双晶型TiO2薄膜的低温制备及表征

采用溶胶-凝胶法低温制备了具有锐钛矿、板钛矿双晶型的TiO2薄膜. 分别利用X射线衍射(XRD)、透射电子显微镜(TEM)、UV-Vis透光率曲线和原子力显微镜(AFM)等手段对所得TiO2溶胶和薄膜进行了性能表征. 采用光催化降解罗丹明B水溶液评价TiO2薄膜的光催化活性. 结果发现, 所得TiO2薄膜具有较高的透明度和光催化活性. 同时, 考察了溶胶回流温度对所制备TiO2薄膜性能的影响, 发现升高溶胶回流温度可以完善薄膜的晶型, 增大薄膜的粗糙度, 从而提高薄膜的光催化活性. 溶胶回流温度为100 ℃时所制备的TiO2薄膜具有最高的光催化活性.     

Preparation of montmorillonite/titania nanocomposite and enhanced electrorheological activity

We prepared a new type of electrorheological particle composed of TiO2 nanocrystallites-coated montmorillonite (MMT/TiO2) nanocomposite by the sol-gel technique. The characterizations including TGA, XRD, TEM, SEM, EDS, and FTIR showed that TiO2 was deposited on the surface of the MMT flakes with anatase nanocrystallite. An obviously enhanced ER effect was found in the MMT/TiO2 nanocomposites based ER fluids compared with pure MMT and TiO2. Furthermore, the temperature and sedimentation stabilities of the MMT/TiO2 ER fluids had also been improved greatly. Interestingly, the content of TiO2 was demonstrated to have an important influence on the ER effect. When the content of TiO2 was about 20 wt%, the ER effect of MMT/TiO2 ER fluid reached its maximum, which was about 5 times that of pure MMT ER fluid and 27 times that of pure TiO2 ER fluid. Based on dielectric analysis, the significant ER enhancement by formation nanocrystallites-coated montmorillonite was attributed to the enhanced interfacial polarization in this nanocomposite particle due to the effective limitation of the long-range drift of active ions in montmorillonite particles.     

聚合物调控氧化钛层柱蒙脱石的结构和性能研究

为了改善氧化钛层柱蒙脱石的结构性能,以长链聚合物-端氨基聚甲基环氧乙烷(PPO-D-2000)为结构调节剂,调控合成了聚合物-氧化钛层柱蒙脱石材料。采用X射线粉末衍射、红外、拉曼光谱、TG/DSC、TEM和BET等手段进行了结构表征。结果表明,相比于小分子量表面活性剂而言,长链聚合物不仅能显著提高氧化钛层柱蒙脱石中的二氧化钛含量,而且比表面积比单独氧化钛柱撑蒙脱石增加了约13%,达到241.52m2/g,尤其是孔径、孔体积等孔道结构参数增加一倍左右。将合成的柱撑蒙脱石材料应用于对水中甲基橙的吸附和光催化性能研究表明,聚合物的调控作用能提高氧化钛层柱蒙脱石的吸附能力,光催化效率也有所改善。因此,聚合物对优化无机层柱粘土材料结构、改善吸附和催化性能具有良好的调控作用,为发展环境催化材料提供了新的途径。     

Preparation and enhanced visible-light photocatalytic H2-production activity of CdS-sensitized Pt/TiO2 nanosheets with exposed (001) facets

CdS-sensitized Pt/TiO(2) nanosheets with exposed (001) facets were prepared by hydrothermal treatment of a Ti(OC(4)H(9))(4)-HF-H(2)O mixed solution followed by photochemical reduction deposition of Pt nanoparticles (NPs) on TiO(2) nanosheets (TiO(2) NSs) and chemical bath deposition of CdS NPs on Pt/TiO(2) NSs, successively. The UV and visible-light driven photocatalytic activity of the as-prepared samples was evaluated by photocatalytic H(2) production from lactic acid aqueous solution under UV and visible-light (λ ≥ 420 nm) irradiation. It was shown that no photocatalytic H(2)-production activity was observed on the pure TiO(2) NSs under UV and/or visible-light irradiation. Deposition of CdS NPs on Pt/TiO(2) NSs caused significant enhancement of the UV and visible-light photocatalytic H(2)-production rates. The morphology of TiO(2) particles had also significant influence on the visible-light H(2)-production activity. Among TiO(2) NSs, P25 and the NPs studied, the CdS-sensitized Pt/TiO(2) NSs show the highest photocatalytic activity (13.9% apparent quantum efficiency obtained at 420 nm), exceeding that of CdS-sensitized Pt/P25 by 10.3% and that of Pt/NPs by 1.21%, which can be attributed to the combined effect of several factors including the presence of exposed (001) facets, surface fluorination and high specific surface area. After many replication experiments of the photocatalytic hydrogen production in the presence of lactic acid, the CdS-sensitized Pt/TiO(2) NSs did not show great loss in the photocatalytic activity, confirming that the CdS/Pt/TiO(2) NSs system is stable and not photocorroded.     

A new photocatalyst: Bi2TiO4F2 nanoflakes synthesized by a hydrothermal method

A pure phase of Bi(2)TiO(4)F(2) nanoflakes with layered Aurivillius structure are synthesized by a simple hydrothermal method. The as-prepared sample is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and UV-vis diffuse reflectance spectroscopy. The OH radicals produced during the photocatalytic reaction is detected by a photoluminescence (PL) technique. The electronic structure is investigated by DFT calculations. The photocatalytic properties of Bi(2)TiO(4)F(2) are explored by degradation of Rhodamine B (RhB) and phenol. The results show that Bi(2)TiO(4)F(2) exhibits much higher photocatalytic performances than Bi(4)Ti(3)O(12) due to the unique layered structure and the existence of F. F acts as an electron trapper, which enhances the separation of photogenerated electron-hole pairs, and lead to higher photocatalytic activity. Reaction with terephthalic acid demonstrates that OH radicals are formed as a result of UV irradiation of Bi(4)TiO(4)F(2) in solution, in agreement with the proposed mechanism. Thus, Bi(2)TiO(4)F(2) can be used as a new efficient photocatalyst.     

Preparation and characterization of ZnS nanoparticles deposited on montmorillonite

ZnS nanoparticles were prepared and deposited on montmorillonite (MMT) in the presence of cetyltrimethylammonium (CTA). UV spectrometry and transmission electron microscopy (TEM) proved the formation of nanoparticles with diameters ranging from 3 nm to 5 nm. Selected-area electron diffraction (SAED) patterns revealed the presence of romboedric ZnS. The band gap energy of nanosize ZnS was estimated at 3.89 ± 0.03 eV. Photoluminescence spectra exhibited a strong emission band between 300 nm and 600 nm explained by the vacant ZnS nanostructure. The prepared ZnS-montmorillonite nanocomposite (ZnS-MMT) was used for the photocatalytic reduction of CO(2) providing a considerably high efficiency that exceeded 5-6-fold the results of commercial TiO(2) Degussa P25. The main reaction products were hydrogen and methane. Methanol and carbon oxide were also observed in about 7-fold lower amounts. The stability of ZnS against oxidation was confirmed by the determination of sulphate using capillary isotachophoresis.     

C-N共掺杂纳米TiO2的制备及其光催化制氢活性

采用TiCN粉末在空气气氛中不同温度下焙烧制得C-N共掺杂的纳米TiO2光催化剂. 利用X射线衍射(XRD)、透射电镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)以及X射线光电子能谱(XPS)等手段对其进行了表征. XRD和XPS结果表明, TiCN中的C和N元素可以被O取代得到C-N共掺杂的TiO2. DRS结果表明, 所制得的C-N共掺杂的TiO2在可见光区域比P25表现出更强的光吸收性能. 以Na2S-Na2SO3体系为牺牲剂, 分别考察了不同温度下焙烧得到的C-N共掺杂的TiO2光催化分解水产氢的活性. 结果表明, 550 ℃焙烧得到的C-N共掺杂的TiO2在紫外光照射下具有最高的光解水产氢活性,产氢速率为41.1 μmol·h-1, 大于P25的光解水产氢活性(26.2 μmol·h-1). 在紫外-可见光照射下, 光解水产氢速率仅为0.2 μmol·h-1, 这可能是由于C-N掺杂引起的可见光范围的吸收对光催化分解水产氢活性的贡献较小.     

One-step fabrication and high photocatalytic activity of porous TiO2 hollow aggregates by using a low-temperature hydrothermal method without templates

Porous TiO2 hollow aggregates have been synthesized on a large scale by means of a simple hydrothermal method without using any templates. The as-prepared products were characterized by means of field emission scanning electron microscopy, XRD, TEM, nitrogen adsorption, UV/Vis diffuse reflectance spectroscopy, and FTIR spectroscopy. The photocatalytic activity of the aggregates was demonstrated through the photocatalytic degradation of Rhodamine B. Structural characterization indicates that the porous TiO2 aggregates are 500-800 nm in diameter and display mesoporous structure. The average pore sizes and BET surface areas of the aggregates are 12 nm and 168 m2 g-1, respectively. Optical adsorption investigations show that the aggregates possess an optical band-gap energy of 3.36 eV. The as-prepared products were substantially more effective photocatalysts than the commercially available photocatalyst P25. The dye degradation rate of the porous TiO2 hollow aggregates is more than twice that of P25. The high photoactivities of the aggregates can be attributed to the combined effects of several factors, namely, large surface areas, the existence of mesopores, and the high band-gap energy. In addition, the as-prepared products can be easily recycled.     

二氧化钛包裹碘单质(I2/TiO2)制备及其光催化降解苯酚

采用水热法,以Ti(SO₄)₂为钛源,KIO₃为掺碘剂制备了具有高可见光活性,高稳定性的二氧化钛包裹碘单质(I₂/TiO₂)光催化剂.利用X射线光电子能谱(XPS)、X射线晶体粉末衍射(XRD)、透射电子显微镜(TEM)和紫外可见漫反射光谱(DRS)等表征手段对样品进行表征.结果表明,I₂/TiO₂中除含有锐钛矿相二氧化钛外、还含有碘单质和碘酸;I₂/TiO₂粒径大小为45 nm左右;在波长384 nm至700 nm范围内,该催化剂有强烈的吸收.探讨了该催化剂的形成过程和可见光催化机理.以苯酚降解反应为探针,测定了I₂/TiO₂光催化活性.结果显示:在全谱光源照射下I₂/TiO₂活性略高于P25,在可见光范围内其活性是P25的3倍多.确定了降解苯酚的最佳条件:全谱光源照射,投加量为0.5 g/L,苯酚浓度大于10 mg/L,溶液pH为3.2.I₂/TiO₂重复使用4次后,催化活性没有明显下降.     

三维有序介孔/大孔TiO2微球的制备、表征及光催化性能

以聚甲基丙烯酸甲酯微球为模板,分别以钛酸四丁酯和四异丙醇钛为钛源,通过溶胶-凝胶法辅助模板法制得TiO2纳米微球前驱体,并用程序升温控制其焙烧温度,最终成功制得了具有三维有序介孔/大孔复合结构的TiO2微球.以罗丹明B(RhB)为模型污染物,探索了以不同钛源制备得到的介孔/大孔复合TiO2微球的光催化性能;并采用XRD、SEM、TEM、UV-vis DRS、比表面积测试、光催化性能测试等对样品的晶粒尺寸、物相、形貌、光吸收、比表面积及性能等进行了分析.结果表明,运用溶胶凝胶法辅助模板法能够合成结晶度高、形貌规整、比表面积大、光催化活性良好的锐钛矿相TiO2微球.     

表面活性剂辅助水热合成氧化钛纳米针溶胶

TiO₂ nanoneedles sol with particle size of 10～15 nanometer was synthesized by hydrothermal method using peroxo titanic acid as the precursor, cetyltrimethyl ammonium bromide(CTAB) as the surfactant. The product was characterized by XRD, TEM, HRTEM and selected area electron diffraction(SAED). The results show that the as-prepared products have high crystallinity and grow along the c-axis, with homogeneous morphology and good monodispersity. In addition, TiO₂ hydrosol possessed good photocatalytic activity for the photocatalytic degradation of methyl orange aqueous solution under the sunlight illumination.     

蒙脱土/二氧化钛复合颗粒电流变液材料的制备及其性能

利用溶胶-凝胶法制备了一种新型的蒙脱土/二氧化钛(MMT/TiO_2)复合电流变 颗粒材料，FT-IR，XRD，SEM分析表明TiO_2以纳米晶的形态包覆于蒙脱土表面。电 流变性能测试表明，MMT/TiO_2复合颗粒的电流变效应比纯蒙脱土电流变液有显著 提高，当颗粒体积分数为25%，直流电场强度为3kV/mm时，TiO_2质量分数为22.7% 的MMT/TiO_2复合颗粒电流变液的静态屈服应力达8.3kPa，此值约为纯蒙脱土电流 变液的4倍。同时发现TiO_2包覆量对电流变效应有重要影响。     

微乳法制备纳米TiO2 /SiO2的结构及光催化研究

Nanosized TiO₂ and TiO₂/SiO₂ particles were prepared by hydrolysis of tetrabutyl titanate (TBOT) and tetraethyl orthosilicate (TEOS) in the TX-100 reverse microemulsion. These particles were characterized by TG-DSC, XRD, FTIR, TEM，N₂ adsorption-desorption. Their photocatalytic activity was tested by degradation of methyl orange. The result shows that TiO₂/SiO₂ nanoparticles are with a monodispersed spherical phase and a uniform size distribution，and TiO₂ particles are dispersed on the surface of SiO₂. The band for Ti-O-Si vibration in FTIR was observed, the Ti-O-Si bond increased the stability of anatase TiO₂, suppressed the phase transformation of titania from anatase to rutile. And due to the addition of SiO₂, the average size of titania decreased from 38 nm in pure TiO₂ to 5 nm in TiO₂/SiO₂. It was found, under UV light irradiation, TiO₂/SiO₂ particles showed higher activity than pure TiO₂, and TiO₂/SiO₂(1/1) particles showed the highest photocatalytic activity on the photocatalytic decomposition of methyl orange, which was influenced by crystal structure, particle size, crystallinity and Surface area Characteristics.     

Synthesis of highly efficient C-doped TiO(2) photocatalyst and its photo-generated charge-transfer properties

Carbon-doped anatase TiO(2) was prepared by a facile hydrothermal process without adding additional carbon source. The as-prepared sample shows highly efficient photocatalytic activity, which only requires 4min and is about 11 times higher than that of Degussa P25 TiO(2) in degradation of methyl orange (MO) dye under UV light irradiation. Moreover, a highly visible-light activity is also observed. UV-vis diffuse reflectance spectra and X-ray photoelectron spectroscopy confirm that the carbon atoms are incorporated into the interstitial positions of TiO(2) lattice and form a strong interaction with titanium atoms and extend photoresponding range to 700nm. Surface photovoltage spectra (SPS) and transient photovoltage (TPV) suggest that the presence of interstitial carbons induce several localized occupied states in the gap, enhance the separation extent and restrain the recombination of the photo-induced electron and hole carriers in TiO(2).     

Enhanced photocatalytic activity of mesoporous TiO2 aggregates by embedding carbon nanotubes as electron-transfer channel

Mesoporous multiwalled carbon nanotubes/titanium dioxide (CNTs/TiO(2)) nanocomposites with low loading amounts (0-0.5 wt%) of CNTs embedded inside mesoporous TiO(2) aggregates has been prepared by a simple one-pot hydrothermal method using titanium sulfate as titanium source. The as-prepared CNTs/TiO(2) samples are carefully characterized, analyzed and discussed. In contrast to previous reports with high CNT loading, our results indicate that a low CNT loading slightly influences the textural properties (including crystallite size, degree of crystallinity, specific surface areas, and pore volume etc.) and UV-light absorption of the mesoporous TiO(2) aggregates. The SEM and TEM results demonstrate that the CNTs are mostly embedded in the mesoporous TiO(2) aggregates. Moreover, chemical bonds are formed at the interface between CNTs and TiO(2), which is confirmed by the Raman, IR and XPS analyses. Significantly, we point out that PL analysis in terms of intensity of PL signals seems to not be a reliable way to monitor the recombination rate in the CNTs/TiO(2) composite, due to the quenching effect of CNTs. Instead, the analysis of transient photocurrent responses is introduced, which definitely reflects CNTs as fast electron transfer channels in chemically-bonded CNTs/TiO(2) composites with low CNT loading. Notably, the positive synergy effects of CNTs and TiO(2) depend on both the CNT loading amount and the state of interfacial contacts. In our study, only these chemically bonded CNTs/TiO(2) nanocomposites with appropriate loading amounts (<0.1 wt%) favor the separation of photogenerated electron-hole pairs and decrease their recombination rate and thus display significantly enhanced photocatalytic activity for degrading acetone in air under UV irradiation, as compared with pristine TiO(2) counterparts and commercial P25 photocatalyst. In contrast, a high CNT loading (>0.1 wt%) results in a decrease in photocatalytic activity; a simple mechanical mixing of CNTs and TiO(2) without forming chemical bonds at the interface also results in inferior photocatalytic performance.     

Ag-TiO2/蒙脱土复合纳米光催化剂的研究

本文以蒙脱土(简称MMT)为载体,利用四氯化钛水解法将纳米TiO2引入到蒙脱土层间,经500℃煅烧后得到稳定结构的TiO2柱撑蒙脱土,再通过化学还原法将金属银负载于其上,合成出载银/二氧化钛柱撑蒙脱土复合光催化剂(Ag-TiO2/MMT).通过XRD、IR、BET、AAS等分析方法对复合光催化剂的物相组成、键合状况、比表面积、元素含量等物化性质进行了表征.对降解亚甲基蓝的光催化活性测试表明具有如下的光催化活性序列:Ag-TiO2/MMT>TiO2/MMT>TiO2(P25),其中Ag-TiO2/MMT由于柱化后具有较大的比表面积和Ag的负载改性而具有最高的光催化活性.     

氟掺杂锐钛矿型TiO2溶胶的制备、表征及催化性能

以四氯化钛为前驱物, 采用改性的沉淀-溶胶-水热晶化法制备了一种具有锐钛矿型结构的氟掺杂的二氧化钛(F-TiO₂)溶胶. 研究了氟掺杂、水热晶化的温度、时间及介质pH值对溶胶粒子的晶型和晶化度的影响. 采用XRD, TG-DTA, TEM, UV-Vis-DRS, FTIR, XPS技术及吸附、表面酸度测定手段对溶胶粒子的结构进行了表征. XRD分析结果表明: 氟的掺入可以降低水热晶化反应的温度或减少反应时间、提高粒子的晶化度, 溶胶粒子具有锐钛矿型结构; TEM分析显示: 粒子呈圆球型, 平均粒径大约为6.5 nm. XPS测定结果表明; 氟在溶胶粒子中以吸附态和结合态两种形式存在; 吸附、表面酸度及光催化活性测定表明: 与P25型TiO₂及纯TiO₂溶胶粒子相比, F-TiO₂溶胶粒子具有更大的吸附能力、更强的表面酸度及更高的光催化活性. 还从光生载流子分离效率等方面探讨了掺杂对催化剂活性影响的机理.     

Electrospun nanofibers of TiO2/CdS heteroarchitectures with enhanced photocatalytic activity by visible light

Herein, we have demonstrated that the electrospun nanofibers of TiO(2)/CdS heteroarchitectures could be fabricated through combining electrospinning technique with hydrothermal process. The configuration, crystal structure, and element composition of the as-prepared TiO(2)/CdS heteroarchitectures were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), resonant Raman spectrometer, X-ray photoelectron spectroscopy (XPS). The results indicated that the high-density hexagonal wurtzite CdS crystalline particles of ca. 6-40 nm in diameter were uniformly and closely grown on anatase TiO(2) nanofibers. Especially, the light-absorption properties as well as photocatalytic characteristics of pure TiO(2) nanofibers and TiO(2)/CdS heteroarchitectures with different amount loading of CdS were also investigated. The absorption of TiO(2)/CdS heteroarchitectures was extended to the visible due to effective immobilization of sensitizing agent CdS on TiO(2). In contrast with the pure TiO(2) nanofibers, the TiO(2)/CdS heteroarchitectures showed excellent photocatalytic activity by using rhodamine B dye as a model organic substrate under visible-light irradiation. It was worth noting that the cooperative photocatalytic mechanism of the TiO(2)/CdS heteroarchitectures was also discussed.     

Synthesis of LaVO4/TiO2 heterojunction nanotubes by sol-gel coupled with hydrothermal method for photocatalytic air purification

With the aim of improving the effective utilization of visible light, the LaVO(4)/TiO(2) heterojunction nanotubes were fabricated by sol-gel coupled with hydrothermal method. The photocatalytic ability was demonstrated through catalytic removal of gaseous toluene species. The nanotube samples were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), surface photovoltage (SPV), Raman spectra and N(2) adsorption-desorption measurements. The characterization results showed that the samples with high specific surface areas were of typical nanotubular morphology, which would lead to the high separation and transfer efficiency of photo induced electron-hole pairs. The as-prepared nanotubes exhibited high photocatalytic activity in decomposing toluene species under visible light irradiation with fine photochemical stability. The enhanced photocatalytic performance of LaVO(4)/TiO(2) nanotubes might be attributed to the matching band potentials, the interconnected heterojunction of LaVO(4) versus TiO(2), and the large specific surface areas of nanotubes.     

BiOCl/蒙脱土复合光催化剂的制备及其光催化活性

为优化BiOCl光催化剂的结构,改善其对有机污染物的吸附性能,进而提高光催化反应活性,采用超声辅助化学沉淀法制备了BiOCl/蒙脱土(MMT)复合光催化剂,并考察了MMT质量分数(w(MMT))对复合光催化剂结构及光催化反应活性的影响。 X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)和紫外-可见漫反射光谱(DRS)等的表征结果表明,所得催化剂呈微球状结构,禁带宽度为3.24 eV。 随着w(MMT)的增加,催化剂的微球状结构逐渐被破坏,但带隙能未发生明显变化。 以8-羟基喹啉为目标物考察了复合催化剂的吸附及光催化反应活性。 结果表明,随着w(MMT)增加,催化剂对8-羟基喹啉的吸附和光催化氧化活性逐渐增加,这可归因于与MMT的复合增大了比表面积并降低了光生载流子复合效率。 当w(MMT)为15%时,催化剂的吸附及光催化性能达到最佳,光照50 min后,8-羟基喹啉的降解率达到85.6%,矿化率达到51.0%。 光生空穴和超氧自由基负离子为主要的氧化活性物种。 复合催化剂还可高效降解邻苯二酚和对氨基苯甲酸。 同时,复合光催化剂表现出较强的化学稳定性,表明其具有较强的实际应用价值,可用于处理含有机酚类污染物的工业废水。