Incorporation of functionalized single-wall carbon nanotubes in dye-sensitized TiO2 solar cells

Effects of incorporation of acid-treated single-wall carbon nanotubes (a-SWCNs) in TiO(2) film and of anchorage of dye-linked, a-SWCNs (hereafter dye-SWCNs) to the TiO(2)/electrolyte interface on photocurrent-voltage characteristics of dye-sensitized solar cells were studied. Compared with an unmodified cell, the modified cell with the a-SWCNs in TiO(2) film showed a 25% increase in short-circuit photocurrent (J(sc)). The J(sc) increase is correlated with improved connectivity between the a-SWCNs and the TiO(2) particles and with enhanced light scattering by TiO(2) clusters formed in the presence of the a-SWCNs. In the case of anchoring dye-SWCNs to the TiO(2)/electrolyte interface, the open-circuit voltage (V(oc)) increased by as much as 0.1 V, possibly due to the basicity of the TiO(2) surface from NH groups of ethylenediamine moieties of the anchored dye-SWCNs.     

Application of tetrahydrofuran dispersant in microemulsion for fabricating titania mesoporous thin film

A new strategy was used to fabricate titania mesoporous thin film by incorporating tetrahydrofuran (THF) into the CTAB/n-butyl alcohol/cyclohexane/water reverse microemulsion as a micelle disperser. Highly dispersed and congregated TiO(2) particles in the microemulsion with and without THF were observed by transmission electron microscopy (TEM), respectively. The photographs observed by field-emission scanning electron microscopy (FE-SEM) show that a uniform titania mesoporous thin film with monodisperse TiO(2) spherical nanoparticles of ca. 20 nm was obtained using the microemulsion with THF.     

The synthesis of mesoporous TiO2/SiO2/Fe2O3 hybrid particles containing micelle-induced macropores through an aerosol based process

Mesoporous SiO(2)/TiO(2)/Fe(2)O(3) particles containing macropores of about 50 nm in diameter have been prepared by an aerosol process using cetyltrimethylammonium bromide (CTAB) as a templating agent. In contrast to the traditional templating effect of CTAB to form ordered mesoporous silicas, the morphology here is vastly different due to the presence of precursor iron salts. The particles have mesoporosity templated by CTAB but additionally have large voids leading to a combined macroporous and mesoporous structure. The morphology is explained through the formation of colloidal structures containing species such as CTA(+)X(-1)Fe(3+) colloids in the aerosol droplets, indicating of a salt bridging effect. This dual porosity has applied implications, as the macropores provide easy entry to the particle interior in potentially diffusion limited situations. Furthermore, the particles encapsulate Fe(2)O(3) and contain TiO(2) leading to the dual functional properties of magnetic response and photocatalytic activity.     

Sea urchin TiO2-nanoparticle hybrid composite photoelectrodes for CdS/CdSe/ZnS quantum-dot-sensitized solar cells

The sea urchin TiO(2) (SU TiO(2)) particles composed of radially aligned rutile TiO(2) nanowires are successfully synthesized through the simple solvothermal process. SU TiO(2) was incorporated into the TiO(2) nanoparticle (NP) network to construct the SU-NP composite film, and applied to the CdS/CdSe/ZnS quantum-dot-sensitized solar cells (QDSSCs). A conversion efficiency of 4.2% was achieved with a short-circuit photocurrent density of 18.2 mA cm(-2) and an open-circuit voltage of 531 mV, which corresponds to ～20% improvement as compared with the values obtained from the reference cell made of the NP film. We attribute this extraordinary result to the light scattering effect and efficient charge collection.     

On the adsorption and condensed film formation of binary mixtures of dodecyl-, tetradecyl-, hexadecyl-, and octadecyl-trimethylammonium bromides at the mercury–electrolyte interface

The adsorption and condensed film formation on mercury at the negative potential region for binary mixtures of dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB), cetyltrimethylammonium bromide (CTAB), octadecyltrimethylammonium bromide (OTAB) is studied in KBr at various temperatures from 5 to 45 °C. The formation of the CTAB condensed film is hindered with the addition of DTAB and TTAB. There are interactions between unlike hydrophobic chains. The strong interactions between the CTAB molecules do not take place when DTAB or TTAB is present above a certain concentration. This hindering is more pronounced in the case of TTAB compared to the same DTAB concentration, i.e. the increase of the chain length hinders the film formation. The initially adsorbed molecules play a templating role in the kinetics of the film formation and in the self-assembling of the molecules. The initial induction time strongly depends on the temperature. The less surface active CTAB can hinder the OTAB film formation in binary mixtures. Also, increased interaction between OTAB and CTAB can be observed, indicating synergy effects in the film formation in some cases. The temperature range that the film is formed can be changed using mixtures of surfactants. Thus, the development of the film can become impossible, more difficult or even easier. Hysteresis phenomena are observed. The capacity versus time curves in the case that condensed film is formed are treated with the Avrami plot formulation, giving values between 1.5 and 2 indicating a progressive one dimensional nucleation with constant growth rate or a decrease of the nucleation rate during the overall film formation. There is generally a marked effect of the chain length of the alkyl chain on the film formation.     

TiO2 films loaded with silver nanoparticles: control of multicolor photochromic behavior

Ag-TiO(2) films exhibiting multicolor photochromism were prepared by photoelectrochemical reduction of Ag(+) to Ag nanoparticles in nanoporous TiO(2) films under UV light. Color of the Ag-TiO(2) film, initially brownish-gray, changes under a colored visible light to the color of the light and reverts to brownish-gray under UV light. Their chromogenic properties were improved by simultaneous irradiation for Ag deposition with UV and blue lights to suppress the formation of anisotropic Ag particles. Nonvolatilization of a color image was also achieved by removing Ag(+) that was generated during the irradiation with a colored light. Once nonvolatilized, the image can be reproduced by UV light, even after the image is discolored under white light. This new effect evidenced that nanopores in the TiO(2) film determine the resonance wavelengths of the Ag particles, as their molds. In addition, solvatochromic behavior of the Ag-TiO(2) film proved that nanospaces left around the Ag nanoparticles affect the resonance wavelengths of the Ag particles.     

Mechanism of photoinduced superhydrophilicity on the TiO2 photocatalyst surface

The physicochemical properties of the H(2)O molecules adsorbed on TiO(2) surfaces during UV light irradiation were fully investigated by near-infrared (NIR) absorption spectroscopy. It was found that the H(2)O molecules adsorbed on the TiO(2) surfaces desorb during UV light irradiation by the heating effect of the light source. Since the amount of the H(2)O adsorbed on the TiO(2) surfaces decreased, the distribution of the hydrogen bonds within the H(2)O molecules decreased, resulting in a decrease in the surface tension of the H(2)O clusters. The decrease in the surface tension of H(2)O under UV light irradiation was found to be one of the most important driving forces in which the H(2)O clusters on the TiO(2) surface spread out thermodynamically, forming H(2)O thin layers. The partial elimination of the hydrocarbons from the TiO(2) surface by the photocatalytic complete oxidation was seen to be the other important factor, providing free spaces on the surface where the H(2)O clusters could spill over and spread out to form the thin H(2)O layers. Moreover, the temperature changes of the TiO(2) powder samples during UV light irradiation were found to show a good correspondence with the changes in the contact angle of the H(2)O droplets on the TiO(2) thin film surfaces. Especially the time scale for the hydrophilic conversion on the TiO(2) surfaces under UV light irradiation was in good agreement with the decrease in the amount of H(2)O molecules adsorbed on the TiO(2) surfaces but not the amount of the hydrocarbons eliminated by the photocatalytic oxidation reactions, showing that the adsorption and desorption of H(2)O molecules are generally quite sensitive to the temperature changes of solid surfaces.     

液相沉积法制备TiO2颗粒表面包覆SiO2纳米膜

研究了用液相沉积法在TiO2颗粒表面包覆SiO2纳米膜的过程.通过透射电镜(TEM)和酸溶实验分析,证实本实验在TiO2颗粒表面包覆了一层连续、致密的SiO2纳米膜.ζ-电位分析表明,颗粒表面只需少量包覆就可以显著改变颗粒表面的电动力学行为.采用 X射线荧光光谱分析仪（XRF）测定SiO2包覆量随包覆过程的变化.通过X射线光电子能谱（XPS）分析,获得Ti 2p、Si 2p及 O 1s电子结合能及其相对强度随包覆过程的变化规律,揭示硅酸分子在TiO2颗粒表面的包覆过程.分析表明,初期形成的活性硅酸分子与TiO2颗粒表面的羟基反应形成Ti－O－Si键,后期形成的硅酸分子与已键合在表面的硅酸发生缩合反应,形成连续致密的硅膜,膜层在陈化过程中继续缓慢生长.     

CTAB-promoted prussian blue-modified electrode and its cation transport characteristics for K+, Na+, Li+, and NH4+ ions

A Prussian blue (PB) film was deposited on a glassy carbon (GC) electrode by cyclic voltammetry in the presence of the cationic surfactant cetyltrimethylammonium bromide (CTAB). The electrode thus formed showed 4-fold enhancements in redox current and charge values in pure KCl electrolyte as well as greater stability than an electrode prepared in the absence of CTAB. This improved performance of a PB+CTAB electrode versus a PB electrode was further demonstrated using SEM, XRD, and electrochemical impedance spectroscopy (EIS) measurements. A comparative study was undertaken on the cation transport characteristics of PB and PB+CTAB electrodes for Na+, Li+, and NH4+ ions. We obtained a CV pattern for a CTAB-promoted PB film, which showed ideal Nernstian behavior at all scan rates from 5 to 140 mV s(-1). Conditions for the formation and preservation of these ideal and stable PB films are discussed. Possible mechanisms for the beneficial effects of CTAB are proposed.     

Room-temperature preparation of nanocrystalline TiO2 films and the influence of surface properties on dye-sensitized solar energy conversion

An extremely easy method is presented for producing surfactant-free films of nanocrystalline TiO2 at room temperature with excellent mechanical stability when deposited on glass or plastic electrodes for dye-sensitized solar energy conversion. Prolonged magnetic stirring of commercial TiO2 nanoparticles (Degussa P25) in either ethanol or water results in highly homogeneous dispersions which are used to prepare TiO2 films with surface properties which depend on the solvent used for dispersing the particles, even after sintering. The optical and mechanical properties of films cast from ethanol and water dispersions are compared, and differences in the extent of surface defects and dye binding are observed. Optical absorption, photoluminescence, and resonance Raman spectra of TiO2 films sensitized with Ru(4,4'-dicarboxylic acid-2,2'-bipyridine)2(NCS)2 ("N3") reveal that the electronic coupling of the dye and semiconductor depends on the surface structure of the film which varies with film preparation. Current-voltage data for illuminated and dark dye-sensitized solar cells are obtained as a function of film preparation, and results are compared to spectroscopic data in order to interpret the microscopic basis for variations in solar cell performance, especially with regard to sintered versus unsintered TiO2 films. The results suggest that surface traps associated with oxygen vacancies play a critical role in determining the efficiency of dye-sensitized solar energy conversion through their influence on the binding and electronic coupling of the dye to the semiconductor.     

溶胶-凝胶法制备薄膜型TiO2光催化剂

用TiCl4作原料,通过溶胶-凝胶法在单晶硅基片上制备了TiO2纳米薄膜,并用XRD,AES,XPS以及紫外反射光谱等手段,对TiO2薄膜的结构进行了研究.结果发现,TiO2薄膜以锐钛矿型晶相存在.TiO2薄膜层与硅衬底间无明显的界面扩散反应.掺杂的Pd在还原前的薄膜中以氧化态存在,还原后则以高分散的金属态存在.掺杂的Pt在还原前后均以金属态存在,但还原后产生颗粒聚集.掺杂Pd的TiO2薄膜经还原后,其紫外吸收强度明显提高,主吸收峰发生红移.     

Deactivation of the TiO2 photocatalyst by coupling with WO3 and the electrochemically assisted high photocatalytic activity of WO3

Patterned TiO2 stripes were formed on a sol-gel crystalline WO3 film by using a chemically modified sol-gel method (pat-TiO2/WO3), and the coupling effect on the photocatalytic activity was studied. Although the photoinduced electron transfer from TiO2 to WO3 was confirmed by labeling and visualization of the reduction sites with Ag particles, the photocatalytic activities of TiO2 for both the gas-phase oxidation of CH3CHO and the liquid-phase oxidation of 2-naphthol decreased significantly with the coupling. This finding was rationalized in terms of the decrease in the rate of the electron transfer from the semiconductor-(s) to 02 with the coupling, which was estimated from the kinetic analysis of the photopotential relaxation. When the excited electrons were removed by a SnO2 underlayer, the WO3 film exhibited a high photocatalytic activity exceeding that of TiO2 for the oxidation of 2-naphthol.     

TiO2纳米膜表面结构形态特征

采用反胶束法制备TiO2纳米溶胶,用浸渍提拉法在不同的条件下制备了三种TiO2多孔纳米薄膜,并利用AFM、SEM、XRD等方法对膜表面结构物理化学特性进行表征.结果表明三种膜基本上由粒径约为59 nm的纳米粒子以不同的方式堆积而成,溶胶刚生成时浸提一次,干燥、焙烧得到膜上纳米粒子分布均匀,所生成的二次粒子粒径最小,二次粒子形成的二次表面粗糙度最小,浸提10次得到膜上纳米粒子间存在较丰富缝隙结构,二次粒子粒径及其形成的表面粗糙度较大,而溶胶制备好陈化6 h后浸提得到的膜上二次粒子粒径最大,表面粗糙度最高.由分形理论估算得到三种膜的分形维数分别是2.22、2.20和2.27. XRD测试表明,膜上TiO2为锐钛矿晶相.这些结果表明,采用不同制备步骤得到的膜,其表面结构形态存在较大的差异.     

紫外光下纳米TiO2 薄膜亲水性机理的电化学研究

The nanometer films of TiO2 were prepared by sol-gel method on ITO（Indium-tin oxide,SnO2:In） substrate. The TiO2 film was the anatase phase with a particle size of 100 nm from the measurements of X-ray diffraction and AFM（Atomic-Force-Microscope）. Electrochemical characteristics of ITO/ TiO2 electrode under UV（ultraviolet）irradiation were investigated using the method of cyclic voltammetry. A new oxidative peak was observed at 0.035 V when the TiO2 electrode was irradiated by 253.7 nm UV light for a certain time. The peak current increased with the irradiation time. It was assumed that the new oxidative peak resulted from Ti3+,which was formed during the UV illumination. The changes of hydrophilicity of the TiO2 thin film on ITO under UV light were also observed. It was assumed that the changes of hydrophilicity of the films may be related with the formation of Ti3+ on the surface when the film was irradiated by UV light.     

Fast transient fluorescence technique (FTRF) for studying vapor-induced latex film formation

A fast transient fluorescence (FTRF) technique was used to study latex film formation induced by organic solvent vapor. Seven different films with the same latex content were prepared separately from poly(methyl methacrylate) (PMMA) particles and exposed to vapor of various chloroform-heptane mixtures in seven different experiments. Latex films were prepared from pyrene (Py)-labeled latex particles and fluorescence lifetimes of Py were monitored during vapor-induced film formation. It was observed that pyrene lifetimes decreased as vapor exposure time increased. A Stern-Volmer kinetic analysis was used for low quenching efficiencies to interpret the decrease in pyrene lifetimes. A Prager-Tirrel model was employed to obtain back-and-forth frequencies, nu, of the reptating PMMA chains during latex film formation induced by solvent vapor. nu values were found to be correlated with chloroform content in vapor mixture. It was observed that polymer interdiffusion obeyed a t(1/2) law during film formation. The results of optical transmission experiments were found to support these findings.     

TiO2/十六烷基三甲基溴化铵有序交替层状纳米复合薄膜的制备与结构表征

近年来有序交替的层状纳米结构薄膜的制备吸引了研究者们的极大关注. 目前, 这类薄膜的制备方法研究得最多的是LB技术[1～3]、基于化学吸附的自组装成膜技术[4,5]和交替沉积组装技术[6～8]. 但这几种方法都有明显的缺陷[9,10], 其中,通过LB技术制备有序交替层状纳米复合薄膜需要昂贵的仪器, 而且由于层间是分子相互作用, 膜的稳定性较差; 基于化学吸附的自组装成膜技术由于需要高反应活性的分子和特殊的基底表面, 并且由于化学反应的产率很难达到100%, 因此通过这种方法制备结构有序的多层膜并不容易; 利用交替沉积的方法制备出具有实用厚度的纳米多层膜需要耗费大量的时间. 最近, 出现了一种称为蒸发诱导的超分子自组装方法, 由这种方法制备的纳米多层膜具有成膜速度快和膜有序度高等优点, 此外还可以通过改变成膜物质浓度和拉膜速度来控制薄膜的厚度, 但与LB膜相比其厚度无法在分子水平上控制. 利用这种方法制备多层膜目前的文献报道仅限于线形SiO2与有机物的组装[10～13]. 本文利用这种方法制备了TiO2/十六烷基三甲基溴化铵纳米复合薄膜并对其结构进行了表征, 结果表明所制备的薄膜具有TiO2/十六烷基三甲基溴化铵有序交替的层状结构.     

双层分等级TiO_2纳米线制备及其光伏性能研究

采用两步溶剂热反应制备了底层为分等级锐钛矿的TiO_2纳米线阵列,上层为分等级锐钛矿的TiO_2纳米线薄膜的双层结构电极.通过XRD和SEM对其组成和形貌进行了表征,并考察了纳米线薄膜对染料敏化太阳电池(DSSC)光伏性能的影响.实验结果表明,分等级锐钛矿的TiO_2纳米线作为DSSC的光阳极,光电转换效率为4.39%,其效率高于光滑的TiO_2纳米线光阳极电池效率(2.07%).     

Adsorption and solar light decomposition of acetone on anatase TiO2 and niobium doped TiO2 thin films

Adsorption and solar light decomposition of acetone was studied on nanostructured anatase TiO2 and Nb-doped TiO2 films made by sol-gel methods (10 and 20 mol % NbO2.5). A detailed characterization of the film materials show that films contain only nanoparticles with the anatase modification with pentavalent Nb oxide dissolved into the anatase structure, which is interpreted as formation of substituted Nb=O clusters in the anatase lattice. The Nb-doped films displayed a slight yellow color and an enhanced the visible light absorption with a red-shift of the optical absorption edge from 394 nm for the pure TiO2 film to 411 nm for 20 mol % NbO2.5. In-situ Fourier transform infrared (FTIR) transmission spectroscopy shows that acetone adsorbs associatively with eta1-coordination to the surface cations on all films. On Nb-doped TiO2 films, the carbonyl bonding to the surface is stabilized, which is evidenced by a lowering of the nu(C=O) frequency by about 20 cm(-1) to 1672 cm(-1). Upon solar light illumination acetone is readily decomposed on TiO2, and stable surface coordinated intermediates are formed. The decomposition rate is an order of magnitude smaller on the Nb-doped films despite an enhanced visible light absorption in these materials. The quantum yield is determined to be 0.053, 0.004 and 0.002 for the pure, 10% Nb:TiO2, and 20%Nb:TiO2, respectively. Using an interplay between FTIR and DFT calculations we show that the key surface intermediates are bidentate bridged formate and carbonate, and H-bonded bicarbonate, respectively, whose concentration on the surface can be correlated with their heats of formation and bond strength to coordinatively unsaturated surface Ti and Nb atoms at the surface. The oxidation rate of these intermediates is substantially slower than the initial acetone decomposition rate, and limits the total oxidation rate at t>7 min on TiO2, while no decrease of the rate is observed on the Nb-doped films. The rate of degradation of key surface intermediates is different on pure TiO2 and Nb-doped TiO2, but cannot explain the overall lower total oxidation rate for the Nb-doped films. Instead the inferior photocatalytic activity in Nb-doped TiO2 is attributed to an enhanced electron-hole pair recombination rate due to Nb=O cluster and cation vacancy formation.     

血红蛋白与NO分子间相互作用的电化学表征

近年来 ,蛋白质的电化学研究引起了人们广泛兴趣[1～ 5] .利用自组装技术[4 ] 或将蛋白质分子固定于双层磷脂膜、水凝胶、表面活性剂膜及 Al2 O3膜上[6～ 9] 等可成为制备蛋白质膜的有效手段 .血红蛋白(Mr=6 50 0 0 )是生物体内一类重要的蛋白 ,由于对其结构已有较清楚的认识 [10 ] ,因而常被选作探讨生物大分子的电化学行为的模型分子 . NO是一种内皮细胞松弛因子、神经递质和免疫系统的媒介体 ,与生物体内的许多生理过程、疾病的产生与治疗有密切关系 [11～ 13] .因此研究蛋白与 NO之间的相互作用并寻求监测 NO的各种途径具有重要意义…     

Formation and characterization of surfactant stabilized silver nanoparticles: a kinetic study

Kinetic data for the silver nitrate–ascorbic acid redox system in presence of three surfactants (cationic, anionic and nonionic) are reported. Conventional spectrophotometric method was used to monitor the formation of surfactant stabilized nanosize silver particles during the reduction of silver nitrate by ascorbic acid. The size of the particles was determined with the help of transmission electron microscope. It was found that formation of stable perfect transparent silver sol and size of the particles depend upon the nature of the head group of the surfactants, i.e., cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulphate (SDS) and Triton X-100. The silver nanoparticles are spherical and of uniform particle size, and the average particle size is about 10 and 50 nm, respectively, for SDS and CTAB. For a certain reaction time, i.e., 30 min, the absorbance of reaction mixture first increased until it reached a maximum, then decreased with [ascorbic acid]. The reaction follows a fractional-order kinetics with respect to [ascorbic acid] in presence of CTAB. On the basis of various observations, the most plausible mechanism is proposed for the formation of silver nanoparticles.