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1.
纳米TiO_2对诸多环境污染物有显著的光催化降解作用,光催化已发展成为新型环境污染治理技术.本文采用阳极氧化法制备出TiO_2纳米管,对比了四种电解液组成(A氟化铵+硫酸铵+水;B氟化铵+硫酸铵+乙酸+水;C氟化铵+硫酸铵+甘油+水;D氢氟酸+二甲基亚砜(DMOS)+乙醇)对催化剂表面形貌及光催化性能的影响.结果表明,电解液A和C都制备出了形貌清晰的TiO_2纳米管,管径约为60~74 nm.样品经400℃煅烧,TiO_2晶型主要为锐钛矿相;经500℃煅烧,出现少量金红石相;经700℃煅烧,晶型全部为金红石相.具有良好形貌的TiO_2纳米管同时具有良好的紫外光吸收能力.当亚甲基蓝初始浓度为10mg·L~(-1),经500℃煅烧的TiO_2纳米管光催化活性最佳,光照30 min亚甲基蓝的降解率达89.98%.亚甲基蓝光催化降解反应符合一级反应动力学,反应速率常数为0.079 30.  相似文献   

2.
在阳极氧化电解液中添加NaBF4制得了具可见光活性的B掺杂TiO2纳米管阵列(B/TNTs)。采用扫描电镜(FE-SEM)、能谱仪(EDS)、X射线衍射(XRD)、傅立叶红外光谱(FTIR)、紫外-可见漫反射光谱(UV-Vis DRS)以及X射线光电子能谱(XPS)对样品进行表征,以亚甲基蓝(MB)的光催化降解为目标反应评价其光催化活性。结果表明:添加NaBF4后,TiO2纳米管表面形貌变化较大;B掺入到TiO2晶格中形成B-O-Ti键;B掺杂使得TiO2纳米管表面羟基量增加、光学带隙能减小、光吸收阀值红移,且B掺杂量越多,其相应值的变化量越大;B掺杂能促进TiO2锐钛矿相的发育,纳米管经550℃煅烧后仍保持未掺杂样品的锐钛矿相结构;NaBF4的最佳添加量为0.6%(w/w)时,所得样品光催化活性最佳,可见光下光催化降解MB的4 h降解率由未添加的39.90%提高至75.15%,且反复使用10次后其光催化性能基本保持不变;总有机碳(TOC)分析结果表明,MB在可见光下能被B/TiO2有效矿化。  相似文献   

3.
以钛酸纳米管为前驱体,通过添加NaF高温水热合成了(001)面暴露的TiO2纳米薄片,并对其催化苯酚光降解行为进行了研究。结果表明经水热反应后,钛酸型TiO2纳米管(NT)转晶成锐钛矿型TiO2纳米薄片(NS),且具有高(001)暴露面。和NT相比,NS对苯酚的光催化降解活性显著提高,其活性随水热温度升高而增加。NS光催化去除苯酚符合一级动力学,其中200 ℃合成的NS反应速率常数k最高,为0.083 min-1。同时,苯酚的光催化反应初活性与其初浓度的关系符合Langmuir-Hinshelwood模型,表明苯酚的光催化降解受吸附控制。  相似文献   

4.
作为光催化技术的核心, 提高TiO2的光催化活性和对可见光的利用率是当前光催化研究中最重要的研究课题. 为了提高TiO2纳米管的可见光催化活性, 采用化学气相沉积法对TiO2纳米管进行了氟掺杂. 扫描电子显微镜(SEM)结果表明退火温度对于TiO2纳米管的形貌完整性有较大影响, 当样品在550和700 °C下退火, 氟掺杂TiO2纳米管结构受损; X射线衍射(XRD)分析表明氟掺杂对TiO2由锐钛矿相转化为金红石相有阻碍作用; X射线光电子能谱(XPS)测试表明化学气相沉积能有效地对TiO2纳米管进行非金属掺杂, 且该方法安全、操作简单. 氟掺杂TiO2纳米管对甲基橙有较高的可见光催化降解活性. 第一性原理计算结果表明氟掺杂对TiO2带隙无显著影响, 费米能级附近的F 2p轨道电子位于价带底部, 与O 2p交联作用较小, 因此对TiO2光吸收带边影响不大. 氟掺杂能促进表面氧空穴的产生, 增加表面酸度与Ti3+, 有利于减少电子-空穴复合率, 从而提高其光催化活性.  相似文献   

5.
以TiO2纳米管为模板,采用多组分自组装结合水热法制备Bi2WO6/TiO2纳米管异质结构复合材料。通过多种技术如X射线衍射(XRD),X射线光电子能谱(XPS),N2吸附-脱附,扫描电镜(SEM),高分辨透射电镜(HRTEM)和紫外可见漫反射吸收光谱(UV-Vis DRS)考察所制备样品的组成、结构、形貌、光吸收和电子性质。Bi2WO6纳米片或纳米粒子分布在TiO2纳米管上,形成异质结构。随后,通过在紫外、可见和微波辅助光催化模式下降解染料罗丹明B(RhB)来评价复合催化剂的光催化活性。与TiO2纳米管和Bi2WO6相比,Bi2WO6/TiO2-35纳米管在多模式下表现出更优异的光催化活性。与紫外和可见降解模式相比,Bi2WO6/TiO2-35纳米管在微波辅助光催化模式下对RhB的降解效率最高。这种增强的光催化活性源于适量Bi2WO6的引入、纳米管独特的形貌特征和降解模式所引起的增强的量子效率。降解过程中的活性物种被证明是h+,·OH和·O2-自由基。而且,在微波辅助光催化模式下,可产生更多的·OH和·O2-自由基。  相似文献   

6.
以TiO2纳米管为模板,采用多组分自组装结合水热法制备Bi2WO6/TiO2纳米管异质结构复合材料。通过多种技术如X射线衍射(XRD),X射线光电子能谱(XPS),N2吸附脱附,扫描电镜(SEM),高分辨透射电镜(HRTEM)和紫外可见漫反射吸收光谱(UV-Vis DRS)考察所制备样品的组成、结构、形貌、光吸收和电子性质。Bi2WO6纳米片或纳米粒子分布在TiO2纳米管上,形成异质结构。随后,通过在紫外、可见和微波辅助光催化模式下降解染料罗丹明B(RhB)来评价复合催化剂的光催化活性。与TiO2纳米管和Bi2WO6相比,Bi2WO6/TiO2-35纳米管在多模式下表现出更优异的光催化活性。与紫外和可见降解模式相比,Bi2WO6/TiO2-35纳米管在微波辅助光催化模式下对RhB的降解效率最高。这种增强的光催化活性源于适量Bi2WO6的引入、纳米管独特的形貌特征和降解模式所引起的增强的量子效率。降解过程中的活性物种被证明是h+,·OH和·O2-自由基。而且,在微波辅助光催化模式下,可产生更多的·OH和·O2-自由基。  相似文献   

7.
TiO2/Gd2O3纳米粉体的制备、表征及光催化活性   总被引:4,自引:0,他引:4       下载免费PDF全文
利用酸催化的溶胶-凝胶法制备了纯TiO2和Gd3+(0.5wt%)掺杂的TiO2纳米粉体,采用XRD、BET、XPS、紫外-可见漫反射谱(DRS)和表面光电压谱(SPS)等技术进行了表征;以亚甲基蓝(MB)的光催化降解为探针反应,评价了其光催化活性;探讨了Gd3+掺杂对TiO2纳米粉体的光催化活性的影响机制。结果表明,TiO2/Gd2O3纳米粒子对MB溶液的光催化活性提高到纯TiO2的1.5倍。掺杂Gd3+可以强烈抑制TiO2由锐钛矿相向金红石相的转变;阻碍TiO2晶粒的生长;提高高温组织稳定性,改善粉体的表面织构特性;形成光生电子的浅势捕获陷阱,抑制e-/h+复合,这些因素共同作用最终导致TiO2/Gd2O3纳米粉体的光催化活性明显提高。XPS分析结果证实,掺杂Gd3+导致粉体的表面羟基含量降低。由于产生了量子尺寸效应,复合粉体的紫外吸收带边蓝移,光的吸收能力略有降低。  相似文献   

8.
以棉花纤维为模板,利用浸渍-热转化两步法制备了Fe3+掺杂的二氧化钛(Fe3+/TiO2)中空纳米纤维光催化材料,并利用扫描电镜(SEM)、X射线衍射(XRD)、紫外-可见光谱(UV-Vis)和ζ电位等技术对其形貌、结构、光吸收特性及其表面状态等进行了表征。以亚甲基蓝(methylene blue,MB)溶液的脱色降解为模型反应,考察了煅烧温度与时间对Fe3+/TiO2中空纳米纤维光催化性能的影响。结果表明:利用该法可以制得棉花纤维形貌的Fe3+/TiO2中空纳米结构材料;所得材料的催化性能除与材料的尺寸、相结构有关外,还与表面荷电性质有关,表面荷电量越高、表面结构缺陷越多、表面活性位越多,催化活性越高。500 ℃下煅烧2 h所得材料表面长有大量的粒子(平均尺寸为12 nm),其中TiO2为锐钛矿结构,表面荷负电荷量最高,催化性能最好,如在太阳光下,2 h可使MB溶液的脱色降解率达93%,6 h完全脱色,而在纯TiO2中空纤维材料上约为70%;该材料还具有良好的催化稳定性能,重复使用5次仍可使MB溶液的脱色降解率保持在90%以上,且该催化剂材料易于离心分离去除。  相似文献   

9.
TiO2纳米纤维无纺布的制备及光催化性能研究   总被引:1,自引:0,他引:1  
以聚乙烯吡咯烷酮(PVP)作为配位剂与钛酸正丁酯(Ti(C4H9O)4)反应制得前驱体,再以乙醇为溶剂,CH3COOH作为催化剂,采用静电纺丝法制得PVP/TiO2复合纳米纤维,经550 ℃、700 ℃和900 ℃焙烧后分别得到以锐钛矿型的TiO2为主、以金红石型TiO2为主和完全金红石晶型的TiO2纳米纤维。对所制得的纳米纤维的结晶度、纯度和形貌,分别采用差热-热重分析(TG-DTA)、红外光谱(IR)、X射线粉末衍射(XRD)、扫描电镜(SEM)等进行了表征。光降解苯酚水溶液的实验结果表明,550 ℃下煅烧得到的以锐钛矿占主体的TiO2纳米纤维,2 h使浓度为50 mg·L-1苯酚水溶液的降解率超过85%,这充分说明这种TiO2电纺纳米纤维具有良好的光催化性能。  相似文献   

10.
以新疆尉犁工业蛭石为载体,采用溶胶-凝胶法制备负载型二氧化钛光催化剂,利用XRD、TG、SEM、IR和低温N2吸附-脱附对负载型二氧化钛进行表征,并以亚甲基蓝为目标降解物对其光催化性能进行研究。讨论了不同TiO2负载量、反应温度和煅烧温度等因素对负载型二氧化钛光催化性能的影响,结果表明:TiO2负载量为4.0wt%,反应温度为40 ℃,煅烧温度为400 ℃时,复合材料光催化效果最好,经60 W紫外灯照射20 min后,TiO2/VMT复合材料对亚甲基蓝溶液的降解率为92.08%。  相似文献   

11.
Single crystals of K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K3RESi2O7 that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K3LuSi2O7, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K3LuSi2O7 crystallizes in space group P63/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P63/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K3GdSi2O7); a=9.88730(10) Å, c=14.3856(3) Å, (K3TbSi2O7); a=9.8673(2) Å, c=14.3572(4) Å, (K3DySi2O7); a=9.8408(3) Å, c=14.3206(6) Å, (K3HoSi2O7); a=9.82120(10) Å, c=14.2986(2) Å, (K3ErSi2O7); a=9.80200(10) Å, c=14.2863(4) Å, (K3TmSi2O7); a=9.78190(10) Å, c=14.2401(3) Å, (K3YbSi2O7). The optical properties of the silicates were investigated and K3TbSi2O7 was found to fluoresce in the visible.  相似文献   

12.
娄太平  张乐  郭军兴 《化学学报》2010,68(6):466-470
研究了在不同温度下的NaNO3和AgNO3水溶液中Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3离子交换行为.实验表明Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3均显示出了高选择性与Na+和Ag+进行离子交换的特征,且对Ag+的选择性高于Na+.升高温度可显著提高Ag/Li和Ag/Na的交换反应速度.  相似文献   

13.
The crystal structures of compounds with nominal compositions Bi6FeP2O15+x (I), Bi6NiP2O15+x (II) and Bi6ZnP2O15+x (III) were determined from single-crystal X-ray diffraction data. They are monoclinic, space group I2, Z=2. The lattice parameters for (I) are a=11.2644(7), b=5.4380(3), c=11.1440(5) Å, β=96.154(4)°; for (II) a=11.259(7), b=5.461(4), c=11.109(7) Å, β=96.65(1)°; for (III) a=19.7271(5), b=5.4376(2), c=16.9730(6) Å, β=131.932(1)°. Least squares refinements on F2 converged for (I) to R1=0.0554, wR2=0.1408; for (II) R1=0.0647, wR2=0.1697; for (III) R1=0.0385, wR2=0.1023. The crystals are complexly twinned by 2-fold rotation about , by inversion and by mirror reflection. The structures consist of edge-sharing articulations of OBi4 tetrahedra forming layers in the a-c plane that then continue by edge-sharing parallel to the b-axis. The three-dimensional networks are bridged by Fe and Ni octahedra in (I) and (II) and by Zn trigonal bipyramids in (III) as well as by oxygen atoms of the PO4 moieties. Bi also randomly occupies the octahedral sites. Oxygen vacancies exist in the structures of the three compounds due to required charge balances and they occur in the octahedral coordination polyhedron of the transition metal. In compound (III), no positional disorder in atomic sites is present. The Bi-O coordination polyhedra are trigonal prisms with one, two or three faces capped. Magnetic susceptibility data for compound (I) were obtained between 4.2 and 350 K. Between 4.2 and 250 K it is paramagnetic, μeff=6.1 μB; a magnetic transition occurs above 250 K.  相似文献   

14.
The near infrared spectra of aqueous solutions of the ethylsulfates of La, Nd, Gd, Tb, Er, Yb, Lu, Y, and Na have been determined from about 0.2 mol-dm–3 to nearly saturation. The extinction coefficients of water have been calculated taking into account the absorption of ethylslfate anions determined in separate experiments. Their values appeared to be nearly the same as that of pure water. The relative contents of free OH groups in 0.5 and 0.7M solutions have been estimated from the absorbances at 1160 nm. They were lower in solutions of the heavy rare-earth ethylsulfates (Tb, Er, Yb, Lu) than in equimolar solutions of the lighter ones (La, Nd), confirming our previous view that secondary hydration of the heavy trivalent rare-earth cations is distinctly stronger than that of the lighter ones. A comparison of the spectra of these aqueous ethylsulfates with those of perchlorates shows that the structure-breaking ability of the C2H5SO 4 ion is much smaller than that of perchlorate anion.  相似文献   

15.
针对银精矿样品复杂,难消解的特点,研究了不同酸溶法和碱熔法对样品的消解情况,建立了硝酸,盐酸,氢氟酸,高氯酸消解银精矿的方法。根据元素灵敏度和抗干扰性,选定各元素的测定波长。通过酸溶样和碱熔样测定结果比对,验证了方法准确性。建立了四酸消解-电感耦合等离子体光谱法测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的方法,元素的线性相关系数均在0.9999以上。通过共存元素干扰实验,确定了银精矿中高含量元素(铜、铅、锌、铁、锑、铋等)对测定元素结果没有影响。方法检出限:Cu 0.0063 mg/L, Pb 0.0159 mg/L ,Zn 0.0090 mg/L,As 0.0192 mg/L, Cd 0.0093 mg/L ,Ca 0.0084 mg/L, Mg 0.0075 mg/L, Mn 0.0081 mg/L。测定下限:Cu 0.0105mg/L,Pb 0.0265 mg/L, Zn 0.0150 mg/L, As 0.0320 mg/L, Cd 0.0155 mg/L, Ca 0.0140 mg/L, Mg 0.0125 mg/L,Mn 0.0135 mg/L。3个样品的相对标准偏差在0.87%~3.56%之间,加标回收率在95.00%~103.56%之间。方法流程短,操作简单,快速,灵敏度和再现性高,结果准确可靠,可以满足银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的测定。  相似文献   

16.
The room temperature structures of the five layer Aurivillius phases A2Bi4Ti5O18 (A=Ca, Sr, Ba and Pb) have been refined from powder neutron diffraction data using the Rietveld method. The structures consist of [Bi2O2]2+ layers interleaved with perovskite-like [A2Bi2Ti5O16]2− blocks. The structures were refined in the orthorhombic space group B2eb (SG. No. 41), Z=4, and the unit cell parameters of the oxides are a=5.4251(2), b=5.4034(1), c=48.486(1); a=5.4650(2), b=5.4625(3), c=48.852(1); a=5.4988(3), b=5.4980(4), c=50.352(1); a=5.4701(2), b=5.4577(2), c=49.643(1) for A=Ca, Sr, Ba and Pb, respectively. The structural features of the compounds were found similar to n=2-4 layers bismuth oxides. The strain caused by mismatch of cell parameter requirements for the [Bi2O2]2+ layers and perovskite-like [A2Bi2Ti5O16]2− blocks were relieved by tilting of the TiO6 octahedra. Variable temperature synchrotron X-ray studies for Ca and Pb compounds showed that the orthorhombic structure persisted up to 675 and 475 K, respectively. Raman spectra of the compounds are also presented.  相似文献   

17.
通过调节B2O3-Bi2O3-ZnO-Al2O3(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO3)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明:添加适量的BBZA玻璃能够有效地将BaTiO3陶瓷烧结温度由1 350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO3的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO3陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO3晶粒表面。优化的BaTiO3陶瓷制备条件如下:BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO3陶瓷介电常数达到1 364,介电损耗低至1.2%。  相似文献   

18.
Tao Lin  Wei Li  Maochu Gong  Yao Yu  Bo Du  Yaoqiang Chen   《Acta Physico》2007,23(12):1851-1856
TiO2,ZrO2-TiO2,andZrO2-TiO2-CeO2 were prepared by co-precipitation method and characterized by X-ray diffraction (XRD), specific surface area measurements (BET), temperature programmed desorption (NH3-TPD), oxygen storage capacity (OSC), and temperature programmed reduction (H2-TPR). The results showed that ZrO2-TiO2-CeO2 exhibited large number of surface strong acid, possessed some oxygen storage capacity, and strong redox property. The three materials were used as supports and the monolith catalysts were prepared with 1% (w) V2O5 and 9% (w)WO3 for selective catalytic reduction (SCR) of NO with ammonia in the presence of excessive O2, and the results of catalytic activity showed that the catalyst used ZrO2-TiO2-CeO2 as support yielded nearly 100% NO conversion at 275 °C at a gas hourly space velocity (GHSV) of 10000 h−1, and it had the best catalytic activity and showed great potential for practical application.  相似文献   

19.
The phase relations in the system In2O3–TiO2–MgO at 1100 and 1350°C are determined by a classical quenching method. In this system, there are four pseudobinary compounds, In2TiO5, MgTi2O5 (pseudobrookite type), MgTiO3 (ilmenite type), and Mg2TiO4 (spinel type) at 1100°C. At 1350°C, in addition to these compounds there exist a spinel-type solid solution Mg2−xIn2xTi1−xO4 (0≤x≤1) and a compound In6Ti6MgO22 with lattice constants a=5.9236(7) Å, b=3.3862(4) Å, c=6.3609(7) Å, β=108.15(1)°, and q=0.369, which is isostructural with the monoclinic In3Ti2FeO10 in the system In2O3–TiO2–MgO. The relation between the lattice constants of the spinel phase and the composition nearly satisfies Vegard's law. In6Ti6MgO22 extends a solid solution range to In20Ti17Mg3O67 with lattice constants of a=5.9230(5) Å, b=3.3823(3) Å, c=6.3698(6) Å, β=108.10(5)°, and q=0.360. The distributions of constituent cations in the solid solutions are discussed in terms of their ionic radius and site preference effect.  相似文献   

20.
The solid-solid interactions between manganese and magnesium oxides in absence and in presence of small amounts of Li2O have been investigated. The molar ratios between manganese and magnesium oxides in the form of Mn2O3 and MgO were varied between 0.05:1 to 0.5:1. The mixed solids were calcined in air at 400-1000°C. The techniques employed were DTA, XRD and H2O2 decomposition at 20-40°C.The results obtained revealed that solid-solid interactions took place between the reacting solids at 600-1000°C yielding magnesium manganates (Mg2MnO4, Mg6MnO8, MgMnO4 besides unreacted portions of MgO, Mn2O3 and Mn3O4). Li2O-doping (0.75-6 mol%) of the investigated system followed by calcination at 600 and 800°C decreased progressively the intensity of the diffraction lines of Mn2O3 (Bixbyite) with subsequent increase in the lattice parameter 'a' of MgO to an extent proportional to the amount of Li2O added. This finding might suggest that the doping process enhanced the dissolution of Mn2O3 in MgO forming solid solution. This treatment led also to the formation of Li2MnO3. Furthermore, the doping with 3 and 6 mol% Li2O conducted at 800°C resulted in the conversion of Mn2O3 into Mn3O4, a process that took place at 1000°C in absence of Li2O. The produced Li2MnO3 phase remained stable by heating at up to 1000°C. Furthermore, Li2O doping of the investigated system at 400-1000°C resulted in a progressive measurable increase in the particle size of MgO.The catalytic activity measurements showed that the increase in the molar ratio of Mn2O3 in the samples precalcined at 400-800°C was accompanied by a significant increase in the catalytic activity of the treated solids. The maximum increase in the catalytic activity expressed as reaction rate constant measured at 20°C (k 20°C) attained 3.14, 2.67 and 3.25-fold for the solids precalcined at 400, 600 and 800°C, respectively. Li2O-doping of the samples having the formula 0.1 Mn2O3/MgO conducted at 400-600°C brought a progressive significant increase in its catalytic activity. The maximum increase in the value of k 20°C due to Li2O attained 1.93 and 2.75-fold for the samples preheated at 400 and 600°C, respectively and opposite effect was found for the doped samples preheated at 800°C.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

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