钛白粉载体对选择性催化还原脱硝催化剂性能的影响

钛白粉(TiO2)是钒钛类选择性催化还原(SCR)脱硝催化剂的载体,TiO2的晶型、比表面积、粒度、孔结构以及SO42-和P2O5含量直接影响所制备的SCR催化剂的性能。一般而言,TiO2的比表面积越大,以其制备的SCR催化剂的比表面积也越大,活性也较高;但对于纳米级TiO2,由于颗粒粒径太小,容易发生烧结,而且形成钒钛化合物,导致催化剂比表面积较载体明显下降,因而活性降低。锐钛型TiO2由于比表面积大和不易被硫化,较金红石型TiO2适合做载体。多孔结构的TiO2使得钒物种在载体表面处于高度分散状态,从而提高催化剂的活性。TiO2中本身含有的少量SO42-和P2O5有助于提高催化剂的性能。     

Pt/WC/TiO2催化剂的制备及其电催化性能研究

以TiO2为载体制备了Pt/WC/TiO2三元复合催化剂,并由XRD、SEM和TEM等表征催化剂样品的形貌和结构特征.用循环伏安法测定了三元复合催化剂在酸性条件下对甲醇氧化的电催化性能,并将其与二元复合催化剂Pt/TiO2和Pt/WC的电催化性能进行比较.结果表明：三元复合催化剂具有更好的催化活性.进一步研究了二氧化钛晶相对Pt/WC/TiO2催化剂电催化活性的影响.     

Preparation of nanoporous MgO-coated TiO2 nanoparticles and their application to the electrode of dye-sensitized solar cells

Sol-gel-derived Mg(OH)(2) gel was coated onto TiO(2) nanoparticles, and the subsequent thermal topotactic decomposition of the gel formed a highly nanoporous MgO crystalline coating. The specific surface area of the electrode that was prepared from the core-shell-structured TiO(2) nanoparticles significantly increased compared with that of the uncoated TiO(2) electrode. The increase in the specific surface area of the MgO-coated TiO(2) electrode was attributed to the highly nanoporous MgO coating layer that resulted from the topotactic reaction. Dye adsorption behavior and solar cell performance were significantly enhanced by employing the MgO-coated TiO(2) electrode. Optimized coating of a MgO layer on TiO(2) nanoparticles enhanced the energy conversion efficiency as much as 45% compared to that of the uncoated TiO(2) electrode. This indicates that controlling the extrinsic parameters such as the specific surface area is very important to improve the energy conversion efficiency of TiO(2)-based solar cells.     

聚乙二醇对TiO2薄膜光致亲水性的促进作用

为了提高TiO₂薄膜的光致亲水性及其持久性, 将聚乙二醇(PEG)2000 引入TiO₂溶胶中, 利用提拉法在载玻片上制备出含PEG的TiO₂薄膜样品, 通过测试样品紫外光照下水滴接触角的变化, 考察不同浓度PEG对TiO₂薄膜光致亲水性能的影响; 并通过测试光照后的亲水薄膜样片暗处放置不同时间后接触角的变化, 比较含PEG的TiO₂薄膜和纯TiO₂薄膜样品的亲水持久性. 结果表明: PEG作为一种非离子型长链分子, 其适量的添加可促进TiO₂薄膜的光致亲水性及其持久性. 基于薄膜样品的傅里叶变换红外(FTIR)光谱和紫外-可见漫反射光谱(UV-Vis DRS)结果, 认为PEG作为空穴捕获剂有助于TiO₂薄膜中Ti³⁺的生成和稳定存在, 进而有助于亲水中心(表面羟基)的形成. 此研究对于TiO₂光自洁涂料的应用很有意义, 也为研究TiO₂的光激发瞬态行为提供了一个可能的简易方法.     

Photocatalytic reactivity of surface platinized TiO2: substrate specificity and the effect of Pt oxidation state

Surface platinized TiO(2) (Pt/TiO(2)) has been frequently studied, but its photocatalytic reactivities reported in the literature are not consistent in some cases. To understand the discrepancies, the effects of Pt speciation on TiO(2) on the photocatalytic degradation (PCD) of a few chlorinated organic compounds (trichloroethylene (TCE), perchloroethylene (PCE), dichloroacetate, etc.) were investigated with several Pt/TiO(2) samples that were prepared differently. The oxidation state of Pt deposits was analyzed by X-ray photoelectron spectroscopy and was found to be the most important factor in determining the initial PCD rates of chlorinated organic compounds. TiO(2) with oxidized Pt species (Pt(ox)/TiO(2)) was less reactive than TiO(2) with metallic Pt (Pt(0)/TiO(2)) for all substrates tested. In particular, Pt(ox)/TiO(2) strongly inhibited the PCD of TCE and PCE whereas it was more reactive than pure TiO(2) for the PCD of other compounds. The photocurrents obtained with the Pt(ox)/TiO(2) electrode were lower than those with the Pt(0)/TiO(2) electrode, which was ascribed to the role of Pt(ox) species as a recombination center. It is proposed that TCE adsorbed on Pt(ox) chemically mediates the charge recombination through the redox cycle of TCE. The Pt effects in photocatalysis are highly substrate-specific and depend on the Pt-substrate interaction as well as the properties of Pt deposits.     

Au掺杂方式对锐钛矿TiO2光催化性能的影响

结合超临界乙醇干燥技术, 采用沉积-沉淀(DP)和共沉淀(CP)法分别制备了具有单一锐钛矿晶相的Au/TiO2和Au(0.2%, 原子分数)-TiO2光催化剂, 通过XRD、BET、TEM、XPS和Raman手段表征样品中Au的掺杂形态, 以光催化降解甲基橙为模型反应考察了样品的光催化活性. 结果表明, DP法制备的Au/TiO2在110 ℃干燥处理后, 表面存在的Au3+能有效地促进锐钛矿TiO2光催化性能, 其一级反应速率常数比纯锐钛矿TiO2提高了3.2倍, 比商用光催化剂Degussa-P25提高了4.1倍, 而当Au3+被还原为Au0后光催化活性下降. 用CP法制备的Au-TiO2并没有较大地提高锐钛矿TiO2光催化性能, 在焙烧温度达到800 ℃时, Au向表面迁移聚集, 造成锐钛矿TiO2晶格氧空位和缺陷位增加, 使光催化活性下降.     

Au-CuO／TiO2催化剂用于CO2中微量H2的脱除

用沉积沉淀法制备了Au-CuO/TiO2催化剂和Au/TiO2催化剂,考察了沉淀温度、沉淀pH、焙烧温度和Cu/Au摩尔比等制备工艺条件对Au-CuO/TiO2催化剂性能的影响,确定了适宜的催化剂制备工艺条件.结果表明,Au-CuO/TiO2催化剂对CO2中微量H2的脱除具有较好的活性和稳定性.还考察了还原和H2S中毒处理先后的顺序对催化剂H2脱除活性的影响.结果表明,Au/TiO2催化剂基本上不受处理顺序的影响,而H2S处理顺序对Au-CuO/TiO2催化剂的性能有较为明显的影响,这说明还原后的Au-CuO/TiO2催化剂形成了Au-Cu合金。     

Fabrication of TiO2 binary inverse opals without overlayers via the sandwich-vacuum infiltration of precursor

A sandwich-vacuum method was demonstrated for the fabrication of titania (TiO(2)) binary inverse opals with an open surface. In this method, a moisture-stable TiO(2) precursor was backfilled into the interstitial spaces of polystyrene binary colloidal crystals (PS bCCs), which served as a template. Removal of the template by calcination yielded TiO(2) binary inverse opals with a 3D-ordered macroporous (3DOM) structure. Optical reflectance spectra revealed the existence of a pseudostop band gap in the 3DOM TiO(2) samples. The position of the pseudostop band gap shifted to the low-wavelength region as the number ratio of small over large PS spheres was increased in the template. The sandwich-vacuum method proved to be simple and rapid for the fabrication of TiO(2) binary inverse opals without overlayers in large domains. The 3DOM TiO(2) materials were used as a photocatalyst for the degradation of benzoic acid. Results showed that in comparison to TiO(2) nanoparticles prepared under the same sintering conditions, the 3DOM TiO(2) materials displayed enhanced photocatalytic activity.     

纳米TiO2光催化剂改性研究进展

TiO2光催化活性高,化学稳定性好,绿色环保及价廉等特点,在污水处理、有机污染物降解、催化制氢、抗菌抗癌及自清洁等方面有巨大的应用前景。然而TiO2半导体禁带宽,光谱范围小,光量子效率低等问题限制了其光催化性能。文章综述了TiO2光催化剂优化改性的研究进展,系统分析了TiO2半导体的结构特征与作用机理,以及TiO2光催化过程的影响因素,着重介绍了TiO2光催化剂多元优化改性方法的优势及不足,最后对未来发展新型TiO2基光催化剂提出了建议。     

Oxygen-deficient titania as alternative support for Pt catalysts for the oxygen reduction reaction

Insufficient electrochemical stability is a major challenge for carbon materials in oxygen reduction reaction （ORR） due to carbon corrosion and insufficient metal-support interactions. In this work, titania is explored as an alternative support for Pt catalysts. Oxygen deficient titania samples including TiO2-x and TiO2_xNy were obtained by thermal treatment of anatase TiO2 under flowing H2 and NH3, respectively. Pt nanoparticles were deposited on the titania by a modified ethylene glycol method. The samples were characterized by N2-physisorption, X-ray diffraction and X-ray photoelectron spectroscopy. The ORR activity and long-term stability of supported Pt catalysts were evaluated using linear sweep voltammetry and chronoamperometry in 0.1 mol/L HC104. Pt/TiO2_x and Pt/TiO2_xNy showed higher ORR activities than Pt/TiO2 as indicated by higher onset potentials. Oxygen deficiency in TiO2-x and TiO2-xNy contributed to the high ORR activity due to enhanced charge transfer, as disclosed by electrochemical impedance spectroscopy studies. Electrochemical stability studies revealed that Pt/TiOE_x exhibited a higher stability with a lower current decay rate than commercial Pt/C, which can be attributed to the stable oxide support and strong interaction between Pt nanoparticles and the oxygen-deficient TiO2-x support.     

Effect of TiO2 nanoparticles on self-assembly behaviors and optical and photovoltaic properties of the P3HT-b-P2VP block copolymer

An ordered nanostructure can be created from the hybrid materials of self-assembly poly(3-hexyl thiophene-b-2-vinyl pyridine) and nicotinic acid-modified titanium dioxide nanoparticles (P3HT-b-P2VP/TiO(2)). TEM and XRD analyses reveal that the TiO(2) nanoparticles (NPs) are preferentially confined in the P2VP domain of P3HT-b-P2VP whereas TiO(2) NPs interact with either pure P3HT or a blend of P3HT and P2VP to produce microsized phase segregation. The morphologies of lamellar and cylindrical structures are disturbed when the loading of TiO(2) NPs is 40 wt % or higher. Cylindrical P3HT-b-P2VP/TiO(2) exhibits a small blue shift in absorption and photoluminescence spectra with increasing TiO(2) loading as compared to P3HT/TiO(2). The NPs cause a slightly misaligned P3HT domain in the copolymer. Furthermore, the PL quenching of P3HT-b-P2VP/TiO(2) becomes very large as a result of efficient charge separation in the ordered nanodomain at 16 nm. Solar cells fabricated from self-assembly P3HT-b-P2VP/TiO(2) hybrid materials exhibit a >30 fold improvement in power conversion efficiency as compared to the corresponding 0.3P3HT-0.7P2VP/TiO(2) polymer blend hybrid. This study paves the way for the further development of high-efficiency polymer-inorganic nanoparticle hybrid solar cells using a self-assembled block copolymer.     

Drying and nondrying layer-by-layer assembly for the fabrication of sodium silicate/TiO2 nanoparticle composite films

Influences of drying and nondrying steps on structures of layer-by-layer (LbL) assembled sodium silicate/TiO(2) nanoparticles films (donated as silicate/TiO(2) films) have been systematically investigated. The nondrying LbL assembly produces highly porous silicate/TiO(2) films with large thickness. In contrast, the silicate/TiO(2) films fabricated with a drying step after each layer deposition are flat and thin without porous structures. In situ atomic force microscopy (AFM) measurements confirm that the sodium silicate and TiO(2) nanoparticles are deposited in their aggregated forms. A N(2) drying step can disintegrate the aggregated silicate and TiO(2) nanoparticles to produce thin silicate/TiO(2) films with compact structures. Without the drying steps, the aggregated silicate and TiO(2) nanoparticles are well retained, and their LbL assembly produces highly porous silicate/TiO(2) films of large thickness. The highly porous silicate/TiO(2) films are demonstrated to be useful as reusable film adsorbents for dye removal from wastewater because they can adsorb a large amount of cationic organic dyes and decompose them under UV irradiation. The present study is meaningful for exploring drying/nondrying steps for tailoring structure and functions of LbL assembled films.     

CdS敏化对TiO2纳米薄膜电极光生电荷转移特性的影响

1991年Gratzel等[1]以敏化的TiO2纳米薄膜电极组成的液体结光电化学太阳能电池(PEC),其光电转换效率(IPCE)达到10%. 最近,选用固态电解质使这种PEC的IPCE达到33%[2].于是用有机染料[3,4]及窄带隙半导体纳米微粒[5]敏化的电极受到了广泛关注.     

掺杂Sb对纳米TiO2薄膜的超亲水性和微结构的影响

用溶胶-凝胶法将纳米TiO2:Sb薄膜沉积在玻璃基板上.研究了掺杂浓度对薄膜的光致超亲水性、薄膜结构和晶相转变的影响.结果表明,纯TiO2薄膜中， TiO2不仅以无定型态存在，而且还以板钛矿和锐钛矿的形式存在.掺杂Sb提高了TiO2由无定型向板钛矿和锐钛矿转变的速率.掺入适量的Sb后， TiO2薄膜表现出更好的光致超亲水性.由XRD谱可算出薄膜的晶粒大小为13.3～20.0 nm.     

TiO2对Ni/Al2O3催化剂CO甲烷化性能的影响

采用溶胶凝胶法制备了一系列不同TiO₂含量的TiO₂-Al₂O₃复合载体,并通过浸渍法制备了NiO/TiO₂-Al₂O₃催化剂。分别考察了不同TiO₂含量的NiO/TiO₂-Al₂O₃催化剂及反应温度对CO甲烷化催化性能的影响。实验结果表明,当复合载体中TiO₂质量分数为30%,反应温度为350～450 ℃时,催化剂催化活性较高。利用N₂吸附-脱附(BET)、X射线衍射(XRD)及H₂程序升温还原(H₂-TPR)等手段对催化剂物化性能进行了表征。结果表明,加入适量的TiO₂能抑制镍铝尖晶石NiAl₂O₄物种的生成,改善NiO的表面分散性能,避免大晶粒NiO的形成,也改善了催化剂的还原性能,从而提高催化剂的CO甲烷化活性。     

Role of micro-structure and interfacial properties in the higher photocatalytic activity of TiO2-supported nanogold for methanol-assisted visible-light-induced splitting of water

This paper deals with the textural, microstructural and interfacial properties of Au/TiO(2) nanocomposites, in relation to their photocatalytic activity for splitting of water. TiO(2) samples of two different morphologies were employed for dispersing different cocatalysts, such as: Au, Pt, Ag or Cu, for the sake of comparison. The samples were characterized using powder XRD, XPS, UV-visible, thermoluminescence, SEM, HRTEM and SAED techniques. Compared to other metal/TiO(2) photocatalysts, Au/TiO(2) with an optimum gold loading of 1 wt% was found to exhibit considerably higher activity for visible light induced production of H(2) from splitting water in the presence of methanol. Further, the sol-gel prepared TiO(2) (s.TiO(2)), having spherical grains of 10-15 nm size, displayed better photoactivity than a Degussa P25 catalyst. The electron microscopy investigations on s.TiO(2) revealed significant heterogeneity in grain morphology of individual TiO(2) particles, exposure of the lattice planes, metal dispersion, and the interfacial metal/TiO(2) contacts. The gold particles were found to be in a better dispersed state. O(2) TPD experiments revealed that the gold nanoparticles and Au/TiO(2) interfaces may serve as distinct binding sites for adsorbate molecules. At the same time, our thermoluminescence measurements provide an insight into Au-induced new defect states that may facilitate the semiconductor-to-metal charge transfer transition. In conclusion, the superior photocatalytic activity of Au/TiO(2) may relate to the grain morphology of TiO(2), dispersion of gold particles, and the peculiar architecture of metal/oxide heterojunctions; giving rise in turn to augmented adsorption of reactant molecules and their interaction with the photo-generated e(-)/h(+) pair. The role played by methanol as a sacrificial reagent in photocatalytic splitting of water is discussed.     

Co掺杂对TiO2光催化剂结构与性能的影响

采用溶胶-凝胶法制备了Co掺杂的TiO2粉末, 利用透射电子显微镜、X射线光电子能谱、紫外可见光谱和X射线衍射技术对粉末进行了表征, 并利用环形光催化反应器对其光催化活性进行了测试. 结果表明, 随焙烧温度的增加, Co/TiO2粉末的晶粒尺寸逐渐增大, 升至873 K时, 钴元素以CoTiO3形式从TiO2中析出, 同时TiO2由锐钛矿型向金红石型发生转变, 相转变过程中晶格常数a和c以及晶胞体积发生收缩. 掺杂钴以后, 粉末的光谱吸收范围被拓展至可见光, 但是其光催化活性却明显降低.     

Influence of TiO_2 Mineralizer on the Crystalline Structure of Cordierite Synthesized from Aluminum Slag

By adding small amount of TiO2, aluminum slag could be used to synthesize cor-dierite, α-Al2O3, TiO2 and dehydrated talc could generate solid solution to accelerate the solid-state reaction to form cordierite. The experimental results show that the content of cordierite increases with the increase of TiO2 added. 3.0% of TiO2 is determined to be the best amount, because all crystalline substances are converted into cordierite at this content. Philips X‘pert plus software analysis shows that when the content of TiO2 is from 0 to 1.0%, cordierite has the same hexagonal structure as the single crystal and the lattice parameters change slightly; when the content of TiO2 is from 1.0 to 2.0%, the cordierite still keeps hexagonal structure but the lattice parameters change greatly; when the content of TiO2 is from 2.0 to 3.5%, the cordierite is converted from hexagonal into rhombic and the lattice parameters change accordingly.     

TiO2纳米微粒对PPV发光性能的影响

采用溶胶凝胶法制备了一系列PPV/TiO₂纳米复合膜,探讨了TiO₂纳米微粒对PPV发光性能的影响.研究发现,这些复合膜的发光性质依赖于TiO₂/PPV的质量比,.在TiO₂/PPV的质量比为1/9时,复合膜中的TiO₂微粒对PPV的荧光具有猝灭作用;当TiO₂/PPV的质量比为1/1时,复合膜中的TiO₂对PPV的荧光具有增强作用.通过FT-IR,UV-Vis,FL光谱和TEM探讨了复合膜微结构与其发光性质的关系.     

Comparison between the effects of TiO2 synthesized by photoassisted and conventional sol-gel methods on the photochromism of WO3 colloids

WO3 colloids can exhibit a blue color under UV-light irradiation due to the absorption of electrons trapped at the energy levels within the forbidden gap and this coloration performance can be improved by TiO2 nanoparticles. In this work, it is found that TiO2 prepared by the photoassisted method (TiO2-P) exhibits stronger enhancement effects than that prepared by the conventional sol-gel method (TiO2-C). Several possible mechanisms have been proposed to account for this phenomenon. The migration of charge carriers toward different directions is promoted since the flat-band potential of TiO2-P colloids is more negative than that of TiO2-C and the contact between WO3 and TiO2 particles is improved in the WO3/TiO2-P system; there are more efficient TiO2 and hole scavengers (i.e., Ti3+ and/or TiO2-O2*- species) in the system containing TiO2-P; the bandgap of TiO2-P becomes narrowed, and so on. In addition, the potential applications of this process are also discussed briefly.