高结晶度氮掺杂介孔TiO_2的制备及光催化活性(英文)

以钛酸丁酯为钛源,尿素为氮源,聚丙烯酰胺(PAM)和聚乙二醇(PEG)为复合模板剂,采用溶胶-凝胶法,在氮气和空气气氛中分段煅烧,制得高结晶度氮掺杂介孔TiO2光催化剂.利用X射线衍射、透射电镜、N2吸附-脱附、X射线光电子能谱和紫外-可见漫反射光谱等技术对其进行了表征.结果表明,当PAM和PEG的质量比为1:4时,先在氮气中600°C煅烧,后在空气中500°C煅烧所得样品是锐钛矿相,具有良好的孔隙结构和较高的结晶度,平均孔径为5.11nm,晶粒尺寸为12.5nm,比表面积110.8m2/g.掺杂介孔TiO2的氮主要以取代氮和化学吸附分子γ-N2的形式存在,少量以间隙氮形式存在.氮掺杂使TiO2的能带变窄,吸收带边明显红移,且使光吸收强度显著增大.光催化降解甲基橙实验结果表明,与未掺杂样品相比,氮掺杂介孔TiO2在可见光作用下表现出较高的催化活性.     

采用溶胶-凝胶-溶剂热路径合成H_3PW_(12)O_(40)/TiO_2和H_4SiW_(12)O_(40)/TiO_2及其光催化降解二硝基甲苯(英文)

以非离子表面活性剂P123为结构导向剂,采用溶胶-凝胶与溶解热相结合方法,制备了两类介孔材料H3PW12O40/TiO2和H4SiW12O40/TiO2,并对其进行了表征.X射线粉末衍射和拉曼光谱分析表明,所制催化剂为锐钛矿晶型,体系中H3PW12O40和H4SiW12O40的Keggin结构经400°C焙烧后仍保持完整.H3PW12O40/TiO2和H4SiW12O40/TiO2的平均粒径分别为15.49和7.75 nm.N2吸附-脱附和扫描电镜结果表明,P123的加入使催化剂的粒径减小,比表面积和孔体积明显增大,其中H3PW12O40/TiO2和H4SiW12O40/TiO2的比表面积分别高达252.2和250.0 m2/g.紫外漫反射吸收光谱表明,与纯TiO2相比,复合催化剂的吸收光谱发生了明显的红移,且吸收强度明显增大.催化剂对DNT降解实验表明,在最佳操作条件下降解率可高达95%.     

二维六方p6mm有序介孔WO_3-TiO_2复合材料的制备及其可见光光催化性能

以非离子型表面活性剂为模板剂,采用蒸发诱导自组装法制备了一系列不同WO3含量的有序介孔WO3-TiO2复合材料,并表征了其孔结构、形貌、孔隙率、光谱性质及组成.结果表明,该材料呈二维六方p6mm对称和锐钛矿晶相结构;与无序WO3-TiO2复合材料相比,其比表面积(152～154m2/g)更大,孔径更均一(5.3nm),且比纯TiO2的帯隙宽度(3.0eV)更窄.将该WO3-TiO2样品用于可见光光催化降解水相中罗丹明B和2,4-二氯苯氧乙酸的反应中,发现WO3含量适当的有序介孔WO3-TiO2样品的光催化活性比无序的样品和纯TiO2的更高.     

(C_5H_7N_2)_3AsMo_(12)O_(40)·5H_2O的合成、表征及光催化性能研究

合成了配合物(C5H7N2)3AsMo12040·5H2O,对其进行了IR和TG/DTA分析,并用X-射线单晶衍射仪测定了晶体结构。配合物晶体属于单斜晶系,P-1空间群。配合物经N—H…N和N—H…O氢键相连组成超分子化合物,氢键稳定了晶体结构。将该配合物掺杂TiO2制备复合催化剂(C5H7N2)3AsMo12040·5H2O/TiO2,以甲醇、丙酮气体消除反应为模式反应评价该配合物和复合催化剂的光催化性能。结果表明,复合催化剂的催化活性优于配合物本身和TiO2。配合物中的有机分子,对有机物有强的亲和性,更容易吸附有机分子利于光催化反应的进行。     

铋掺杂介孔二氧化钛的制备及光催化动力学

以介孔分子筛(KIT-6)为载体,采用溶液浸渍法合成了铋(Bi)掺杂的介孔二氧化钛(TiO₂)光催化剂。利用XRD、TEM、SEM、XPS、N₂吸附-脱附法和拉曼光谱法等技术手段对材料的结构和形貌进行表征。通过紫外-可见吸收光谱法考察了催化剂对罗丹明B光催化降解效率,进一步考察了Bi的掺杂量对光催化反应速率的影响,并对光催化降解动力学进行了初步研究。结果表明,Bi掺杂的介孔TiO₂具有较窄的孔径分布(3~4 nm),而且吸收范围扩展到可见光区,其光催化活性明显高于商品TiO₂(P25)。随之Bi掺杂量的提高,反应速率常数也增大,其光催化降解罗丹明B的反应均符合准一级动力学方程。     

高热稳定性有序介孔TiO_2/活性炭制备及其孔-孔协同光催化性能

以十六烷基三甲基溴化铵(CTAB)表面活性剂和钛酸四丁酯分别为造孔模板和钛源,通过超声辅助溶剂挥发自组装技术制备有序介孔氧化钛(ordered mesoporous Ti O2,OMPT)及其活性炭负载体(ordered mesoporous Ti O2/AC,OMPTA).为探讨OMPTA结构与性能之间的关系,采用超声辅助溶胶-凝胶技术合成了无孔氧化钛/活性炭(nonporous Ti O2/AC,NPTA)负载体,利用热重-差热(TG-DTA)、X射线衍射(XRD)、氮气吸附-解吸、透射电子显微镜(TEM)和紫外漫反射(DRS)等手段对制备材料结构进行表征.以酸性红B(acid red B,ARB)的光催化降解为探针实验,评价OMPTA的光催化性能和使用寿命,提出了孔-孔协同光催化扩增机制,并探讨了催化条件(染料浓度、催化剂浓度和溶液p H)对协同扩增效果的影响.结果表明:相对于纯OMPT,OMPTA具有晶粒生长的高活化能、较小的粒径尺寸和对有序介孔结构的高热稳定性,这归功于活性炭的吸附力和非晶相层对晶粒生长的阻碍作用.由于孔-孔协同光催化扩增效应,导致OMPTA在NPTA、OMPT-AC、OMPT、P25和NPT中具有更高的催化活性.热处理温度强烈影响OMPTA的光催化活性,其中OMPTA-500具有最高的光催化活性,这归功于其具备完善的结晶性、相对高浓度的羟基和Ti3+离子.同时,OMPTA-500在重复使用过程中也具有很高的光催化性能.当使用OMPTA-500为催化剂对ARB降解时,最佳的催化条件为催化剂浓度1 g/L,ARB浓度15 mg/L,p H 5.     

介孔TiO_2-SO_4~(2-)的合成及表征

在不使用有机模板剂的条件下,以工业硫酸钛溶液为原料合成了高热稳定的锐钛矿型介孔TiO_2-SO_4~(2-).用X射线衍射、N2吸附、扫描电镜、X射线能谱、傅里叶变换红外光谱和紫外-可见光谱对样品进行了表征,并考察了其光催化性能.结果表明,硫酸根在焙烧过程中与前驱体介孔偏钛酸孔壁上自由羟基的键合起到了孔结构导向及支撑作用,500℃焙烧后样品仍具有202.2m2/g的比表面积及2.8nm的平均孔径.焙烧产物TiO_2-SO_4~(2-)中S=O的强电子诱导效应不仅使邻近的Ti成为超强酸中心,还使二氧化钛的吸收光谱产生30nm的红移,光催化活性显著提高.     

大孔-介孔氮掺杂二氧化钛的制备及其光催化性能测试

以嵌段共聚物为模板剂,甲酰胺为氮源,结合溶胶凝胶法制备了具有可见光活性的大孔-介孔氮掺杂二氧化钛(N-TiO2)材料.通过X射线衍射、低温N2吸附-脱附、扫描电镜、紫外-可见吸收光谱等手段,考察了嵌段共聚物对样品微结构和可见光活性的影响.结果表明,样品主要以锐钛矿相和板钛矿相混合形式存在;改变嵌段共聚物的浓度,可以制得晶粒粒径9～12 nm,孔径10～14 nm,禁带宽度2.98～2.76 eV的大孔-介孔N-TiO2,且随着模板剂加入量的增加,大孔孔径增大,孔壁增厚.对甲基橙溶液的室内自然光降解实验表明,大孔-介孔N-TiO2具有良好的光催化活性,随着嵌段共聚物加入量的增加,样品对甲基橙的降解时间缩短,降解率提高.     

H_3PW_(12)O_(40)/TiO_2(锐钛)的超声制备及降解染料的研究

采用超声法,在80℃下,制备了H3PW12O40/TiO2(锐钛)复合催化剂,并采用XRD、FT-IR等方法对样品进行了表征。通过染料刚果红和亚甲基蓝为模拟污染物的光催化降解实验考察了复合催化剂的光催化活性。结果表明,在太阳光下,复合光催化剂的催化活性高于单体TiO2,H3PW12O40/TiO2(锐钛)在90min内,对溶液中刚果红的去除率达99.17%,对亚甲基蓝溶液的TOC去除率达73.17%。复合催化剂在反复实验5次后,仍能保持有效的催化性能。     

Si掺杂介孔SO_4~(2-)/TiO_2的非模板剂法合成及表征

在不使用模板剂的条件下,以工业硫酸氧钛溶液为原料合成介孔偏钛酸前驱体,再经正硅酸乙酯浸渍焙烧制备了具有良好热稳定性的Si掺杂介孔SO42-/TiO2.采用X射线衍射、N2吸附-脱附、扫描电镜、X射线能谱和傅里叶变换红外光谱等表征方法对样品的组成和结构进行了分析,并考察了该材料在亚甲基蓝氧化降解反应中的光催化性能.结果表明,在焙烧过程中,被吸附在偏钛酸孔道内的正硅酸乙酯发生水解,并与偏钛酸孔壁上的自由羟基形成Ti-O-Si键;Si进入二氧化钛骨架中,对孔结构起到了支撑作用,从而提高了介孔SO42-/TiO2的热稳定性.700℃焙烧2 h后,Si掺杂介孔SO42-/TiO2材料的比表面积仍达到189 m2/g,平均孔径为2.8 nm.400℃焙烧的样品在亚甲基蓝降解反应中表现出较好的光催化活性.     

Preparation and Photocatalytic Activity of Mesoporous TiO2 Photocatalyst Co‐doped with Fe and H3PW12O40

The mesoporous titanium dioxide (MTiO₂) photocatalysts co‐doped with Fe and H₃PW₁₂O₄₀ were synthesized by template method using tetrabutyl titanate (Ti(OC₄H₉)₄), Fe(NO₃)k₃9H₂Oand H₃PW₁₂O₄₀ as precursors and Pluronic P123 as template. The as‐prepared photocatalyst was characterized by N₂ adsorption‐desorption measurements, X‐ray diffraction (XRD), scanning electron microscopy (SEM) and UV‐vis adsorption spectroscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl blue (MB) (50 mg/L) in an aqueous solution. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of ca. 10 nm with high surface area of ca. 150 m²/g. The results of MB photodecomposition showed that co‐doped mesoporous TiO₂ exhibited higher photocatalytic activities than un‐doped, single‐doped mesoporous TiO₂ under UV and visible light irradiation. It was shown that the co‐doped MTiO₂ could be activated by visible light and could thus be used as an effective catalyst in photo‐oxidation reactions. The synergistic effect of Fe and H₃PW₁₂O₄₀ co‐doping played an important role in improving the photocatalytic activity.     

Preparation and Photocatalytic Activity of Ce,H3PW12O40 co-doped TiO2 Hollow Fibers

A series of Ce, H3PW12O40 co-doped TiO2 hollow fibers photocatalysts have been prepared by sol-gel method using ammonium ceric nitrate, H3PW12O40 and tetrabutyltitanate as precursors and cotton fibers as template, followed by calcination at 500 ℃ in N2 atmosphere for 2 h. Scanning electron microscopy, X-ray diffraction, nitrogen adsorption-desorption mea- surements, and UV-Vis spectroscopy are employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The photo- catalytic performance of the samples has been studied by photodegradation phenol in water under UV and visible light irradiation. The results show that the TiO2 fiber materials have hollow structures, and the co-doped TiO2 hollow fibers exhibit higher photocatalytic activities for the degradation of phenol than un-doped, single-doped TiO2 hollow fibers under UV and visible light. In addition, the recyclability of co-doped TiO2 fibers is also confirmed that the TiO2 fiber retains ca. 90% of its activity after being used four times. It is shown that the co-doped TiO2 fibers can be activated by visible light and may be potentially applied to the treatment of water contaminated by organic pollutants. The synergistic effect of Ce and H3PW12O40 co-doping plays an important role in improving the photocatalytic activity.     

Hydrothermal Synthesis of H3PW12O40/TiO2 Nanometer Photocatalyst and Its Catalytic Performance for Methyl Orange

H3PW12O40/TiO2 nanometer photocatalyst was prepared by one step hydrothermal synthesis from H3PW12O40′nH2O and Ti(OBu)4,simultaneously realizing the load and modification of H3PW12O40.The catalyst was ...     

微波增强H3PW12O40／TiO2光催化降解染料和水杨酸的研究

以孔雀石绿为模型分子, 考察了微波无极灯的形状、微波功率和溶液初始浓度对光催化降解效果的影响. 并且在最佳微波反应条件下, 考察了通过溶胶-凝胶再结合程序升温水热法制备的复合材料H3PW12O40/TiO2对刚果红、酸性黑、酸性品红和水杨酸的光催化降解情况. 结果表明, 微波无极灯具有更好地增强H3PW12O40/TiO2光催化降解有机污染物的作用.     

Tunable Synthesis of Core-shell α-Fe2O3/TiO2 Composite Nanoparticles and Their Visible-light Photocatalytic Activity

Uniform α-Fe₂O₃/amorphous TiO₂ core-shell nanocomposites were prepared via a hydrolysis method and α-Fe₂O₃/anatase TiO₂ core-shell nanocomposites were obtained via a post-calcination process. The structure and morphology of the products were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy. Amorphous TiO₂ nanoparticles with diameters of ten to several tens nanometer were formed on the surface of α-Fe₂O₃ nanoparticles and the coverage density of the secondary TiO₂ nanoparticles in the composite can be controlled by varying the concentration of Ti(BuO)₄ in the ethanol solution. The visible-light photocatalytic properties of different products towards Rhodamine B(RhB) were investigated. The results show that the α-Fe₂O₃/amorphous TiO₂ exhibits a good photocatalytic property owing to the extension of the light response range to visible light and the efficient separation of photogenerated electrons and holes between α-Fe₂O₃ and amorphous TiO₂.     

Synthesis of Cs2.5H0.5PW12O40/TiO2 Nanocomposites with Dominant TiO2 {001} Facets and Related Photocatalytic Properties

TiO₂ nanosheets with dominant {001} facets, coupled with Cs_2.5H_0.5PW₁₂O₄₀, were successfully synthesized by a one‐step hydrothermal reaction. The photocatalytic activity of nanocatalysts was evaluated by the degradation of Rhodamine B under UV light irradiation. The results showed that both the addition of Cs_2.5H_0.5PW₁₂O₄₀ and the exposed {001} facets of TiO₂ have a positive effect on the photocatalytic activity. The improved photoactivity of nanocomposites in comparison with that of TiO₂ nanosheets could be attributed to the synergistic effect between Cs_2.5H_0.5PW₁₂O₄₀ and TiO₂ which facilitates the separation of photo‐induced hole‐electron pairs.     

Photocatalytic Activity of Fe and Ce Co‐doped Mesoporous TiO2 Catalyst under UV and Visible Light

The catalysts of un‐doped, single‐doped and co‐doped mesoporous titanium dioxide (MTiO₂) were prepared by a template method with tetrabutyltitanate (Ti(OC₄H₉)₄) as a Ti source material and Pluronic P123 as a template. The photo‐absorbance of the obtained catalysts was measured by UV‐vis absorption spectroscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl orange (MO) (50 mg/L) in an aqueous solution. It was shown that the co‐doped MTiO₂ could be activated by visible light and could thus be used as an effective catalyst in photo‐oxidation reactions. The effect of Fe and Ce co‐dopants on the material properties was investigated by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and N₂ adsorption‐desorption isotherm measurement. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of ca. 10 nm with high surface area of ca. 150 m²/g. The photocatalytic activity of MTiO₂ co‐doped with Fe and Ce was markedly improved due to the synergistic actions of the two dopants.     

孔道结构H3PW12O40/TiO2的制备及其可见光光催化降解水溶性染料的性能

 采用溶胶-凝胶方法制备了孔道结构复合材料H3PW12O40/TiO2,采用ICP-AES,UV/DRS,31P MAS NMR,TEM和N2吸附等技术对其组成和结构进行了表征. 结果表明,催化剂中活性组分H3PW12O40的基本骨架结构未发生改变,H3PW12O40的担载量为22.29%,催化剂平均粒径为40 nm,具有双孔结构,其平均微孔和介孔孔径分别为0.61和3.06 nm. 考察了催化剂可见光光催化降解6种水溶性染料的性能. 结果表明,6种染料均可不同程度地被降解和矿化. 通过对染料中性红的光催化降解实验,比较了H3PW12O40/TiO2,Degussa P-25和锐钛矿结构TiO2的可见光光催化活性,其中,H3PW12O40/TiO2活性最高,且催化剂最易分离,可循环使用.     

Preparation and Photocatalysis of Mesoporous TiO2 Nanofibers via an Electrospinning Technique

Mesoporous TiO₂ nanofibers have been synthesized by a new method that combines sol-gel chemistry and electrospinning technique. The obtained mesoporous TiO₂ nanofibers were characterized with scanning electron microscopy(SEM), X-ray diffraction(XRD), transmission electron microscopy(TEM) and nitrogen adsorption-desorption isotherms. The photocatalytic performance was evaluated by the photocatalytic degradation of Rhodamine B under UV light irradiation. The results show that mesoporous TiO₂ nanofibers exhibit higher photocatalytic activity compared with nonporous TiO₂ nanofibers.     

MoO3/TiO2 和WO3/TiO2 光催化分子氧氧化甲烷的活性

以Ｓｏｌ－Ｇｅｌ法制备的、表面积和孔径相近的含水ＭｏＯ３／ＴｉＯ２、ＷＯ３／ＴｉＯ２为催化剂,光催化分子氧氧化甲烷,初步研究表明,催化剂的活性高于ＴｉＯ２,且有少量的甲醇生成。