铁、镧共掺杂介孔TiO2微球的制备及光催化性能研究

以钛酸异丙酯为钛源,利用三嵌段共聚物EO106 PO70 EO106(F127)修饰的溶胶-凝胶法合成了La、Fe共掺杂的单分散TiO2介孔微球.并通过X射线衍射(XRD)、场发射扫描电镜(FESEM)、能谱分析(EDX)、透射电镜(TEM)、BET、X射线光电子能谱(XPS)、紫外-可见光漫反射技术对样品的物相组成及微观结构进行了表征,利用紫外光照射降解亚甲基蓝溶液的方法测定其光催化性能.结果表明:与纯TiO2介孔微球相比,La3+的掺入抑制了TiO2晶粒的长大,La3+和Fe3+共掺入TiO2介孔微球的紫外-可见光的吸收带边发生红移,禁带宽度减小;在紫外光照射下,1at;La3+掺杂以及Fe3+、La3+共掺TiO2介孔微球的光催化活性均高于纯TiO2,其中1at;Fe/1at;La-TiO2的光催化性能最好.     

Sm,C掺杂改性纳米TiO2及其可见光催化性能研究

通过溶胶-凝胶法制备了Sm、C分别单掺杂和共掺杂纳米TiO2光催化剂,采用XRD、FESEM、TEM、XPS、UV-Vis-DRS、PL、Nano-sizer纳米粒度分析仪等对样品进行表征,以光催化降解亚甲基蓝(MB)作为评价模型,研究了不同样品对MB的光催化降解效果.结果表明,Sm单掺杂抑制了TiO2从锐钛矿向金红石的相转变,抑制晶粒长大,C的单掺杂则促进了TiO2的相转变,Sm或(和)C的掺杂均能细化TiO2晶粒,拓展TiO2在可见光区的光谱响应范围,降低光生e-/h+对的复合几率.Sm、C的掺杂均能有效提高TiO2的光催化活性,且共掺杂时存在协同效应,当n(Sm)∶n(C)∶n(Ti)=0.01∶0.3∶1、热处理温度500 ℃时,Sm/C-TiO2样品在普通日光灯下催化降解MB的一级表观速率常数是相同条件下纯TiO2的4.3倍.     

可见光响应型Fe掺杂SiO2/TiO2光催化材料的制备及降解水中腐殖酸的研究

采用溶胶凝胶法制备了可见光响应型Fe掺杂SiO2/TiO2光催化材料,并采用TG-DTA、XRD、UV-vis、TEM及XPS等手段对其进行了表征.以水中腐殖酸的降解为探针反应,考察了可见光照射下Fe-SiO2/TiO2的光催化活性.XRD结果表明,Fe离子掺杂可抑制催化剂晶粒尺寸,600℃焙烧后的Fe-SiO2/TiO2为锐钛矿相结构.Ur-vis吸收光谱分析可看出Fe离子掺杂提高了催化剂对可见光的吸收能力,并使催化剂的吸收带边产生了红移.XPS光谱表明,催化剂表面存在着Fe2+和Fe3+.实验结果表明,Fe-SiO2/TiO2在可见光下对腐殖酸的光催化降解率优于SiO2/TiO2和TiO2.Fe-SiO2/TiO2具有较高光催化活性的主要原因为:Fe离子掺杂不仅使SiO2/TiO2催化剂的粒径减小和对可见光的吸收增强,而且在催化剂表面产生了有利于光生e--h+对分离的Fe3+/Fe2+氧化还原循环电对.     

Li2 CO3-Y3+共掺杂TiO2纳米材料的制备及光催化性能的研究

采用溶胶-凝胶法制备了Y3+-TiO2纳米粒子,利用X-射线衍射仪(XRD)、扫描电镜(SEM)、紫外-可见光谱(UV-vis)等仪器对样品的物化性质进行了表征.以对亚甲基蓝为目标降解物,考查了Y3+掺杂对纳米TiO2光催化活性的影响.实验结果表明,掺杂浓度摩尔比为0.03的Y3+有利于提升TiO2光催化活性,能有效提高对亚甲基蓝的光催化降解效率.对TiO2纳米粒子进行了Y3+和Li2 CO3共掺杂,Li2 CO3共掺Y3+-TiO2相比于Y3+-TiO2对亚甲基蓝的光催化降解效率有了进一步的提升,同时对相关机理进行了详细的论证,推测Li2 CO3在本研究中起到空穴补偿剂而不是电荷补偿剂的作用.     

水分散性N掺杂TiO2的制备及其光催化性能研究

采用多羟基法一步合成了具有可见光催化活性的水分散性N掺杂TiO2纳米颗粒,其中四异丙醇钛(TIIP)作为钛源,二乙二醇(DEG)作为反应溶剂,谷氨酸作为表面修饰剂和氮源.所得TiO2纳米颗粒在pH≥6.54的水溶液中可以很好的分散,并能稳定保持一星期.以甲基橙为目标降解物,研究了水分散性N掺杂TiO2在可见光下的光催化活性.结果显示,与未经掺杂的TiO2相比,所制得的N掺杂TiO2有良好的可见光催化活性.除此之外还通过改变气体氛围和添加捕获剂对水分散性N掺杂TiO2降解甲基橙(MO)的光催化机理进行了研究.本方法制备的TiO2因具有优越的水分散性和良好的可见光催化活性,在光动力治疗(PDT)中有极好的应用前景.     

生物质改性纳米TiO2的制备及其结构表征

采用溶胶-凝胶法制备了系列生物质改性复合纳米TiO2.以亚甲基蓝溶液为模拟污染物,考察了其可见光催化活性,并确定了最佳制备工艺.通过X射线光电子能谱(XPS)、X射线衍射(XRD)、场发射扫描电镜(FESEM)、紫外-可见漫反射光谱(UV-Vis-DRS)、荧光光谱(PL)等手段对催化剂样品进行了表征.实验结果表明,催化剂对亚甲基蓝的光催化降解适应一级反应动力学,复合TiO2和纯TiO2的反应速率常数分别为0.4990 h-1和0.0305 h-1,且复合催化剂实现了C、N、S、P、K等多元素的共掺杂.相比纯TiO2,复合TiO2的比表面积增大,结晶度升高,光生载流子复合率降低,吸收边带红移,禁带宽度窄化了0.09 eV.     

胶原纤维为模板制备Gd掺杂纤维状二氧化钛及光催化性能研究

以胶原为模板剂、硫酸钛为钛源、硝酸钆为掺杂源制备了钆掺杂纤维结构TiO2(Gd-TiO2).通过扫描电镜(SEM)、X射线衍射仪(XRD)、紫外可见漫反射光谱(UV-Vis-DRS)、X射线光电子能谱(XPS)对样品的表面形貌、晶相组成、紫外吸收带、元素组成及化合价态进行了分析.以甲基橙为目标降解物,研究了样品的光催化性能并确定钆的最佳掺杂量.结果表明:600℃煅烧温度下2;Gd-TiO2纤维结构完好、光催化效果最好,光反应30 min后其降解率达到91.89;,比起未掺杂试样大大提高.钆掺杂会改变TiO2的晶粒尺寸并能够抑制TiO2从锐钛矿相向金红石相转变,掺杂后紫外吸收带发生蓝移.     

TiO2∶Fe的EPR谱及其光催化特性研究

采用溶胶-凝胶法制备了TiO2∶ Fe材料,测试并分析了材料的电子顺磁共振谱,其结果显示溶胶凝胶法制备的Fe掺杂TiO2粉末在g=1.99和4.3处具有明显信号峰,归属于信号对应离子,并利用其积分值半定量分析了掺杂到晶体表面和内部Fe离子数目的多少及二者比值,发现对离子掺杂到内部而言直至掺杂浓度为0.6;仍未达到饱和,而对离子掺杂到表面而言,当掺杂浓度为0.4;时,该信号强度不再增强,掺杂到晶体表面的Fe离子数量达到饱和.使用紫外可见光谱仪测定了所制材料的光催化性能,所制的Fe掺杂TiO2纳米材料最佳掺杂浓度为0.1;,对甲基橙降解率是17.83;,比未掺杂材料降解率(16.31;)提高了9.32;,增强了光催化活性,其余掺杂浓度(0.0372;,0.2;,0.4;和0.6;)样品的光催化活性均比未掺杂样品的低,降低了光催化活性.     

稀土Sm掺杂对纳米TiO2结构和可见光催化性能的影响

采用溶胶-凝胶法制备了纯TiO2和稀土Sm掺杂TiO2纳米粉体( Sm-TiO2),通过XRD、XPS、FT-IR、UV-Vis-DRS、PL和Nano-sizer纳米粒度仪等对样品进行表征,以亚甲基蓝( MB)的光催化降解为探针反应,探讨稀土Sm掺杂对纳米TiO2的结构和可见光催化性能的影响。结果表明,Sm掺入TiO2后在表面存在Sm3+和Sm2+两种价态, Sm掺杂抑制了TiO2从锐钛矿向金红石的相转变,阻碍纳米晶粒生长,增加了纳米粉体表面羟基含量;适量的Sm掺杂能使TiO2吸收光谱的阈值波长红移,有效降低光生e-/h+的复合率,提高TiO2光催化活性。热处理温度500℃时,掺杂1.0wt;Sm的纳米TiO2样品在普通日光灯下对MB在6 h内的光催化降解效率达97;,明显高于同等条件下Degussa公司产品P25的降解率56;。     

镧掺杂混晶结构TiO2纳米粉体的制备及其光催化性能

以钛酸四丁酯为Ti源,采用溶胶-凝胶自蔓燃法制备了镧掺杂的La-TiO2(简写为LT)纳米粉体.利用X射线粉末衍射(XRD)、红外光谱(FIIR)、透射电子显微镜(TEM)等对掺杂型TiO2粉体的晶型结构与颗粒尺寸等进行表征.利用紫外-可见光吸收光谱(UV-vis)研究了H2O2改性、镧掺杂量以及混晶结构对TiO2纳米粉体降解甲基橙的影响.结果表明:镧掺杂混晶TiO2粉体的光催化活性明显优于未掺杂的锐钛矿TiO2粉体.当La3+掺杂量为0.5;,合成温度为475℃(金红石相含量为26.0;)时,得到的TiO2粉体光催化活性最好.H2O2的加入有助于TiO2光催化剂表面的电子-空穴对生成,提高光催化剂对甲基橙的降解率,当H2O2浓度为6;时,光照3h后,降解率达到了91.97;.     

Syntheses and structures of N-phenylmaleimidetriazoles and by-products

The syntheses, properties, and structures of N-phenylmaleimidetriazole derivatives are described. Intermediates and by-products are also discussed. 1b. a = 43.997(7) Å, 5.7610(9) Å, 8.245(1) Å, = 99.339(4), C₂/c; 2a. a = 13.646(4) Å, b = 7.744(2) Å, c = 10.612(3) Å, = 91.979(6), P2₁/c. 3a. a = 22.245(1) Å, b = 22.245(1) Å, 10.010(1) Å, P42/n. 3a. a = 11.727(2) Å, b = 14.075(3) Å, c = 16.080(3) Å, = 105.859(3), = 105.331(3), = 98.187(3), P-1. 3b. a = 8.561(3) Å, b = 14.755(5) Å, c = 22.771(7) Å, = 97.006(5), P2₁/c. 3c. a = 10.500(2) Å, b = 12.189(2) Å, c = 13.040(2) Å, = 109.091(3), = 106.089(3), = 101.022(3), P-1. 8a. a = 16.389(8) Å, b = 5.749(3) Å, c = 19.316(3) Å, = 97.467(9), P2₁/n. 8b. a = 5.822(2) Å, b = 10.114(3) Å, c = 16.705(4) Å, = 84.681(5), = 82.840(5), = 75.769(4), P-1. 9b. a = 11.251(1) Å, 13.335(3) Å, 13.376(3) Å, = 102.456(4), P2₁/n. 9c. a = 15.836(3) Å, b = 8.236(2) Å, c = 5.447(3) Å, = 92.551(3), P2₁/c. 10a. a = 13.177(2) Å, b = 14.597(2) Å, c = 5.5505(8) Å, = 110.979(2), Cc. 11a. a = 14.720(2) Å, b = 13.995(2) Å, c = 38.245(6) Å, = 94.430(3), P2₁/n. 12b. a = 15.067(5) Å, b = 20.378(6) Å, c = 8.669(5) Å, = 99.16(4), = 99.32(3), = 105.23(3), P-1. 13b. a = 8.2824(6) Å, b = 10.5245(7) Å, c = 15.518(1) Å, = 92.305(1), = 100.473(1), = 100.124(1), P-1. 15a. a = 15.357(3) Å, b = 7.778(2) Å, c = 22.957(2) Å, Pbca. 16b. a = 18.0384(4) Å, b = 12.474(3) Å, c = 20.078(5) Å, Pbca.     

Sol-gel synthesis and characterization of adsorbent and photoluminescent nanocomposites of starch and silica

Using sol-gel method, mesoporous and photoluminescent silica nanocomposites of soluble starch have been synthesized and characterized. Different ratios of H₂O, TEOS and EtOH were used at fixed template (soluble starch) and catalyst (NH₄OH) concentrations to obtain materials of different performances in terms of heavy metal binding from a solution which has been monitored using Cd(II) as representative divalent heavy metal ion. Optimum material was obtained when H₂O, TEOS and EtOH were used in 14:1:2 ratio. This sample was not only an efficient metal ion adsorbent but also had an intense luminescence in ultra-violet region and potentially may be used in silicon-based UV-emitting devices. Metal binding by the material was further enhanced after calcination (at 800 °C in air) while its luminescence had a multipeak profile in UV-visible region. In a batch adsorption study, calcined hybrid composite (0.25 g/L) could remove 98.5% Cd(II) from 100 mg/L Cd(II) solution in 2 h. The chemical, structural and textural characteristics of the synthesized materials have been investigated using Fourier Transform Infrared Spectroscopy (FTIR), X-rays Diffraction (XRD), Thermal Analysis (TGA/DTA), Photoluminescence (PL), Brunauer-Emmett-Teller Analysis (BET) and Scanning Electron Microscopy (SEM).     

晶体中负离子配位多面体结晶方位、形变与晶体压电、铁电性

本文研究了压电、铁电晶体中负离子配位多面体的结晶方位与形变,提出了压电晶体中同一种负离子配位多面体的结晶方位是一致的.在铁电晶体中,负离子配位多面体发生形变,伴随着晶体发生顺电-铁电相变,并从这一基本过程出发,对铁电体相变的形成机理进行了讨论.     

Biocrystallization in Bacterial and Fungal Cells and Spores

A series of X-ray diffraction experiments were performed for the first time to study stress-induced biocrystallization (structural response to stress) in the bacteria E. coli, the spore-forming bacteria Bacillus cereus, and in cells and spores of the mycelial fungus Umbelopsis ramanniana. High-intensity areas with spacings of 90 and 44 Å are indicative of a periodically ordered arrangement (most likely nanocrystalline) of the bacterial nucleoid. For the starved bacteria Bacillus cereus, a peak at a spacing of 45 Å is also assigned to nanocrystalline complexes of DNA with the Dps protein. The spores of the fungus Umbelopsis ramanniana VKM F-582, as well as the spores of Bacillus cereus, form ordered arrays of DNA molecules with DNA-condensing acid-soluble proteins SASPs. Starved dehydrated mycelial cells of the fungus Umbelopsis ramanniana form ordered structures with spacings from 27 to 55 Å. A series of peaks reflect the formation of a number of ordered protein arrays, apparently with DNA, with continuously varying characteristic interplanar spacings.     

Preparation and characterization of PbSe nanopowder and quasi-ceramics

By means of the reduction of Pb(II) and Se(IV) with hydrazine, oval monodispersed PbSe nanoparticles characterized by sizes ～100 nm and the cubic symmetry were obtained. Their compaction and sintering into quasi-ceramic state were performed. The samples were investigated by means of scanning electron microscopy, X-ray diffraction and FTIR spectroscopy. The results obtained are discussed.     

Simulation and Experiment in X-ray Topography and Diffractometry

X-ray double crystal topography and high resolution diffractometry reveal very small deformations of the crystal lattice. However, this information can be directly obtained from the topographs or diffractometer curves only if certain conditions are fulfilled. Generally a deformation model has to be used, that is compared to the measurements by simulation calculations based on the dynamical diffraction theory. Trial and error allow to adapt the parameters of the model. An example illustrates that with a few parameters an automatic fit is possible.     

Melting and short-range order in liquids and glasses

A theory is proposed to explain two-dimensional melting based on the gauge-invariant Lagrangian with spontaneous breaking (Higgs mechanism) or the SU(2) gauge field to U(1) symmetry. The first-order phase transition in two-dimensional melting may be strongly related to the asymptotic freedom-like interaction of the SU(2) gauge field in the case when the distance between each excited disk is shorter than a critical length, 2/ boxv;mboxv, near the melting temperature.     

Structural and spectral studies of N-trans-cinnamylidene-m-toluidine and N-trans-cinnamylidene-m-chloroaniline

N-trans-cinnamylidene-m-toluidine (1) C₁₆H₁₅N, and N-trans-cinnamylidene-m-chloroaniline (2) C₁₅H₁₂NCl form isomorphous crystals which are monoclinic, space group P2_l/c, with unit cell dimensionsa=5.967(2),b=13.793(3),c=15.048(5) Å, =91.97(3)° anda=5.868(2),b=13.788(4),c=15.191(4) Å, =91.87(3)°, respectively. The single-crystal X-ray structure determinations of the title compounds revealtrans structures. Ring (A) C_10–15 and ring (B) C_1–6, are practically planar in both structures with dihedral angels of 61.3(3) and 63.6(2)°, respectively.¹H nmr, u.v. and i.r. spectra are also reported.     

Chemistry and Electrocrystallization of Organic Metals and Superconductors

Abstract

Considerable variation in the conditions of electrochemical crystal growth of TMTSF₂X (i.e., constant current versus constant potential, ambient versus inert atmosphere, etc.) and in the purity of the constituents (donor, electrolyte, solvent) does not significantly affect the unusual low-temperature properties of this class of materials. Our results suggest that the electrocrystallization procedure may be self-purifying by selecting for conducting crystal phases with constituents having specific oxidation potentials and solubility properties. However, doping solutions with structurally and chemically similar constituents (i.e., TMTTF, and IO^? ₄ in CIO^? ₄) leads to their incorporation in the crystal structure where they have a profound effect. Several mole percent of these dopants suppress superconductivity in the PF^? ₆ and CIO^? ₄ salts, and increase and broaden the metal-insulator phase transition.     

Hydrothermal Synthesis and Morphology of Thomsonite and Edingtonite

The hydrothermal treatment of different glasses of the composition 2 Na₂O–8 CaO–10 Al₂O₃– 20 SiO₂ and 2 BaO–2 Al₂O₃–6 SiO₂ at one kilobar pressure in a temperature-range between 80 °C and 230 °C lead to the formation of the zeolite-minerals thomsonite (orthorhombic symmetry space-group Pbmn, a = 13.05 Å, b = 13.09 Å and c = 13.22 Å), and edingtonite (orthorhombic symmetry, space-group: P2,2,2, a = 9.55 Å, b = 9.67 Å and c = 6.52 Å). Under the chosen hydrothermal conditions both mineral phases are formed in the whole temperature interval.