金属镍掺杂g-C3N4的制备及其光降解性能

采用浸渍法制备不同掺杂量的负载型光催化剂Ni/g-C3N4,并考察其在可见光照下对亚甲基蓝的光降解性能.利用XRD、FT-IR、SEM、TEM、XPS、N2-sorption和ICP-OES等手段表征Ni/g-C3N4样品.研究表明,Ni/g-C3N4催化剂的光催化活性随着金属镍粒子掺杂量的增加而增大,随着亚甲基蓝浓度的增大而减小,其中金属镍掺杂量4.0wt;的样品4-Ni/g-C3N4表现出优异的光催化活性和光降解稳定性.这是由于4-Ni/g-C3N4样品的光降解过程中产生了超氧自由基、羟基自由基和空穴等活性物质,其中超氧自由基起主导作用.金属Ni0离子在光生电子作用下生成Ni2+,O2分子得到电子生成O2·-自由基.这些活性物质的产生有助于光生电子-空穴对的分离和抑制其复合速率,从而实现可见光下高效催化降解亚甲基蓝.     

混合阴离子磷酸盐RbCd6(P2O7)2P3O10的热学与光学特性研究

利用高温固态反应技术合成了一种新型磷酸盐RbCd6(P2 O7)2 P3O10,并用高温熔盐法自发结晶获得了其单晶.X射线单晶衍射分析表明,该物质结构中含有两种孤立的聚阴离子:P2O7二聚体与P3O10三聚体.两种不同的聚阴离子基元共存于一种结构中,在磷酸盐体系中很少见.这一发现不仅丰富了磷酸盐的结构化学,而且为混合阴离子材料的设计提供了新视角.此外,对该物质的热稳定性及光学性能进行了表征.     

Au3Ag合金的快速凝固及晶体生长过程的分子动力学模拟

采用常温、常压分子动力学模拟技术,研究了液态Au3Ag合金在不同冷却条件下形成晶体及非晶的过程.模型采用EAM作用势,计算了不同温度,不同冷却条件下的偶分布函数及非晶转变温度;分析了不同冷却条件下体系的相变热力学及动力学过程;最后采用液固两层构型法,描述了晶体的生长过程.     

WO3（001）极性表面及氢吸附特性的第一性原理研究

采用基于密度泛函理论的第一性原理方法对WO3 (001)的极性表面及其氢吸附特性进行了理论计算.通过对比WO表面和纯氧表面的表面化学势研究了两个极性表面的热力学稳定性,并分别计算了表面的几何结构和电子结构.结果表明:在贫氧环境中WO表面比较稳定,而在富氧环境中纯氧表面更稳定,WO表面和纯氧表面分别呈现n型半导体和p型半导体特性,表面原子通过调整W-O键长和键角实现表面弛豫.氢原子在两个极性表面不同吸附位置的计算表明:对WO表面和纯氧表面,W5c位和O1c位分别是稳定的吸附位置,且两者具有不同的反应特性.     

红外飞秒激光诱导Ce3+掺杂闪烁晶体的上转换发光研究

本文研究了红外飞秒激光照射下Ce3+ 掺杂的YAP和LSO两种闪烁晶体的上转换发光现象.实验发现在飞秒激光泵浦下,这两种晶体的荧光均来自于Ce3+离子的5d-4f跃迁.荧光强度与泵浦光功率之间的依赖关系揭示了Ce3+:YAP和Ce3+:LSO晶体的上转换过程皆由三光子吸收过程所主导.分析表明,Ce3+:YAP和Ce3+:LSO晶体中的三光子吸收是三光子同时吸收.     

Ag3PO4/GO复合材料制备及其光催化性能研究

采用原位沉淀法以GO为基体负载Ag3PO4纳米颗粒制备Ag3PO4/GO复合材料,利用扫描电镜(SEM)、X射线衍射(XRD)等方法对其进行表征,结果显示,Ag3PO4纳米颗粒呈现近似球状,巨在GO薄膜表面均匀分布.光催化降解RhB结果表明,Ag3PO4/GO复合材料在可见光下具有很好的光催化性能,光照60 min后,RhB降解率可达95.7;,较之纯Ag3PO4有着显著增加.催化剂重复使用4次,降解率仍然达到80.7;,表现出较好的稳定性.降解机理研究表明,h+是降解RhB的主要活性物质.     

LiB3O5晶体946nm,473nm倍频增透膜的研制

采用离子辅助沉积技术在LiB3O5晶体上制备了946nm,473nm倍频增透膜,并测量了薄膜的性质.测试结果表明, 该增透膜具有较低的剩余反射、高的环境稳定性和良好的附着力.进一步测量了薄膜在波长1064nm多脉冲辐照下的激光损伤阈值,获得了两种不同的损伤形貌,并对损伤原因作了初步的探讨.此工艺下镀制的LiB3O5晶体用于瓦级全固态蓝光激光器,获得了3.8W波长为473nm的连续蓝光输出.     

Cr3+掺杂Al2O3-YAG共晶的生长及光谱性能研究

采用光学浮区法成功地生长出了质量良好的共晶.通过XRD分析,确认了共晶组成中仅含有Al2O3和YAG两种晶相,发现随着Cr的掺入,两相的晶胞参数相对于纯单晶略有增大.通过SEM观察发现共晶组织中两种晶相无序交错排布,共晶间距约10 μm左右.测量了室温下掺Cr共晶的吸收光谱、激发光谱和发射光谱.在402nm和556nm的激发波长下,共晶的发射谱均表现出了较好的R线发射,并在掺杂浓度达到0.4 wt;时达到极大值.其激发谱与吸收谱峰位基本一致,说明从激发态向基态跃迁时,发生无辐射跃迁的概率很小.通过与两种单晶的光谱的对比,确认进入Al2O3中八面体的Cr3+在共晶的光谱性质中起主要作用.     

立方晶系Ca2Si声子色散和热力学性质的第一性原理计算

采用模守恒贋势和超软贋势两种方法分别计算立方晶系Ca2Si的声子色散关系、声子态密度和热力学特性.运用线性响应方法和有限位移方法确定立方晶系Ca2Si的声子色散关系和声子态密度,得到立方晶系Ca2Si的声子振动模式是各向异性,且立方晶系的Ca2Si是不稳定结构.在声子色散关系确定的基础上分别计算定容热容、焓、熵和自由能随温度的变化关系,得到Cv-T曲线在低温条件下符合德拜第三定律;当T=1000K时,立方晶系Ca2Si的热熔Cr=21J·mol-1 ·K-1;在高温条件下,随着温度的增加Cv→3R.通过分析声子色散、振动关系和热力学特性得到立方晶系Ca2Si的振动系统由声子和电子组成.     

LaBr3∶Ce晶体中包裹体的性质及成因探究

LaBr3∶Ce单晶拥有优良的闪烁性能,但是,一些微缺陷(例如包裹体)经常出现在晶体中,这种包裹体对晶体的闪烁性能有一定的不利影响.通过Bridgman垂直下降法生长得到LaBr3∶Ce晶体,发现包裹体主要出现在晶体生长的尾部,偏光显微镜下显示存在两种包裹体,一是气孔,二是固体颗粒.X射线衍射、差热分析和拉曼光谱分别测试了含有包裹体和不含包裹体的晶体样品,然而没有发现不同于LaBr3∶Ce基体的成分.因此,推测包裹体是结构和组分与基体几乎完全相同的物质组成,根据测试结果,包裹体的形成可以用组分过冷理论来解释.     

The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

An X-ray structure analysis of three trimethylarsine-boron trihalide adducts has been undertaken. Crystals of (CH₃)₃AsBCl₃ and (CH₃)₃AsBBr₃ are monoclinic with space groupP2₁/m (No. 11) withZ=2 while those of (CH₃)₃AsBI₃ are orthorhombic with space groupPnma (No. 62) withZ=4. For (CH₃)₃AsBCl₃,a=6.497(3) Å,b=10.735(3) Å,c=7.070(2) Å,=111.8(3)°,V=458.4(3) ų,R=0.0343. For (CH₃)₃AsBBr₃,a=6.672(4) Å,b=11.135(7) Å,c=7.199(4) Å,=111.5(1)°,V=497.7(5) ų,R=0.0434. For (CH₃)₃ÅsBI₃,a=13.113(7) Å,b=11.733(5) Å,c=7.387(3) Å,V=1136.5(5) ų,R=0.0329. The As-B bond lengths are 2.065(6), 2.04(1), and 2.03(1) Å, respectively, for the chloride, bromide, and iodide. These and other structural parameters are discussed with reference to previous predictions based on vibrational spectra and previous structural studies on the trimethyl-phosphine and trimethylamine adducts.     

Crystal and molecular structures of three trimethylamine-boron halide adducts: (CH3)3NBCl3, (CH3)3NBBr3, and (CH3)3NBI3

X-ray diffraction data from single crystals of the trimethylamine complexes of the three boron halides, BCl₃, BBr₃, and BI₃, lead to aP2₁/m monoclinic cell containing two molecules for each complex. The unit cell dimensions area = 6·68(1),b = 10·247(3),c = 6·502(6) Å, =116·2(1)° (chloro);a = 6·86(1),b = 10·612(4),c = 6·737(6) Å, = 115·8(1)° (bromo);a = 6·92(2),b = 10·86(1),c = 7·147(6) Å, = 93·9(1)° (iodo). The structures were solved by three-dimensional sharpened Patterson functions and show only the chloro and bromo compounds to be isomorphous. Refinement of 662,718 and 954 observed reflexions for the chloro, bromo and iodo complexes, respectively, using anisotropic thermal parameters yielded conventionalR factors of 0·045, 0·087 and 0·054.The molecules are shown to possess a B—N dative bond, a staggered conformation, and effective 3m (C _3v) symmetry. Average C—N bond lengths are 1·52(1) Å for all three complexes. Boronhalogen bond lengths average 1·864(4), 2·04(2) and 2·28(2) Å, while B—N bond distances are 1·609(6), 1·60(2) and 1·58(3) Å, respectively, for the chloro through iodo compounds. Bond angles are approximately tetrahedral with the C—N—C angle decreasing by several degrees in the Cl Br I series.Based in part on a dissertation submitted by Patty H. Clippard to the Rackham School of Graduate Studies of the University of Michigan, January 1969 in partial fulfillment of the requirements of the Ph.D. Degree.     

Second harmonic generation properties of Ca3(O3C3N3)2 ‐Sr3(O3C3N3)2 solid solutions

Solid solutions of the second harmonic generation (SHG) materials Ca₃(O₃C₃N₃)₂ (CCY) and Sr₃(O₃C₃N₃)₂ (SCY) were prepared via exothermic solid state metathesis reactions from appropriate amounts of the corresponding metal chlorides and potassium cyanate at 525 °C. The change in SHG intensity caused by the successive cation substitution is reported. Differential thermal analyses are used to explore the SCY–K(OCN) phase diagram as a medium for the growth of SCY crystals.     

Crystal Growth and Spectroscopic Characterisation of BiB3O6:RE3+ (RE3+ = Pr3+, Nd3+, Gd3+, Er3+, Tm3+)

Large single crystals of optical quality of BiB₃O₆:RE³⁺ (RE³⁺ = Pr³⁺, Nd³⁺, Gd³⁺, Er³⁺, Tm³⁺) were grown from nearly stoichiometric melts using the top‐seeding growth technique to dimensions up to 12 x 12 x 18 mm³. Absorption spectra were measured in the wavelength range from 10000 cm^‐1 to 30000 cm^‐1 with an absorption spectrometer to estimate the doping concentration of RE³⁺. For the determination of the phonon energies and the quenching behaviour of the host lattice IR and Raman spectra were recorded.     

Growth and characteristic of Sr3Tb(BO3)3 crystal

A new borate single crystal of Sr₃Tb(BO₃)₃ with dimension Ф20×25 mm² has been grown by the Czochralski method. The grown crystal was characterized by DTA–TGA, FTIR and X-ray powder diffraction analysis. The results showed the crystal with [BO₃]^3? is congruently melting at 1351.35 °C which belongs to hexagonal structure. The hardness of Sr₃Tb(BO₃)₃ crystal is 422.5 VDH, and is equal to 5.0 moh. The thermal expansion coefficients were determined to be 2.08×10^?5/°C along (1 0 0) direction and 7.43×10^?6/°C along (0 0 1) direction and the transmission spectrum was measured in 320–1800 nm at room temperature. The magnetic properties of the single crystal were studied which showed its paramagnetism and magnetic anisotropy. The specific Faraday rotation of single crystal was measured at room temperature in 532, 633, and 1064 nm wavelength. The Verdet constants and magneto-optical figures of merit were investigated. The primary emphasis is laid to explore a new magneto-optical material, all the magneto-optical properties of Sr₃Tb(BO₃)₃ are comparing to the ones of TGG.     

Growth and magnetic‐optical properties of Sr3Gd(BO3)3 and Sr3TbxGd1‐x(BO3)3 single crystals

Single crystals of Sr₃Gd(BO₃)₃ (SGB) and Sr₃Tb_xGd_1‐x(BO₃)₃ (TSGB) with dimension Ø 20 mm×20 mm have been grown by Czochralski method. The grown crystals were characterized by X‐ray powder diffraction analysis which showed the crystals belong to hexagonal structure with lattice parameters of a=b=1.254 nm, c=0.926 nm (SGB) and a=b=1.253 nm, c=0.925 nm (TSGB). In TSGB, x=17.7% was obtained by X‐ray fluorometry which showed the segregation coefficient of Tb is closed to 1. The transmission spectrum was measured, which indicated the crystals have high transmittance in 400‐1100 nm region. The Faraday rotation of single crystals at 532 nm wavelength was measured at room temperature. Finally, the Verdet constants were investigated, (SGB) V=17.9 degcm^‐1T^‐1 and (TSGB) V=21.3 degcm^‐1T^‐1. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

3-Methyl-3a,4-Dihydro-3H-Thiochromeno[4,3-c]isoxazol

Abstract  The crystal structure of the title compound, C₁₁H₁₁NOS, was determined by an X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P2₁/c with cell parameters a = 10.533(2) ?, b = 12.7826(19) ?, c = 7.6491(17) ?, β = 107.997(17)^°, V = 979.5(3) ?³ and Z = 4. The S containing heterocycle adopts a sofa conformation, whereas the 5-membered ring adopts an envelope conformation. The crystal packing is characterized by weak C–H···N contacts and π-stacking interactions. Graphical Abstract  The title compound, 3-methyl-3a,4-dihydro-3H-thiochromeno[4,3-c]isoxazol was synthesized by an 1,3 dipolar cycloaddition reaction and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that the aromatic 6-membered ring is planar, whereas the ring containing the S atom adopts a sofa conformation and the 5-membered ring an envelope conformation. The methyl group is in an equatorial position.      

Second harmonic generation in Na3Gd2(BO3)3 crystals

Na₃Gd₂(BO₃)₃ crystals with dimensions up to 22 × 20 × 5 mm³has been grown from NaBO₂ flux by the top‐seeded solution growth (TSSG) method for the first time. Differential scanning calorimetry (DSC) result shows that Na₃Gd₂(BO₃)₃ melts incongruently. The infrared spectrum indicates that Na₃Gd₂(BO₃)₃ contains characteristic triangular [BO₃]^3– groups responsible for the nonlinear optical effect. For the as‐grown crystal, the transmittance exceeds 80% in the wavelength range of 315 nm to 2670 nm, and the UV cutoff wavelength is 207 nm. The damage threshold is 0.47 GW cm^–2 at 1064 nm. Moreover, Na₃Gd₂(BO₃)₃ crystal exhibits an optical second harmonic generation effect which is 1.3 times as large as that of KH₂PO₄ (KDP). (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)