纳米TiO2微球的制备及其光催化性能研究

以四氯化钛为钛源,采用无模板溶剂热法合成了纳米TiO_2微球,采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、紫外-可见分光光度计(UV-Vis)、N_2吸附-脱附等分析方法对样品进行表征,考察水热反应时间对纳米TiO_2微球的形成及光催化降解气相苯的影响。结果表明:纳米TiO_2微球是由锐钛矿相纳米颗粒自组装形成的分级微/纳结构,光吸收出现"蓝移",比表面积高达239.2m~2/g;纳米TiO_2微球的结构参数对其最终的光催化性能影响较大,在水热温度180℃、水热反应时间24h条件下制备的纳米微球表现出最高的光催化活性,其矿化率高于商用P25TiO_2近2倍;纳米TiO_2微球优异的光催化性能得益于其优良的结晶度、相对大的比表面积和丰富的介孔结构。     

二氧化钛纳米棒自组装微米球的制备、性能及其生长机理

用水热法在180℃一步合成了TiO2纳米棒自组装微米球,并对其光催化性能和形成机理进行了分析。采用X-射线衍射(XRD),扫描电镜(SEM),透射电镜(TEM)和氮气吸附(BET)对催化剂的物相、颗粒粒径及比表面积进行了表征,结果显示产物为金红石型结构,呈纳米棒自组装微米球形貌,微米球中纳米棒的直径约为30纳米。氮气吸附解附实验表明微米球比表面积为31.2m2/g,介孔的尺寸为3.88nm。催化实验显示其在可见光下的催化能力优于P25。     

醇热法制备球形TiO2及其光催化活性研究

以钛酸四丁酯为钛源,乙醇和丙三醇混合液为溶剂,采用醇热法制备球形二氧化钛(TiO_2)。考察了丙三醇的用量对产物结构和性能的影响。以盐酸四环素为目标物,考察了制得的纳米TiO_2的光催化活性。研究结果表明:丙三醇与乙醇的体积配合比1∶0.2制得的球形纳米TiO_2对盐酸四环素的光催化降解效果最佳,在纳米TiO_2光催化剂投加量为1g/L,盐酸四环素为0.1g/L,紫外光或模拟太阳光照2h条件下,对盐酸四环素的降解率分别达到98.58%和90.00%。     

纳米TiO_2的光催化性能改进及其在环境保护中的应用研究

基于纳米二氧化钛光催化性能的广泛应用及其在应用时效率偏低的问题,从抑制TiO2内载流子的复合、提高催化剂的比表面积和改变催化剂的结构与表面性质3个方面综述了修饰纳米二氧化钛以提高其光催化性能的各项措施,并从污水处理、空气净化、抗菌除臭等方面评述了纳米TiO2在环境保护领域中的应用。     

分级微/纳结构ZnO的制备及其光催化性能

分别采用溶剂热法和草酸盐法制得具有分级微/纳结构但形貌迥异的两种ZnO材料,以亚甲基蓝溶液(MB)作为目标降解物对其光催化性能进行评价。结果表明:溶剂热法所制得的ZnO呈花状微球形貌,由纳米片自组装而成;草酸盐法所制得的ZnO为微米棒状形貌,以纳米颗粒为基本单元发展而来。草酸盐法ZnO材料具有更为优异的光催化性能,其对亚甲基蓝溶液的降解反应速率常数是溶剂热法ZnO材料的7.65倍。活性自由基物种鉴定结果证实,两种ZnO材料在受到紫外光激发时均能产生·OH和·O₂^-活性自由基。两种ZnO样品光催化性能的差别源于能带结构不同所引起的活性自由基生成数量上的差异。较之溶剂热法ZnO,草酸盐法ZnO在受紫外光激发时产生的·OH和·O₂^-数量更多,且以强氧化能力的·OH为主,因而表现出更为优异的光催化性能。     

升温速率对氧化锌空心微球形貌及性能的影响

以乙酸锌为锌源,采用溶剂热技术,在2.92、1.46、0.97、0.73、0.49℃/min 5组不同升温速率下制备了氧化锌空心微球。分别采用XRD和SEM对样品的物相结构和形貌特点进行了表征,用荧光分光光度计测试了样品的室温光致发光性能,研究了升温速率对产物形貌的影响。结果表明:随着升温速率下降,氧化锌空心微球断面的小晶粒逐渐溶解,所形成的较大晶粒延空心微球的径向连接在一起,形成光滑的纳米棒,纳米棒的末端逐渐显现出比较清晰的六棱锥状结构。微球的结晶度逐渐提高,晶粒的平均粒径呈现先减小后增大的规律,紫外发射峰发生了红移。     

TiO_2纳米颗粒/纳米棒阵列复合薄膜的制备及其光电催化性能

以金属钛箔为钛源,采用双氧水和盐酸体系,通过水热法制备合成TiO2纳米棒阵列薄膜,并通过调节双氧水和盐酸的用量,调控TiO2纳米棒阵列薄膜的微观形貌和物相构成。结合溶剂挥发自组装法将TiO2纳米颗粒引入纳米棒阵列中,得到复合型TiO2光催化剂。以亚甲基蓝为模拟污染物,考察TiO2复合薄膜的光催化活性。通过扫描电镜(SEM)和X射线衍射(XRD)测试对TiO2复合薄膜的物相和表面形貌等进行了表征,并采用电化学交流阻抗法(EIS)分析其表面电荷转移特性。TiO2纳米颗粒/纳米棒阵列复合薄膜在光电协同条件下,展示出高的光电催化活性。     

甲醇介质中溶剂热合成六方CdS中空纳米球

以甲醇为溶剂, 硝酸镉和硫脲为原料, 通过溶剂热法合成了CdS中空纳米球, 采用TEM、EDS和XRD对样品形貌和结构进行了表征. TEM与EDS分析显示产物主要为洋葱状CdS中空纳米球, 外径为5～17nm, 空腔直径为3～14nm. XRD分析结果表明,CdS中空纳米球为六方纤锌矿结构. 并初步考察了醇类溶剂对形成CdS纳米结构的影响. 结果表明,当以无水乙醇或正戊醇为溶剂时,产物分别为CdS颗粒团簇或CdS纳米颗粒组装的微球,说明甲醇对中空结构的形成起了重要作用. 以甲醇作溶剂时, 中空纳米球的形成可能是CdS纳米片层高压下卷曲形成的.      

中空结构纳米TiO2微球的可控制备

纳米TiO_2作为一种氧化还原能力强、化学性质稳定、来源广泛和环境友好的多功能材料,被认为是非常有前景的半导体光催化材料之一。在各种形貌的纳米TiO_2中,中空结构TiO_2微球因具有密度低、比表面积大、渗透性好和稳定性高的特点而受到越来越多研究者的青睐。寻求工艺简单、重复性好和产物形貌可控的中空纳米TiO_2微球的制备方法显得尤为重要。中空纳米TiO_2微球的制备方法根据制备原理可分为溶胶-凝胶法、水热法、溶剂热法、喷雾干燥法和层层自组装法等;根据制备过程中是否加入模板剂又可分为硬模板法、软模板法和无模板法。本文针对硬模板法、软模板法和无模板法进行了综述。其中,硬模板是最早应用于中空TiO_2微球制备的方法,最终所得中空TiO_2的形貌、空腔大小和表面所带电荷与所用模板剂种类密切相关。目前常用的模板剂有三大类,包括聚合物、碳球和无机氧化物。而在制备模板剂过程中需要消耗大量的时间和有机溶剂,造成成本升高和环境污染。软模板法是目前最高效的一种制备方法,其制备机理与硬模板法较为相似,主要区别在于模板剂的选择上,前者的模板剂大多为刚性较强的无机粒子,而软模板剂通常为乳液液滴、超分子胶束、聚合物聚集体/囊泡等强度较低的气体或者液体。相比于硬模板法其最明显的优势在于后期对于模板剂的去除较为容易,不需要高温处理,多次洗涤即可除去,因此具有效率高、工艺简单等优势。无模板法是一种最具应用潜力的中空TiO_2微球制备方法。此法大多为一步反应,因此其可控性较差,尚未实现大范围应用与生产。但是,该法具有制备步骤少、成本低和产率高等优势,在后期的批量生产和规模化制备中空TiO_2微球方面具有潜在的优势。目前,对于中空纳米TiO_2微球的研究除了有效且成熟的制备工艺外,其高效的光催化性能也是研究者追求的目标。笔者认为通过以下三方面可以进一步提高中空纳米TiO_2的光催化性能:其一,多种半导体材料的复合可拓宽其在可见光下的响应区域;其二,非金属阴离子(氮、碳)或金属(铁、铜)离子参杂等可提高光诱导二氧化钛电子空穴对的分离效率;其三,金属氧化物的表面修饰或双原位聚合改性等多种手段共同作用可降低电子-空穴对的重组。延长光生载流子的寿命、提高光催化活性将成为今后中空TiO_2微球研究的重点。     

原位表面修饰纳米CdS粒子的表面结构和光学性能

采用微乳液法合成了纳米尺度硫化镉粒子,并用硫醇和咪唑对粒子进行了原位表面修饰.对纳米硫化镉粒子的形貌与表面结构进行了表征,证实了表面修饰剂与粒子间的键合.电镜观察和紫外-可见吸收光谱的测定发现,表面修饰明显地提高了纳米粒子在溶剂中的分散性,改变了纳米粒子的表面结构,消除了粒子表面导致无辐射弛豫的缺陷,因而提高了纳米粒子分散于溶剂体系的荧光性能.修饰剂与溶剂间的相互作用决定了表面修饰粒子在溶剂中的分散性,对纳米粒子的光学性能也有一定的影响.     

Template-free synthesis of titania architectures with controlled morphology evolution

Template-free synthesis of TiO₂ architectures with controlled morphology evolution has been developed through solvothermal reaction in 1,4-dioxane. By simply varying the molar ratio of the concentrated HCl over Titanium isopropoxide (TTIP) from 0 to 5.0, series of morphologies including nanoparticle-built microspheres, nanoparticle-built microspheres decorated with nanorods, nanorod cauliflowers, and nanorod dendrites have been obtained. The influence of several key factors on the morphology control of TiO₂ has been systematically investigated. These parameters include the mass (molar) ratio of HCl/TTIP, solvothermal reaction temperature and time, acid species (concentrated nitric acid), and solvent type (tetrahydrofuran and 1,3-dioxane). The mechanism for the formation of the TiO₂ architectures with controlled morphology evolution has been discussed. The application of the TiO₂ architectures as water splitting photocatalyst and lithium–ion battery anode has been demonstrated. And the corresponding structure–property correlation has been discussed.     

Influence of nitric acid-assisted hydrothermal conditions on the characteristics of TiO2 catalysts and their activity in the oxidative steam reforming of methanol

Titania (TiO₂) nanoparticles (NPs) with different morphologies (spherical, rod-shaped, and mixed) were prepared by hydrothermal treatment of different nitric acid (HNO₃)/titanium (IV) isopropoxide (TTIP) molar ratios (0.25, 0.5, 1.0, and 1.7) at different hydrothermal temperatures (90, 150, 200, and 250 °C), hydrothermal times (6, 12, and 24 h), and calcination temperatures (500, 625, and 750 °C). The crystalline structure, morphology, and surface texture of the obtained TiO₂ NPs were characterized by X-ray diffraction, nitrogen adsorption–desorption isotherm, field emission-scanning electron microscopy, and high resolution-transmission electron microscopy analyses. Under a larger HNO₃: TTIP molar ratio, higher hydrothermal temperature, and higher hydrothermal time, the spherical mixed anatase–rutile phase TiO₂ NPs were converted to a nanorod (NR)-shaped rutile phase (TiO₂-R). The TiO₂-R NRs gave the highest methanol conversion level (65%) and hydrogen yield (45%) in the oxidative steam reforming of methanol at 400 °C.     

One‐Dimensional Densely Aligned Perovskite‐Decorated Semiconductor Heterojunctions with Enhanced Photocatalytic Activity

By using one‐dimensional rutile TiO₂ nanorod arrays as the structure‐directing scaffold as well as the TiO₂ source to two consecutive hydrothermal reactions, densely aligned SrTiO₃‐modified rutile TiO₂ heterojunction photocatalysts are crafted for the first time. The first hydrothermal processing yielded nanostructured rutile TiO₂ with the hollow openings on the top of nanorods (i.e., partially etched rutile TiO₂ nanorod arrays; denoted PE‐TNRAs). The subsequent second hydrothermal treatment in the presence of Sr²⁺ transforms the surface of partially etched rutile TiO₂ nanorods into SrTiO₃ nanoparticles via the concurrent dissolution of TiO₂ and precipitation of SrTiO₃ while retaining the cylindrical shape (i.e., forming SrTiO₃‐decorated rutile TiO₂ composite nanorods; denoted STO‐TNRAs). The structural and composition characterizations substantiate the success in achieving STO‐TNRA nanostructures. In comparison to PE‐TNRAs, STO‐TNRA photocatalysts exhibit higher photocurrents and larger photocatalytic degradation rates of methylene blue (3.21 times over PE‐TNRAs) under UV light illumination as a direct consequence of improved charge carrier mobility and enhanced electron/hole separation. Such 1D perovskite‐decorated semiconductor nanoarrays are very attractive for optoelectronic applications in photovoltaics, photocatalytic hydrogen production, among other areas.     

Synthesis of size-tunable ZnO nanorod arrays from NH3·H2O/ZnNO3 solutions

Well-aligned crystalline ZnO nanorod arrays were fabricated via an aqueous solution route with zinc nitrate and ammonia as precursors. Dip-coating was firstly utilized to form a ZnO film on ITO substrate as a seed layer for subsequent growth of ZnO nanorods. The effects of NH₃·H₂O/ZnNO₃ molar ratio, ZnNO₃ concentration, growth temperature and time on nanorod morphology were respectively investigated. It was found that the size of nanorod is mainly determined by the molar ratio and concentration. XRD demonstrates that ZnO nanorods are wurtzite crystal structures preferentially orienting in the direction of the c-axis. SEM confirms that ZnO nanorods grew up perpendicular to the substrate. The diameter and length were tunable in a broad range from 80 nm to 500 nm and 250 nm up to 8 μm, respectively. The aspect ratio changed from 3 to 17 mainly dependent on composition of the aqueous solution.     

Structural and magnetic properties of nanocomposites based on nanostructured polyaniline and titania nanotubes

Nanocomposites consisting of self-assembled polyaniline (PANI) nanostructures and titania nanotubes (TiO₂-NT) were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous dispersion of TiO₂-NT (outer diameter ~10 nm), without added acid. The influence of initial mole ratio of aniline to TiO₂ (80, 20, and 5) on the morphology, electrical conductivity, molecular structure, crystallinity, and magnetic properties of synthesized PANI/TiO₂ nanocomposites was studied. Transmission electron microscopy, Raman spectroscopy, and X-ray powder diffraction proved that the shape and structure of TiO₂-NT in the final nanocomposites were preserved. The shape of PANI nanostructures formed in the nanocomposites was influenced by the initial aniline/TiO₂-NT mole ratio. Nanotubes and nanorods are predominant PANI nanostructures in the nanocomposite prepared with the highest aniline/TiO₂ mol ratio of 80. The decrease of aniline/TiO₂ molar ratio induced more pronounced formation of nanorod network. The electrical conductivity of PANI/TiO₂ nanocomposites was in the range (1.3–2.4) × 10^?3 S cm^?1. The nanocomposites exhibit weak ferromagnetic behavior. Approximately order of magnitude lower values of coercive field and remanent magnetization were obtained for nanocomposite samples in comparison to pure PANI.     

Sb‐Doped SnO2 Nanorods Underlayer Effect to the α‐Fe2O3 Nanorods Sheathed with TiO2 for Enhanced Photoelectrochemical Water Splitting

Here, a Sb‐doped SnO₂ (ATO) nanorod underneath an α‐Fe₂O₃ nanorod sheathed with TiO₂ for photoelectrochemical (PEC) water splitting is reported. The experimental results, corroborated with theoretical analysis, demonstrate that the ATO nanorod underlayer effect on the α‐Fe₂O₃ nanorod sheathed with TiO₂ enhances the PEC water splitting performance. The growth of the well‐defined ATO nanorods is reported as a conductive underlayer to improve α‐Fe₂O₃ PEC water oxidation performance. The α‐Fe₂O₃ nanorods grown on the ATO nanorods exhibit improved performance for PEC water oxidation compared to α‐Fe₂O₃ grown on flat fluorine‐doped tin oxide glass. Furthermore, a simple and facile TiCl₄ chemical treatment further introduces TiO₂ passivation layer formation on the α‐Fe₂O₃ to reduce surface recombination. As a result, these unique nanostructures show dramatically improved photocurrent density (139% higher than that of the pure hematite nanorods).     

Sonochemical assisted impregnation of Bi2WO6 on TiO2 nanorod to form Z-scheme heterojunction for enhanced photocatalytic H2 production

In this work, Bi₂WO₆/TiO₂ nanorod heterojunction was prepared by sonochemical assisted impregnation method. After loading 2 wt% Bi₂WO₆ on TiO₂ nanorods, the photocatalytic hydrogen production rate of 2026 µmol/h/g was achieved. Compared to commercial P25 and TiO₂ nanorods, ∼13 and ∼3 folds enhanced activity was observed. The excellent photocatalytic performance of Bi₂WO₆/TiO₂ nanorod photocatalyst was mainly attributed to i) reduction of bandgap due to heterojunction formation, ii) quick transport of photogenerated charge carriers, and iii) efficient charge carrier separation supported by UV-DRS, photocurrent measurement, Impedance study, and photoluminescence spectra analysis. The Z-scheme band alignment for Bi₂WO₆/TiO₂ nanorod heterojunction was proposed based on the Mott-Schottky measurement. This result demonstrated the effective utilization of Z-scheme heterojunction of Bi₂WO₆/TiO₂ for photocatalytic reduction application.     

CdS-sensitized ZnO nanorod arrays coated with TiO2 layer for visible light photoelectrocatalysis

A novel ZnO/CdS/TiO₂ nanorod array composite structure was fabricated by depositing CdS-sensitized layer onto ZnO nanorod arrays via chemical bathing deposition and subsequently coated by TiO₂ protection layer via a vacuum dip-coating process. The films were characterized by x-ray diffraction, field emission scanning electron microscopy, energy dispersive spectrum, and UV–Vis diffuse reflectance spectroscopy. For the films severed as the photoanodes, linear sweep voltammetry and transient photocurrent (i _ph) were investigated in a three-electrode system. The photoelectrocatalytic activity was evaluated by the degradation of methylene blue (MB) under visible light irradiation. The results show that the oriented ZnO nanorods are adhered by relatively uniform CdS-sensitized layer and coated with TiO₂ layer. Both the coated and uncoated CdS-sensitized ZnO nanorod arrays exhibit the visible light response and the photoelectrocatalytic activity on the degradation of MB under visible light irradiation. The ZnO/CdS/TiO₂ nanorod array film possesses stable and superior photoelectrocatalytic performance owing to the TiO₂ thin layer protecting the CdS from photocorrosion.     

TiO2 nanorod films grown on Si wafers by a nanodot-assisted hydrothermal growth

We report the controlled hydrothermal growth of rutile TiO₂ nanorods on Si wafers by using an anatase TiO₂ nanodot film as an assisted growth layer. The anatase nanodot film was prepared on the wafer by phase-separation-induced self-assembly and subsequent heat-treatment at 500 °C. The nanodots on the wafer were then subjected to hydrothermal treatment to induce the growth of rutile TiO₂ nanorod films. The size and dispersion density of the resulting TiO₂ nanorods could be varied by adjusting the Ti ion concentration in the growth solution. The TiO₂ nanorods were of the rutile phase and grew in the [001] direction. The growth mechanism reveals that the growth of the rutile nanorods was wholly dependent on the existence of rutile TiO₂ seeds, which could be formed by the dissolution-reprecipitation of the anatase nanodots during hydrothermal treatment or under the high-temperature conditions of the subsequent heat-treatment of the as-prepared nanodots. In controlling the rutile nanorod growth, the anatase nanodots show more efficiency than a dense anatase film. Preliminary evaluations of the rutile nanorod films have demonstrated that the wettability changed from highly hydrophobic to superhydrophilic and that the photocatalytic activity was enhanced with increasing nanorod dispersion density.     

Rutile TiO2 nanorod arrays directly grown on Ti foil substrates towards lithium-ion micro-batteries

Nanosized rutile TiO₂ is one of the most promising candidates for anode material in lithium-ion micro-batteries owing to their smaller dimension in ab-plane resulting in an enhanced performance for area capacity. However, few reports have yet emerged up to date of rutile TiO₂ nanorod arrays growing along c-axis for Li-ion battery electrode application. In this study, single-crystalline rutile TiO₂ nanorod arrays growing directly on Ti foil substrates have been fabricated using a template-free method. These nanorods can significantly improve the electrochemical performance of rutile TiO₂ in Li-ion batteries. The capacity increase is about 10 times in comparison with rutile TiO₂ compact layer.