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.     

(001)晶面主导的TiO2纳米片表面的F-对其光催化性能的影响

采用水热法以HF为晶面控制剂制备了TiO2纳米片,并用NaOH溶液对其处理,以甲基橙、甲基紫、罗丹明B和亚甲基蓝四种染料为降解对象,研究了处理前后TiO2纳米片的光催化性能并提出了机理.通过X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS)等测试对处理前后TiO2纳米片的结构、形貌以及表面组成进行了表征.结果表明用NaOH溶液处理前后,样品均为边长24 nm、厚度6～7 nm、(001)晶面含量为84;的锐钛矿TiO2纳米片,但是处理后的样品表面F-、表面羟基和吸附水的数量都减少了,而且处理后样品的光催化活性降低.未经NaOH溶液处理的样品具有更高的光催化活性,归因于氟较氧更强的电负性可使TiO2表面吸附更多的水,促进了价带空穴对水的氧化,从而生成更多的羟基自由基.     

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.     

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℃.     

炭黑吸附水热法制备纳米TiO2粉体及其光催化降解甲基橙

利用炭黑吸附钛酸异丙酯水热法制得锐钛矿型TiO2纳米粉体.采用热重/差热分析(TG-DTA)、X-射线衍射(XRD)、扫描电镜(SEM)、比表面积吸附(BET)和紫外-可见光谱(Uv-vIS)等分析方法对不同煅烧机制下所得粉体的物相、颗粒度、分散性和光吸收性能进行表征.同时利用纳米TiO2粉体对甲基橙进行了光催化降解,研究了其光催化性能.结果表明,炭黑的吸附阻止了纳米TiO2超细颗粒的团聚和烧结,制得的颗粒分散均匀、具有单一锐钛矿晶型结构的TiO2纳米粉体.经500℃煅烧获得的TiO2粉体粒径约为15 nm,比表面积为76.31 g/m2.在紫外灯照射下,由于炭黑的吸附和纳米TiO2的光催化形成协同效应,甲基橙的光催化降解率在6min达到99;.     

不同形貌的钨酸铋纳米材料的制备及其光催化性能

利用水热法通过调节溶液pH值和表面活性剂CTAB浓度制备了不同结构与形貌的钨酸铋纳米材料,用X射线衍射(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)等测试方法对产物进行了结构与形貌的表征,并研究了不同结构与形貌的钨酸铋样品对甲基橙的可见光催化降解性能.结果表明,在低pH值时样品为Bi2WO6相纳米片,随着pH值的增加,样品中出现了Bi3.84W0.16O6.24相八面体纳米颗粒,高pH值时,样品则为纯Bi3.84W0.16O6.24相八面体颗粒.随着表面活性剂浓度的增加,Bi2WO6纳米片有自组装的趋势,最终形成花瓣状结构.光催化甲基橙实验结果表明不同形貌的钨酸铋样品对甲基橙有不同的催化降解活性,片状Bi2WO6相纳米片高于Bi3.84W0.16O6.24相八面体颗粒.     

表面活性剂辅助法制备纳米Z nO及光催化性能研究

以Zn(NO3)2·6H2 O、氨水和不同的表面活性剂为原料,采用沉淀法制备了具有不同微观形貌和尺寸的纳米ZnO,研究表面活性剂对纳米ZnO光催化降解甲基橙性能的影响.通过X射线衍射仪(XRD)、扫描电镜(SEM)和紫外可见分光光度计(UV-Vis)等对所制备纳米ZnO的物相、形貌及光吸收性能进行表征,并对其进行光催化性能测试.结果表明,以CTAB为表面活性剂所制备的纳米ZnO,粒径均匀、分散性良好、无明显团聚现象,并且对甲基橙的光催化降解性能最好,在2 h内降解率可达90.6;.     

TiO2-ZnTiO3纳米复合薄膜的制备及光催化性能

将ZnO粉末加入TiO2溶胶中制备出TiO2/ZnTiO3复合薄膜.利用X射线衍射仪、扫描电子显微镜、X射线光电子能谱、紫外-可见吸收光谱对其形貌、晶体结构、化学组成和光谱响应特征进行了表征.以亚甲基蓝(MB)溶液的脱色降解为模型反应,考察了不同ZnO掺入比例对复合薄膜光催化性能的影响.结果表明,所得材料的光催化性能与复合结构中TiO2的结晶结构有关.Ti/Zn=6∶1时,所得复合薄膜由锐钛矿相TiO2与钙钛矿相ZnTiO3构成,薄膜中晶粒尺寸较小(约为30 nm)、结晶度较高、催化性能最好.在紫外光下5h可使亚甲基蓝(MB)溶液脱色降解率达到94;,明显高于纯TiO2薄膜(87;).     

水热法制备Nd3+-介孔TiO2/GO复合材料及光催化性能研究

采用水热法首先制备稀土Nd3+掺杂介孔TiO2,进而复合氧化石墨烯(GO)合成了系列Nd3+-介孔TiO2/GO复合材料.通过X射线衍射(XRD)、透射电镜(TEM)、孔结构分析(BJH与BET)、X射线光电子能谱(XPS)和紫外-可见漫反射(UV-vis)等测试手段对样品的微观结构、形貌、样品表面各元素价态及谱学性质进行表征,并以甲基橙模拟污染物测试其光催化性能.结果表明,所制样品均为锐钛矿结构TiO2,晶粒尺寸在3~4 nm之间;从UV-vis测试结果分析可知,与Nd3+-介孔TiO2和TiO2/GO相比,稀土Nd3+和GO的协同效应更能有效减小TiO2半导体禁带宽度,从而增加其对可见光的吸收.此外,不同光照射下光催化降解甲基橙的实验表明,所制备样品均有较强的紫外及可见光光催化性能,其中系列Nd3+-介孔TiO2/GO复合体系可见光光催化性能更为显著.     

Ce/TiO2纳米管阵列的制备及光催化性能的研究

采用电化学阳极氧化法在钛表面制备TiO2纳米管阵列,并用稀土铈对其修饰改性.以甲基橙为目标降解物,考察了Ce3+溶液浓度、甲基橙溶液的初始浓度和初始pH对铈改性的TiO2纳米管光催化活性的影响.结果表明:Ce3+溶液的浓度存在一个最佳值,当Ce3+溶液浓度为0.01 mol/L,在10 mg/L,pH =3的甲基橙溶液中光催化活性最好.光照4h后,甲基橙的降解率达83％.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.     

Synthesis of spinacine and spinacine derivatives: crystal and molecular structures of Nπ-hydroxymethyl spinacine and Nα-methyl spinaceamine

The natural amino acid L-Spinacine (4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridine-6-carboxylic acid) has been synthesized following a new pathway which gives a chemically and optically pure product with an excellent yield. The crystal structures of a synthetic intermediate, N^π-hydroxymethyl-spinacine, and a spinacine derivative, N^α-methyl-spinaceamine, have been investigated through X-ray diffraction: Spi(πMeOH)·H₂O, monoclinicP2 _i,a=8.571(1),b=6.682(1),c=8.588(1) Å, and β=94.67(1)^o. Spm(αMe)·2HCl·H₂O, triclinicP l,a=7.492(4),b=10.799(3),c=7.040(2) Å, α=91.88(2), β=98.36(3) and γ=73.34(3)^o. Spi(πMeOH) crystallizes with a water molecule and displays a zwitterionic character. The carboxylate group is in equatorial position and forms a short electrostatic interaction of 2.618(2) Å between one of its oxygens and the protonated nitrogen of the tetrahydropyridine ring. The crystal packing is assured by strong O?H???O, O?H???N, N?H???N intermolecular hydrogen bonds and C?H???O close contacts. The biprotonated compounds Spm(αMe) crystallizes with two Cl^? anions and a water molecule. The positive charge on the imidazole ring is delocalized on the conjugated moiety N=C?N. The crystal is built up by clusters formed by two biprotonated Spm(αMe) molecules, four Cl^? anions and two water molecules linked together by hydrogen bonds.     

X-ray Crystal Structures of [Et3NH][{(CO)5Mo(P(OCH2CMe2CH2O)O)}2H] and (CO)5Mo{μ-Ph2POPPh2}Mo(CO)5, Two Complexes Derived from the Hydrolysis of Coordinated Chloro-Phosphorous-Donor Ligands

Abstract X-ray crystal structures of [Et₃NH][{(CO)₅Mo(P(OCH₂CMe₂CH₂O)O)}₂H], 3, and (CO)₅Mo{μ-Ph₂POPPh₂}Mo(CO)₅, 2, are reported. Crystallization of 3 occurs in P-1 space group with a = 9.6944(19) ?, b = 10.814(2) ?, c = 19.730(4) ?, α = 94.24(3)°, β = 92.23(3)°, γ = 113.47(3)°, Z = 4. Crystallization of 2 occurs in C2/c space group with a = 10.357(2) ?, b = 20.149(4) ?, c = 17.155(3) ?, α = 90°, β = 97.28(3)°, γ = 90°, Z = 8. Compound 2 is a bimetallic complex with a P–O–P bridging group containing bond distances similar to that of other complexes in which two metal centers are bridged by a single R₂POPR₂ ligand. Compound 3 contains intermolecular hydrogen bonded P–O–H–O–P linkages with bond distances comparable to those seen in similar structures with intramolecular hydrogen bonding suggesting that the distance is a function of the nature of the bond and not affected by the cis arrangement of the ligands about the metal center. Graphical abstract X-ray Crystal Structures of [Et ₃ NH][{(CO) ₅ Mo(P(OCH ₂ CMe ₂ CH ₂ O) O)} ₂ H] and (CO) ₅ Mo{μ-Ph ₂ POPPh ₂ }Mo(CO) ₅ , Two Complexes Derived from the Hydrolysis of Coordinated Chloro-Phosphorous-Donor Ligands Samuel B. Owens Jr., Abha A. Kaisare and Gary M. Gray X-ray crystal structures of [Et₃NH][{(CO)₅Mo(P(OCH₂CMe₂CH₂O)O)}₂H], 3, and (CO)₅Mo{μ-Ph₂POPPh₂}Mo(CO)₅, 2, have been determined.      

Preparation,spectral studies and X-ray crystal structure of 1,3,5-triphenyl-1,5-pentanedione,C23H20O2

1,3,5-triphenyl-1,5-pentanedione, C₂₃H₂₀O₂, has been prepared and characterized by spectroscopic methods and single crystal X-ray analysis. Crystals are monoclinic, space groupP2₁/n, a=28.124(4),b=5.997(1),c=10.434(1)Å, -98.42(1)Å,Z=4. The structure has been refined to a finalR-value of 0.040 for 1625 reflections withF _o>3(F _o). The compound contains the two carbonyl groups in a mutuallycis arrangement.     

Isotope Effects in Liquid Crystal Systems: I: Phase Relationships in the Dodecylamine-H2O,Dodecylamine-D2O Systems

The phase diagrams and heats of fusion and transition have been determined for the dodecyl amine (-NH₂)/H₂O and dodecyl amine (-ND₂)/D₂O systems using direct optical observation and differential scanning calorimetry.     

Spherulitic crystallization of β‐In2Te3 by physical vapour deposition

Different morphologies of indium telluride (In₂Te₃) including novel spherulites were crystallized using the physical vapour deposition (PVD) method, by varying the difference in the growth and source zone temperature (ΔT) of a dual zone horizontal furnace assembled indigenously. Whiskers and kinked needles of In₂Te₃were grown at ΔT = 250 K and 300 K respectively, maintaining the growth zone at 500 °C. At high supersaturation (Δ T = 400 K), spherulitic crystals were obtained. The stoichiometric composition of these crystals has been confirmed using energy dispersive analysis by x‐rays (EDAX). The structure of β‐In₂Te₃ spherulitic crystals is identified as zinc blende with lattice parameter a = 6.159 Å, from x‐ray diffraction (XRD) studies. The scanning electron microscope (SEM) images revealed the radial structure of the grown spherulites. The growth mechanism for the spherulitic crystallization of β‐In₂Te₃ crystals has been discussed based on the theoretical models. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)