热处理过程对纳米TiO2结构和性能的影响

以钛酸丁酯为钛源,采用溶胶-凝胶法制备纳米TiO2,结合TG-DTA,XRD,TEM等分析了不同热处理温度对纳米TiO2的晶型结构、晶粒粒径及微观形貌的影响.以甲基橙溶液为目标降解物,探讨了热处理温度对纳米TiO2光催化活性影响.利用Eastman的粒子生长理论对晶粒生长的动力学过程进行初步分析.研究表明:随着热处理温度升高,TiO2粒径逐渐从11.2 nm增大到78.6 nm;热处理温度为450～ 550℃时,纳米TiO2晶粒以锐钛矿为主,温度升至650℃时,出现了锐钛矿和金红石的混合相(质量比A∶R =9∶1),此时晶粒对甲基橙的降解率达到97.75;.而煅烧温度高于850℃后,TiO2几乎完全为金红石相,光催化活性显著下降.50;锐钛矿型TiO2转变金红石型TiO2的温度约为730℃,锐钛矿和金红石相晶粒表观活化能分别18.15 kJ/mol和42.56 kJ/mol;晶粒生长最快温度分别为546℃和1280℃.     

Ce掺杂TiO2纳米粉体的制备及其光催化性能研究

以钛酸丁酯为前驱体,冰醋酸为螫合剂,以硝酸铈为掺杂剂,采用溶胶.凝胶法制备了铈掺杂TiO2纳米粉体.研究了铈掺杂对TiO2相组成和晶粒尺寸的影响及不同掺杂量对TiO2光催化活性的影响,确定了Ce的最佳掺杂量.结果表明:Ce掺杂缩小了TiO2的锐钛矿相→金红石相(A→R)的相变温区范围,抑制了TiO2的晶粒增长.热处理温度升高,二氧化钛的比表面积下降.掺杂适量的铈提高了TiO2的光催化活性,Ce掺杂为0.05;摩尔分数时Ce-TiO2的光催化活性达到最佳,甲基橙降解率可达90;左右.     

乙醇与冰乙酸用量对混晶TiO2光催化性能影响

在溶胶凝胶工艺路线中,选择了不同的乙醇与冰乙酸用量,并对前驱体进行540℃保温2 h的热处理,制备了锐钛矿/金红石混晶TiO2粉体.利用扫描电子显微镜、能谱分析仪、X射线衍射仪等对样品进行了形貌、元素以及相组成的表征;样品粉体的光催化性能由罗丹明B的降解率评价.实验结果表明,样品为混晶结构,乙醇与冰乙酸用量对锐钛矿/金红石的含量有影响;当乙醇用量为90 mL,冰乙酸用量为5 mL时,制得的TiO2粉体光催化效率最高,反应3 h后对罗丹明B的降解率达到83.9;,反应速率常数k值为0.00982 min-1.     

爆轰法合成超小TiO2的光催化性能分析

颗粒尺寸是影响TiO2光催化活性的重要因素,颗粒越小其光催化效率越高.在密闭的反应釜内引爆用含钛前驱体、硝酸铵、黑索金与一定量的聚苯乙烯小球制备的浆状混合炸药制备了超小的TiO2纳米颗粒.研究了炸药配比对TiO2的形貌、分散性、颗粒尺寸的影响,并通过降解甲基橙溶液表征超小TiO2的光催化性能.结果发现:制备的TiO2由金红石相与锐钛矿相组成,大部分颗粒呈球形或不规则四边形,尺寸在10nm左右,少量颗粒尺寸大于20nm,结晶度较好.炸药配比对TiO2的结晶度、颗粒大小、分散性等有较大影响.TiO2的禁带宽度在2.8eV左右,低于锐钛矿相与金红石相的禁带宽度,能够提高太阳光的利用率.爆轰制备的超小TiO2催化降解甲基橙溶液50min时,甲基橙的降解率为30;,明显高于爆轰法制备的颗粒较大的TiO2与铜粒子掺杂的纳米TiO2的光催化速率,光催化性能得到明显提高.     

TiO2/蒙脱石复合物中纳米TiO2的相变与光催化性能

以TiOSO4.2H2O为TiO2的前驱体、蒙脱石为基体,采用水解-插层复合法,在不同热处理温度下制备了系列TiO2/蒙脱石纳米复合样品。采用XRD研究了样品中TiO2物相和晶粒大小等属性的变化,研究了样品对亚甲基蓝溶液的吸附脱色性和光催化脱色性。结果表明,热处理温度对TiO2/蒙脱石中TiO2物相与相对含量、晶粒大小和光催化脱色性等有很大影响。经700℃热处理的TiO2/蒙脱石复合样品锐钛矿晶粒仅为13.7 nm,光催化脱色率高达42.7%,总脱色率达79.8%;经1100℃热处理后,锐钛矿相对含量高达55.7%,锐钛矿晶粒为55.8 nm,光催化脱色率仍为32.5%,总脱色率高达46.6%;TiO2/蒙脱石复合样品中的TiO2与纯纳米TiO2样品相比,具有更高的锐钛矿相向金红石相转变的温度、更小的TiO2晶粒尺寸、更强的光催化脱色性。蒙脱石结构层对TiO2的相转变和晶粒长大具有明显的阻滞作用。     

不同晶型TiO2的制备与光催化性能研究

采用溶胶凝胶法,利用不同温度热处理制备了不同晶体结构的TiO2纳米晶.利用XRD、SEM、EDS、XPS等分析方法对样品的晶体结构、形貌、化学元素组成以及价态进行了表征.结果表明400 ℃、500 ℃热处理TiO2为锐钛矿晶型,600 ℃ 热处理为锐钛矿金红石混合晶型,700 ℃热处理为金红石晶型,单颗粒子呈现类似球形形貌.以罗丹明B为目标污染物,测试了样品的光催化性能,结果表明400 ℃热处理TiO2具有最高的光催化活性,3 h后对罗丹明B的降解率达到94.6;,其反应速率常数达到0.969 h-1.     

La掺杂TiO2薄膜的制备及其光电流研究

采用溶胶凝胶-浸渍提拉法在ITO导电玻璃表面制备了纯TiO2薄膜和La掺杂TiO2薄膜,对其进行350℃、450℃、550℃保温2h热处理.利用XRD、SEM、EDS、XPS对样品结构、形貌、成分进行表征,利用电化学工作站对薄膜进行光电流测试,研究了La掺杂以及不同热处理温度对TiO2薄膜结构及光电流的影响.结果表明:La掺杂有细化TiO2晶粒和抑制锐钛矿相向金红石相转变的作用.随热处理温度提高,纯TiO2薄膜与La掺杂TiO2薄膜光电流密度均先增大后减小,450℃热处理后纯Ti02薄膜光电流密度为180 μA·cm-2,此温度下La掺杂TiO2薄膜光电流密度为650 μA·cm-2,是纯TiO2薄膜的3.6倍.     

热处理对TiO2薄膜的影响及其光催化性能探究

以钛酸丁酯为前驱体,采用溶胶-凝胶法制备TiO2薄膜,探究不同热处理温度对TiO2薄膜的影响及其在紫外光催化下对亚甲基蓝的降解性能,通过热重分析仪(TG-DTG)、X射线衍射仪(XRD)、比表面积和孔结构分析仪、扫描电镜(SEM)、接触角测试对薄膜的热稳定性、晶相组成、比表面积和孔结构、表面形貌、接触角进行表征分析.结果表明:TiO2的晶型随着热处理温度的升高而发生从锐钛矿型到金红石型的相转变;不同热处理温度下TiO2不同晶型影响紫外光催化降解亚甲基蓝的效果;450℃热处理后的TiO2薄膜结构致密,孔径分布窄,在紫外光照射下对亚甲基蓝的降解率最好,经紫外光照射60 min后,其降解率为100;,且接触角最小为7.8°,表现出超亲水性.     

锡掺杂二氧化钛相变过程和微结构分析

本文采用溶胶凝胶法制备了锡掺杂纳米二氧化钛,通过高分辨透射电镜法(HRTEM),X-射线衍射法(XRD)等分析手段对样品的相变过程进行了表征.XRD和HRTEM测试表明纯二氧化钛在烧结温度高于500℃时出现金红石相,而25mol; Sn2+掺杂二氧化钛凝胶在300℃烧结2h后少量锐钛矿相析出的同时结晶出金红石相.实验结果表明Sn2掺杂抑制了锐钛矿和金红石相的晶粒长大;Sn2+掺杂明显地促进了锐钛矿向金红石的转变.Sn2氧化后形成Sn4+,Sn4+置换Ti4+而引起二氧化钛晶格膨胀的同时晶格畸变应力增加.     

高热稳定性锐钛矿型Nd掺杂纳米TiO2的制备与表征

以钛酸丁酯为原料,采用溶胶凝胶法合成了纯TiO2与Nd掺杂TiO2纳米粉体,对其进行了350℃至850℃的热处理.利用XRD、SEM、和EDS对粉体的晶型结构,微观形貌和元素成分进行表征,研究了Nd掺杂对TiO2晶粒尺寸以及晶型转变的影响.结果表明:样品晶粒尺寸达到纳米级别,Nd掺杂后TiO2晶粒尺寸减小.纯TiO2在550℃时已经有金红石生成,750℃完成锐钛矿向金红石的转变;Nd掺杂TiO2在750℃时仍然是锐钛矿,850℃时有少许金红石生成,Nd掺杂提高了TiO2锐钛矿结构的热稳定性.     

CsI-LiCl共晶材料的坩埚下降法生长与闪烁性能研究

本文采用坩埚下降法,在真空密封的石英坩埚中成功生长出CsI-LiCl与CsI-LiCl:Na共晶闪烁体。通过扫描电子显微镜(SEM)观察晶体微结构表明该共晶中LiCl相与CsI相存在周期性的层状排列,CsI相的厚度在5 μm左右。共晶样品的X射线激发发射谱显示在CsI-LiCl和CsI-LiCl:Na共晶样品存在缺陷发光,在CsI-LiCl样品中还观察到了纯CsI的自陷激子(STE)发光。CsI-LiCl样品在α粒子激发下的多道能谱中观察到明显的全能峰,这一结果证明CsI-LiCl共晶可用于热中子探测的潜力。     

静电纺丝法制备CeO2微纳米纤维及其除氟性能

以聚丙烯腈(PAN)为载体,六水合硝酸铈[Ce(NO₃)₃·6H₂O]为原料,采用静电纺丝法制备了Ce(NO₃)₃/PAN纤维,在空气中热处理得到CeO₂微纳米纤维,通过XRD、BET和SEM对CeO₂微纳米纤维进行表征。采用静态吸附实验探讨了CeO₂微纳米纤维去除水溶液中氟离子的性能,考察了溶液pH值、初始氟离子浓度及共存阴离子等对吸附性能的影响。结果表明,pH=3时,CeO₂微纳米纤维对F^-的吸附性能最佳,CeO₂吸附量随着F^-浓度的增大呈上升趋势。CeO₂微纳米纤维对F^-的吸附等温线遵循Langmuir模型,二级动力学模型能很好地描述CeO₂微纳米纤维对F^-的吸附过程。CeO₂微纳米纤维的除氟性能优良,可为其实际应用提供理论参考。     

Selinidin: Crystal structure generated by C–H···O, C–H···π and π-π interactions

The title compound, 9,10-dihydro-8,8-dimethyl-2-oxo-2H,8H-benzo[1,2-b:3,4-b']dipyran-9-yl-2-methyl-2-butenoate, C₁₉H₂₀O₅, was isolated from the roots of Selinum vaginatum. The compound crystallizes into monoclinic space group P2 ₁ with unit cell parameters: a = 12.830(2) Å, b = 9.041(1) Å, c = 14.983(1) Å, β = 95.09(1)°, Z = 4. The crystal structure has been determined using direct methods and refined by full-matrix least-squares to a final R value of 0.0529 for 3142 observed reflections. There are two independent molecules, A and B, per asymmetric unit. In both the molecules, the coumarin nucleus is planar. However pronounced differences are observed in the conformation of dihydropyran ring which has a half-chair conformation with an 8β-9α orientation in molecule A and is intermediate between half-chair and sofa in molecule B. Differences also occur in the conformation of the 2-methylbutenoyloxy side chain at C9 due to the different geometry of C–H···π interactions in molecules A and B. Molecules A and B are connected by π–π interactions between their coumarin fragments forming dimers. The dimers interact through C–H···O and C–H···πhydrogen bonds.     

Chromene and Imidazole Based D-π-A Chemosensor Preparation and Its Anion Responsive Effects

We have designed and synthesized the colorimetric chemosensor through the reactions of 2-(4H-chromen-4-yildene)malonitrile and 4-imidazolecarboxaldehyde. Due to its well conjugated D-π-A system and the existence of NH- fragment in structure, we expected that the chemosensor can detect anion using NH- fragment in the imidazole moiety of the structure. In this regard, UV-Vis absorption spectra were measured to investigate sensing properties of the probe toward different anions in DMSO. This chemosensor can detect both fluoride and cyanide ion with absorption change in intensity. In addition, pH sensing property was also investigated upon the addition of hydroxide ion. These properties are related to the deprotonation effect. The ICT system in this molecule was also observed by the computational approach using Material Studio 4.3 package.     

电子显微分析在表征纳米晶体化学组分中的应用

纳米材料的化学组分及含量影响其光、电、声、热、磁等物理性能,电子显微分析是表征纳米晶体化学组分的重要方法之一.本文综述了X-射线能谱(EDS)、X-射线波谱(WDS)、电子能量损失谱(EELS)和选区电子衍射(SAED)等现代电子显微分析技术在表征纳米晶体化学组分、形貌、尺寸和结构等方面的应用及其研究进展,并比较了这些分析方法存在的差异,提出了其应用中存在的不足及今后的研发方向.     

4- and 5-nitroindane

Mononitration of indane produces a mixture of 4- and 5- nitroindanes. Crystallization from mixtures occurs after distillation improves composition of a major component to above 80%. 4-Nitroindane: triclinic, space group (#2),a=7.332(4) Å,b=8.304(4) Å,c=8.358(4) Å, =61.43(4)°, =67.60(4)°, =70.15(4)°,V=405.4(4) ų,Z=2. Non-H-atoms are nearly planar, aliphatic H's are eclipsed. 5-Nitroindane: monoclinic, space groupP2₁/c (#14),a=10.946(8) Å,b=15.643(10) Å,c=9.415(6) Å, =92.34(5)°,V=1611(2) ų,Z=8. Non-H-atoms in the two molecules differ in torsion of the nitro group with respect to indane and fold of the nonbenzylic methylene group. Semiempirical calculations (PM3) suggest that distorsion from planarity may be associated with the two lowest energy vibrational modes. Uv, ir, ms, proton, and¹³C-nmr spectra are correlated with the solid state structures.     

6<Emphasis Type="Italic">S</Emphasis>,8α-Dihydroxy-14,15-Dihydrocarapin (Khayanone) from the Stem Bark of <Emphasis Type="Italic">Khaya Senegalensis</Emphasis> (Meliaceae): Isolation and its Crystal Structure

Khayanone was isolated from the stem bark of African mahogany, Khaya senegalensis (Meliaceae), and characterized as 6S,8α-dihydroxy-14,15-dihydrocarapin on the basis of spectral analysis and single crystal X-ray diffraction study. The compound crystallizes in the tetragonal space group P4 ₁ 2 ₁ 2 with unit cell parameters: a = 13.2315(19) Å, c = 29.118(6) Å, Z = 8. The crystal structure has been solved by direct methods and refined to R = 0.0375 for 4552 unique reflections. The six-membered rings A and B exist in boat conformations, rings C and D in chair conformations, and the furan ring is planar. The crystal structure is stabilized by O-H···O and C-H···O interactions. This is the first report about 6S configuration of mexicanolide revealed by X-ray diffraction analysis. The configuration of oxygenated C-6 in mexicanolide-group limonoids is discussed.     

Nuclear magnetic resonance: a powerful tool to study liquid crystals

Nuclear magnetic resonance (NMR) is a spectroscopic technique widely used to investigate materials and soft matter in particular. In this brief review, the main uses of NMR techniques to investigate different aspects of liquid crystals, such as the orientational and dynamic properties, the supramolecular structure and average molecular conformations, are described. In the second part of the paper, the case study of a ‘de Vries’ liquid crystal is reported and the main results obtained by combining different NMR techniques are discussed.     

X-ray analysis of sideroxol from <Emphasis Type="Italic">Sideritis leptoclada</Emphasis>

Sideroxol (1), a kaurane diterpene which has the ent-7α,18-dihydroxy-15β,16β-epoxykaurane structure (MW = 320.47, C₂₀H₃₂O₃) was obtained from the acetone extract of Sideritis leptoclada plant as well as from some other Sideritis species. It crystallizes in the orthorhombic space group P2₁, 2₁, 2₁ with a = 10.967(3), b = 24.555(5), c = 6.372(4) Å, Dc = 1.240 g cm⁻³, Z = 4, and refines to R = 0.065 for 721 independent reflections. The skeleton consists of three fused six-membered rings and a five-membered ring with fused epoxide. The six membered rings exhibited slightly distorted chair conformation. In addition to sideroxol, two kaurane and five kaurene diterpenes were isolated from the hexane and acetone extracts of the studied plant.     

Photoluminescence characteristics of Mg- and Si-doped GaN thin films grown by MOCVD technique

We have studied the optical, structural and surface morphology of doped and undoped GaN thin films. The p- and n-type thin films have been successfully prepared by low-pressure MOCVD technique by doping with Mg and Si, respectively. The different carrier concentrations were obtained in the GaN thin films by varying dopant concentrations. Photoluminescence (PL) studies were carried to find the defect levels in the doped and undoped GaN thin films at low temperature. In the undoped GaN thin films, a low intensity and broad yellow band peak was observed. The donor–acceptor pair (DAP) emission and its phonon replicas were observed in both the Si or Mg lightly doped GaN thin films. The dominance of the blue and the yellow emissions increased in the PL spectra, as the carrier concentration was increased. The XRD and SEM analyses were employed to study the structural and surface morphology of the films, respectively. Both the doped and the undoped films exhibited hexagonal structure and polycrystalline nature. Mg-doped GaN thin films showed columnar structure whereas Si-doped films exhibited spherical shape grains.