醇为溶剂时所制备Bi2WO6样品在可见光激发下对罗丹明B的降解活性,结果表明,以乙二醇为溶剂时,Bi2WO6光催化活性最佳,主要是由于在乙二醇中制备的Bi2WO6分散性好,粒径小,对紫外-可见光具有较大波长范围的吸收所致。另外,研究了以水为溶剂时溶液pH及添加表面活性剂等对所制备Bi2WO6光催化活性的影响,结果表明,反应温度为140～150℃,pH在1.0附近及添加SDS后所制备Bi2WO6光催化活性较佳。荧光光谱分析发现,添加表面活性剂的样品发射荧光的强度较弱,表明载流子复合程度低,因而光催化效率高。     

单层与双层WSe2纳米片层的光致发光

采用气相沉积法制备了WSe₂二维纳米材料,对其低温光致发光谱进行了研究。结果表明：随着WSe₂层数的增加,其光致发光强度单调下降;当WSe₂层数从单层增加为双层时,其发光强度急剧下降,表明其能带结构已从直接带隙转变为间接带隙。进一步研究了双层WSe₂的变温光致发光谱,发现随着温度的升高,双层WSe₂发光峰中A峰峰位的变化基本符合半导体带隙的温度变化规律,而I峰峰位红移与温度基本成线性关系,表明双层WSe₂同时存在间接和直接跃迁,且直接跃迁和间接跃迁特性不同。     

NiFe_2O_4纳米粉末的制备及磁性研究

以硝酸铁、硝酸镍以及柠檬酸为原料,采用凝胶-热分解法制备了N iFe2O4纳米粉末。利用X射线衍射确定了粉体的相结构、比表面积和晶格常数,扫描电子显微镜(SEM)观察了颗粒的形貌,振动样品磁强计(VSM)测量样品的磁性能。结果表明:所制备的样品均为尖晶石结构,颗粒粒径为36nm~68nm,且颗粒的粒径随着热处理温度的升高而增大,样品的比饱和磁化强度最大可达54.63 emu/g。同时,文章也对反应的动力学原理进行了研究,得出N iFe2O4纳米颗粒形成的活化能为15.8kJ/mol。     

Gd2O3:Eu3+纳米晶的燃烧合成及光致发光性质

采用柠檬酸作燃烧剂用燃烧合成法制备了Gd2O3:Eu3+纳米晶.用X射线衍射仪(XRD)、高分辨透射电子显微镜(HRTEM)和荧光分光光度计等对Gd2O3:Eu3+纳米晶的结构、形貌和发光性能进行了分析.结果表明:不同柠檬酸与稀土离子配比(C/M)制备的样品经800℃退火1 h后,均得到了纯立方相的Gd2O3:Eu3+纳米晶,晶粒尺寸约为30 nm,尺寸分布较窄,其中以C/M=1.0时制备的纳米晶结晶性最好,发光强度最大.Gd2O3:Eu3+纳米晶主发射峰位置均在612 nm处(5D0→7F2跃迁),激发光谱中电荷迁移态发生红移,观察到Gd3+向Eu3+的有效能量传递.对柠檬酸与稀土离子配比(C/M)对结晶度、发光性质等的影响也进行了分析和讨论.     

Gd_2O_3∶Er/Yb纳米线、纳米片的制备与发光性质

采用水热法制备了Gd2O3∶Yb3 /Er3 纳米线和纳米片,并研究了制备过程中溶液的pH值对产物形貌的影响以及样品形貌对发光性质的影响。将稀土氧化物溶于硝酸并与NaOH反应,使溶液pH值至预期值,将生成物离心、烘干和灼烧,得到最终产物。研究发现,制备样品过程中,中性溶液中易于形成纳米片,而碱性溶液中则会形成纳米线,而且碱性越强越容易形成纳米线。在980nm激光激发下,与纳米片相比,纳米线中Er3 的4I13/2→4I15/2的红外发射强度显著减弱,而2H11/2/4S3/2→4I15/2和4F9/2→4I15/2的上转换发射相对增强,而且2H11/2/4S3/2→4I15/2与4F9/2→4I15/2的荧光分支比略有增大。纳米线与纳米片相比,比表面积减小,由表面效应引起的无辐射弛豫过程的减弱导致了上述光谱的变化。     

Gd2O3：Er/Yb纳米线、纳米片的制备与发光性质

采用水热法制备了Gd₂O₃:Yb³⁺/Er³⁺纳米线和纳米片,并研究了制备过程中溶液的pH值对产物形貌的影响以及样品形貌对发光性质的影响。将稀土氧化物溶于硝酸并与NaOH反应,使溶液pH值至预期值,将生成物离心、烘干和灼烧,得到最终产物。研究发现,制备样品过程中,中性溶液中易于形成纳米片,而碱性溶液中则会形成纳米线,而且碱性越强越容易形成纳米线。在980nm激光激发下,与纳米片相比,纳米线中Er³⁺的⁴I_13/2→⁴I_15/2的红外发射强度显著减弱,而²H_11/2/⁴S_3/2→⁴I_15/2和⁴F_9/2→⁴I_15/2的上转换发射相对增强,而且²H_11/2/⁴S_3/2→⁴I_15/2与⁴F_9/2→⁴I_15/2的荧光分支比略有增大。纳米线与纳米片相比,比表面积减小,由表面效应引起的无辐射弛豫过程的减弱导致了上述光谱的变化。     

SiO2纳米线簇、C-Si-O纳米球的制备及形貌、红外光谱和光致发光光谱研究

以二茂铁和硅油作为催化剂和原料,利用高温裂解硅油为C,Si,O源,在常压N₂和H₂混合气氛的化学气相沉积管式炉中制备了大量直径为5—40 nm、长数百纳米的非晶SiO₂纳米线簇及粒径为100—300 nm的C-Si-O实心纳米球. 利用透射电子显微镜、扫描电子显微镜对产物形貌进行表征.Fourier红外吸收谱显示出非晶SiO₂所具有的474,802和1100 cm^-1三个特征峰;SiO₂纳米线簇的光致发光光谱具有较强440 nm蓝光发光峰;而C-Si-O（原子数之比为1.13∶1∶2.35）纳米球具有奇特的红绿蓝（625,540,466 nm）三色光致发光谱. 关键词： 2纳米线簇')" href="#">SiO₂纳米线簇 C-Si-O纳米球 高温裂解 Fourier红外谱     

基于银纳米三角片与罗丹明6G的荧光共振能量转移法检测钴离子

以罗丹明6G和牛血清白蛋白的复合物为荧光探针,银纳米三角片为猝灭剂,研究了银纳米三角片与荧光复合物的荧光共振能量转移现象,建立了测定钴离子的荧光分析法。研究发现,一定浓度的荧光复合物与银纳米三角片混合后,由于荧光复合物在银纳米三角片上吸附而发生荧光共振能量转移,荧光猝灭达到80%左右。当钴离子存在时,银纳米三角片与罗丹明6G荧光共振能量转移被破坏,荧光逐渐恢复。随着钴离子浓度的增加,体系荧光值的恢复率(I/I₀)与钴离子的浓度(c_Co2+)有良好的线性关系,线性回归方程为I/I₀=1.054+21.72 c_Co2+,相关系数r2为0.996 2。通过对自然水样进行加标回收检测,实现了钴离子的定量检测,回收率在90.4%～115.1%之间。建立了一种可靠的选择性检测钴离子的荧光分析方法。     

Gd2O3:Eu3+纳米晶的燃烧合成及光致发光性质

采用柠檬酸作燃烧剂用燃烧合成法制备了Gd₂O₃:Eu³⁺纳米晶.用X射线衍射仪(XRD)、高分辨透射电子显微镜(HRTEM)和荧光分光光度计等对Gd₂O₃:Eu³⁺纳米晶的结构、形貌和发光性能进行了分析.结果表明：不同柠檬酸与稀土离子配比(C/M)制备的样品经800℃ 退火1 h后，均得到了纯立方相的Gd₂O₃:Eu³⁺纳米晶，晶粒尺寸约为30 nm，尺寸分布较窄，其中以C/M=1.0时制备的纳米晶结晶性最好，发光强度最大.Gd₂O₃:Eu³⁺纳米晶主发射峰位置均在612 nm处 (⁵D₀→⁷F₂跃迁)，激发光谱中电荷迁移态发生红移，观察到Gd³⁺向Eu³⁺的有效能量传递.对柠檬酸与稀土离子配比(C/M)对结晶度、发光性质等的影响也进行了分析和讨论.     

Temperature-dependent Raman scattering study of cation-deficient Aurivillius phases: Bi2WO6 and Bi2W2O9

Temperature-dependent Raman scattering experiments were performed on Bi(2)WO(6) and Bi(2)W(2)O(9). Significant changes in the phonon properties of Bi(2)WO(6) were observed as the temperature was increased due to decreased distortion from the B2cb structure. It was shown that instability of the 57 cm(-1) mode that behaved as a soft mode under pressure is not responsible for the Pca2(1) to B2cb phase transition taking place in Bi(2)WO(6) at 933 K. This result confirmed that this mode is not related to the [Formula: see text] tilt mode, which disappears upon change in symmetry from Pca2(1) to B2cb. Bi(2)W(2)O(9) does not exhibit any structural phase transition in the 298-800 K range. However, the temperature dependence of Raman bands indicated that the Bi(2)W(2)O(9) structure evolves with decreasing temperature from 800 to 298 K towards a more symmetric structure that was reported above 2.8 GPa at room temperature. This structural change is driven by displacement of the W atoms and is different from that exhibited by Bi(2)WO(6) and other members of the Aurivillius family but similar to that exhibited by WO(3). Our results also show that Bi(2)W(2)O(9) belongs to the small group of compounds that show the presence of low wavenumber modes characterized by unusually small linewidths.     

A facile preparation strategy for hollow-structured Bi2O3/Bi2WO6 heterojunction with high visible light photocatalytic activity

A hollow-structured heterojunction consisting of Bi₂WO₆ nanoplatelets and Bi₂O₃ nanoparticles was successfully prepared by a facile solvothermal process. Bi₂O₃/Bi₂WO₆ heterojunction is the aggregate of some hollow spheres with diameter ranging from several hundred nanometers to 1.5 μm and is connected to each other by tube-like cavums. On the basis of scanning and transmission electron microscopy observation and X-ray diffraction analysis of the samples synthesized at different reaction stages, a possible growth mechanism was proposed for the growth of hollow-structured Bi₂O₃/Bi₂WO₆ heterojunction. Its photocatalytic activity was evaluated by degradation of rhodamine B under visible-light irradiation (λ>400 nm). The results indicate that the hollow-structured Bi₂O₃/Bi₂WO₆ heterojunction exhibits much higher photocatalytic activity than both pure Bi₂WO₆ and pure Bi₂O₃. The improved photocatalytic performance can be ascribed to the heterojunction of Bi₂O₃ and Bi₂WO₆ in the framework in which the hierarchical hollow structure possesses good permeability and large surface area. More importantly, the hollow-structured Bi₂O₃/Bi₂WO₆ heterojunction is not only highly stable but also easy to be separated by simple sedimentation for recycle.     

Thermostimulated Luminescence of PbWO4, Bi2WO6, and Y2WO6 Ceramics

Thermostimulated luminescence (TSL) of PbWO₄, Bi₂WO₆, and Y₂WO₆ ceramics on x-ray excitation is investigated. The spectral luminosity of the thermostimulated luminescence is analyzed. The thermal activation energies conforming to the corresponding thermostimulated luminescence peaks are determined. It is established that on emptying trapping centers radiative recombination occurs at the intrinsic-luminescence centers associated with tungsten-oxygen complexes WO₄ ^2–.     

Edge assisted epitaxy of CsPbBr3 nanoplates on Bi2O2Se nanosheets for enhanced photoresponse

Bi$_{2}$O$_{2}$Se has been proved to be a promising candidate for electronic and optoelectronic devices due to their unique physical properties. However, it is still a great challenge to construct the heterostructures with direct epitaxy of hetero semiconductor materials on Bi$_{2}$O$_{2}$Se nanosheets. Here, a two-step chemical vapor deposition (CVD) route was used to directly grow the CsPbBr$_{3}$ nanoplate-Bi$_{2}$O$_{2}$Se nanosheet heterostructures. The CsPbBr$_{3}$ nanoplates were selectively grown on the Bi$_{2}$O$_{2}$Se nanosheet along the edges, where the dangling bonds provide the nucleation sites. The epitaxial relationships between CsPbBr$_{3}$ and Bi$_{2}$O$_{2}$Se were determined as ${[200]}_{\rm Bi_{2}O_{2}Se}||{[110]}_{\rm CsPbBr_{3}}$ and ${[110]}_{\rm Bi_{2}O_{2}Se}||{[200]}_{\rm CsPbBr_{3}}$ by transmission electron microscopy characterization. The photoluminescence (PL) results reveal that the formation of heterostructures results in the remarkable PL quenching due to the type-I band arrangement at CsPbBr$_{3}$/Bi$_{2}$O$_{2}$Se interface, which was confirmed by ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe measurements, and makes the photogenerated carriers transfer from CsPbBr$_{3}$ to Bi$_{2}$O$_{2}$Se. Importantly, the photodetectors based on the heterostructures exhibit a 4-time increase in the responsivity compared to those based on the pristine Bi$_{2}$O$_{2}$Se sheets, and the fast rise and decay time in microsecond. These results indicate that the direct epitaxy of the CsPbBr$_{3}$ plates on the Bi$_{2}$O$_{2}$Se sheet may improve the optoelectronic performance of Bi$_{2}$O$_{2}$Se based devices.     

Structural and thermochemical properties of methyl ethyl sulfide alcohols: HOCH2SCH2CH3, CH3SCH(OH)CH3, CH3SCH2CH2OH,and radicals corresponding to loss of H atom

Sulfide alkoxy radicals are important intermediates during the partial oxidation of alkyl sulfides in atmospheric chemistry and in combustion. The atmospheric reaction sequence to formation of the alkoxy radicals includes (1) initial reaction with OH to create a radical on a carbon site, (2) the carbon radical then associates with ³O₂ to form a peroxy radical, and (3) an NO radical reacts with the peroxy radical to form an alkoxy radical (RO?) plus NO₂. This study determines structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (Δ_fH°, S°, and C_p(T)) of 3 corresponding alcohols HOCH₂SCH₂CH₃, CH₃SCH(OH)CH₃, and CH₃SCH₂CH₂OH of methyl ethyl sulfides studied in order to characterize the thermochemistry of the respective alkoxy radicals. The lowest energy molecular structures were calculated using the B3LYP density functional level of theory with the 6‐311G(2d,d,p) basis set. Standard enthalpies of formation (Δ_fH°₂₉₈) for the radicals and their parent molecules were calculated using B3LYP/6‐31 + G(2d,p), CBS‐QB3, M062x/6‐311 + g(2d,p), and G3MP2B3 methods. Isodesmic reactions were used to determine ?_fH° values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31 + G(d,p) level theory. The contributions for S°₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by CBS‐QB3 calculations, with contributions from torsion frequencies replaced by internal rotor contributions. Group additivity and hydrogen bond increment values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxide molecules and their radicals.     

WO3 oxide film formation on tungsten in O2/H2 discharges

The features of tungsten oxidation in a flowing O₂ or O₂/H₂ mixture glow discharge with a hollow cathode are investigated in the cathode, plasma, and afterglow regions at T = 300–350 K. The structure and composition of the samples are analyzed via reflection high-energy electron diffraction, reflection X-ray diffraction, electron probe microanalysis, and X-ray photoelectron spectroscopy. The results of analysis show that the metal surface is covered by a thin film (5–10 nm thick) of amorphous porous hydrated tungsten oxide (WO₃) after its exposure to the discharge and storage in air. The study of the film composition using a time-of-flight mass spectrometer indicates that the WO₃ film contains (WO₃) _n (n = 1–6) clusters and water molecules adsorbed in the pores. After exposure of the polycrystals to the O₂/H₂ discharge, the selective intense oxidation of individual grains is detected in the cathode region; the surrounding areas are subjected to weaker oxidation. The thicknesses of the WO₃ films on neighbouring grains differ by more than tenfold. Such grains can be the source of tungsten dust in plasma installations.