Surface states and resonances in field emission from low-index facets of clean tungsten

The energies, widths, and shapes of features observed in the total energy distributions in field emission from W(1 0 0) and W(1 1 1) are compared with the results of a full-potential LAPW calculation of the surface density of states based on a supercell model of the crystal structure at the metal–vacuum interface. The Swanson hump on W(1 0 0) is attributed to two bands of surface states and surface resonances of d_z² symmetry that are highly localised at , and a second peak observed at lower energy is attributed to a band of surface resonances, also of d_z² symmetry, centred at from along . The energy scale of the calculated total energy distribution is compressed by about 20% relative to the experimental data. The present calculation yields strong evidence that the broad asymmetric peak observed on W(1 1 1) is due to emission from a band of surface resonances. Further calculations for W(1 1 1) are proposed both to test the accuracy of the band model and to take into account the velocity factor that enters in a calculation of the emission current.     

Photosensitization of TiO2 nanoparticulate thin film electrodes by CdS nanoparticles

Surface photovoltage spectra (SPS) measurements of TiO₂ show that a large surface state density is present on the TiO₂ nanoparticles and these surface states can be efficiently decreased by sensitization using CdS nanoparticles as well as by suitable heat treatment. The photoelectrochemical behavior of the bare TiO₂ thin film indicates that the mechanism of photoelectron transport is controlled by the trapping/detrapping properties of surface states within the thin films. The slow photocurrent response upon the illumination can be explained by the trap saturation effect. For a TiO₂ nanoparticulate thin film sensitized using CdS nanoparticles, the slow photocurrent response disappears and the steady-state photocurrent increases drastically, which suggests that photosensitization can decrease the effect of surface states on photocurrent response. Electronic Publication     

金属氢化物电极表面处理方法及其表面氧化膜研究 Ⅰ.富镍表面处理及氧化膜的光电化学方法研究

发展了两种贮氢合金表面处理新方法．光电子能谱和循环伏安实验表明,经过处理后得到了富镍表面层,可提高电极的反应性能．采用光电化学方法对不同处理的电极表面由动电位氧化形成的氧化膜进行了表征,分别观察到与表面膜吸附氢氧化和氧化还原反应有关的阳极光电流和阴极光电流,同时依照电极在循环过程中的光电流变化区分了两种处理方法所得到的表面层抗氧化性能之差异．通过粉末单电极初期充放电实验,证实了电极经方法１处理以后其放电性能得到提高．     

Effects of 3,4-dihydrophenyl groups in water-soluble phospholipid polymer on stable surface modification of titanium alloy

The surface of a titanium (Ti) alloy substrate was modified by a simple and quick process using a water-soluble polymer, and the effects of 3,4-dihydroxyphenyl (DHP) groups in the polymer side chain on the modification process were examined. The polymers (PMDP) composed of both 2-methacryloyloxyethyl phosphorylcholine (MPC) unit and 3,4-dihydroxyphenyl methacrylate unit were synthesized for surface anchoring. The Ti alloy substrate was coated with PMDP using an aqueous solution of the polymer. A PMDP layer with a thickness of 20 nm was formed on the Ti alloy substrate simply by dip coating for 10 s without drying. Even when the Ti alloy substrate with PMDP coating was immersed in the aqueous medium for 1 week, no change in the thickness was observed, i.e., the PMDP layer was bound to the surface very stably. Oxidation of the DHP groups reduced the stability of the polymer layer significantly. Thus, the DHP groups play a significant role in achieving stable binding. Protein was adsorbed on the Ti alloy substrate; however, this was not observed for the PMDP-coated Ti alloy substrate. In conclusion, we confirmed the effects of DHP groups in PMDP on the stability of the coating on the Ti alloy substrate. Moreover, we found that surface treatment using PMDP was simple, quick, and reliable, and thus, it has great potential for improving biofouling of Ti alloy substrates used in medical devices.     

电沉积-置换法制备Pt/Ti对电极及其对染料敏化太阳能电池性能的提升

采用电沉积-置换法在Ti片上制备了染料敏化太阳能电池(DSSC)的对电极Pt/Ti. 形貌表征结果显示, 与传统热解法制备的Pt/FTO对电极相比, Pt/Ti对电极Ti基底上Pt催化颗粒的粒径和分散性得到显著改善. 光电流-光电压特性曲线测试结果表明, 以Pt/Ti为对电极的DSSC与以Pt/FTO为对电极的DSSC相比, 光电转化效率提高了20.8%. 由于Pt颗粒分散性和粒径的改善所引起的Pt催化性能的提高、 Pt/Ti对电极更低的电阻以及Ti基底更好的反光性能是提升DSSC性能的原因.     

表面离化源工作参数对离子迁移率谱的影响

根据表面离化过程中样品分子在离化材料表面直接离化的特点,设计了一种样品离化和离子注入一步完成的面-网结构表面离化源.以金属钼为离化材料,三乙胺为测试样品,研究了离化源温度、离子门开门脉冲宽度和高度对离子谱图的影响.结果表明,离子流信号强度随离化温度升高迅速增强但离化源寿命缩短,理想的离化温度约为400℃；增加开门脉冲宽...     

Photoelectrochemical oxidation of methanol on oxide nanosheets

Photoelectrochemical oxidation of alcohol on various nanosheet electrodes such as Nb6O17, Ca2Nb3O10, Ti(0.91)O2, Ti4O9, and MnO2 system host layers were measured to evaluate the photocatalysis of water photolysis with alcohol as a sacrificial agent. The nanosheet electrodes were prepared by the layer-by-layer (LBL) method, using electrostatic principles. The highest photooxidation current density was observed in methanol solution for Nb6O17 and Ca2Nb3O10 nanosheets, while the density was lower for Ti(0.91)O2, Ti4O9, and MnO2 nanosheets in decreasing order. The rank in the photocurrent density was in agreement with that in the photocatalytic activity, which means that the degree of photooxidation of the alcohol determines the activity of the alcohol in the water photolysis process. The photocurrent was independent of the number of nanosheet layers on the electrode, indicating that only the mono-nanosheet layer attached directly on a substrate acts as a photoelectrocatalyst and that the interlayer space is not important. Consequently, higher photooxidation current on the Nb6O17 mono-nanosheet layer means that the charge separation of electron and hole under illumination is very large and that the hole-capturing process by CH3OH is very quick compared with the surface recombination on the Nb6O17 nanosheet. The adsorption of a transition metal cation on the nanosheet acted as the surface recombination center, because the photocurrent decreased after the adsorption. The photocatalytic mechanism has been discussed in detail in terms of various photoelectrochemical behaviors.     

基于表面金属有机化学方法的硅胶表面氧化钛的制备及表征

以普通硅胶为载体, 采用表面金属有机化学合成技术, 通过“一锅”反应制备了硅胶表面金属有机钛化合物, 然后经高温煅烧获得了硅胶表面氧化钛. 采用傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)、 热重分析(TG-DTA)及原子力显微镜(AFM)对硅胶表面金属有机钛化合物和表面氧化钛进行了结构表征. 结果表明, 高温煅烧过程中, 硅胶表面金属有机钛化合物不仅脱除了有机配体, 并且通氧使其表面“再生”羟基, 确保了钛的四配位形式不变; 氧化钛通过Si—O—Ti键锚定在硅胶表面, 呈分散、 孤立状态分布. 高温煅烧后, 硅胶的骨架结构保持完好.     

Photoelectrocatalytic disinfection of E. coli suspensions by iron doped TiO2

Photoelectrocatalytic disinfection of E. coli by an iron doped TiO(2) sol-gel electrode is shown to be more efficient than disinfection by the corresponding undoped electrode. Thus, the improvements in photocatalytic efficiency associated with selective doping have been combined with the electric field enhancement associated with the application of a small positive potential to a UV irradiated titanium dioxide electrode. The optimum disinfection rate corresponds to the replacement of approximately 0.1% of the Ti atoms by Fe. The enhanced disinfection associated with iron doping is surprising because iron doping decreases the photocurrent, and photocurrent is generally taken to be a good indicator of photoelectrocatalytic efficiency. As the level of iron is increased, the character of the current-voltage curve changes and the enhancement of photocurrent associated with methanol addition decreases. This suggests that iron reduces the surface recombination which in the absence of iron is reduced by methanol. Therefore the enhanced photocatalysis is interpreted as due to iron reducing surface recombination, by trapping electrons. It is proposed that at low iron levels the photo-generated electrons are trapped at surface Fe(III) centres and that consequently, because the electron-hole recombination rate is reduced, the number of holes available for hydroxyl radical formation is increased. It is also proposed that at higher iron levels, the disinfection rate falls because electron hole recombination at iron centres in the lattice reduces the number of holes which reach the surface. Our conclusion that the optimum electrode performance is a balance between surface and bulk effects is consistent with the proposal, of earlier authors for photocatalytic reactions, that the optimum dopant level depends on the TiO(2).     

Synthesis and properties of a new AIE macrocyclic emitter with triarylamine backbone

A new macrocyclic AIE emitter composed of triarylamine backbone was successfully synthesized through convenient homocoupling procedure and easily purified by silica gel column chromatography, and recrystallization. The optical and electrochemical properties of the compound have been investigated. Intriguingly, the compound shows dual emission both 423 nm and 505 nm. This result implied that the violet emission was originated from an isolated component of the emitter, whereas the yellowish-green emission simultaneously exhibited AIE nature. The compound exhibits enough thermal stability and high glass transition temperature to be applied for organic devices.     

TiCl4(THF)2 impregnation on a flat SiOx/Si(1 0 0) and on polycrystalline Au foil: determination of surface species using XPS

TiCl₄(THF)₂ was impregnated by spin-coating on a Si(1 0 0) wafer covered with a thin SiO_x layer and on a polycrystalline Au foil. The nature of the surface species was determined at room temperature and after annealing, by X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM). A mixed Si:O:Ti interfacial layer was formed on the silicon substrate while in the case of Au, TiOCl_x and TiO_x were the main surface species at room temperature. Annealing at 723 K leads to the total desorption of the Cl atoms, and in both cases a significant amount of Ti atoms was reduced to the Ti³⁺ state. AFM measurements revealed a homogenous distribution of nano-sized TiO_x clusters with semi-ellipsoid shape and increased contact area with the underlying silica.     

Visible-light driven Gd2Ti2O7/GdCrO3 composite for hydrogen evolution

A series of Gd(2)Ti(2)O(7)/GdCrO(3) composites are prepared by solid state combustion method using Gd(NO(3))(3), TiO(2), Cr(2)O(3) as metal source and urea as a fuel. The composites are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-visible diffuse reflectance spectra (DRUV-vis), Brunauer-Emmett-Teller (BET) surface area measurements, photoluminescence spectra (PL), X-ray photoelectron spectroscopic (XPS) studies, photocurrent measurements etc. The photocatalytic activity of the composites is examined towards hydrogen production without using any co-catalyst under visible light illumination. The rate of formation of hydrogen is measured by the photocatalytic activity measurement device and gas chromatography (GC). The highest efficiency is observed over the composite GTC (Cr:Gd:Ti = 1:1:1). On the basis of photocurrent measurements and PL, a mechanism for the enhanced photocatalytic activity has been discussed.     

ZnO/BiVO4-V2O5异质结构光生电荷性质及可见光下表面光电流行为

利用水热法合成了花状和球状ZnO微纳材料,并与硝酸铋和偏钒酸铵溶液体系反应构筑了ZnO/BiVO4-V2O5复合体系.利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)及X射线衍射(XRD)对材料进行了系统的表征.利用表面光伏(SPV)、表面光电流(SPC)和瞬态光伏(TPV)技术研究了ZnO/BiVO4-V2O5表面光生电荷的产生和传输机制.结果显示该复合材料在可见区产生了良好的光电响应,获得了较高的光生载流子的分离效率,光生电荷的寿命也同时增加.在单色弱可见光(波长500 nm)照射下,复合材料产生良好重复性的表面光电流响应.     

煅烧温度对纳米TiO2光电响应的影响

自从Graetzel及其合作者在液结太阳能电池研究方面取得重大突破以来,纳米晶多孔膜电极越来越引起人们的兴趣。TiO2纳米结构电极是由纳米粒子烧结在一起的三维海绵状结构,电解液可渗透到电极内部,因而电荷的传输较复杂。如何提高纳米结构电极的光电转换效率是一个值得大力研究的问题。本文探索了煅烧温度对TiO2纳米结构电极电荷传输特性的影响,旨在为提高太阳能转换中光电转换效率而寻找有效途径。     

Some interesting properties of black hydrogen-treated TiO2 nanowires and their potential application in solar energy conversion

Hydrogen treatment has been proposed as a simple and effective strategy to enhance the performance of Ti O2 nanostructures for applications such as photocatalysis and photoelectrochemical(PEC) water splitting. While some studies have suggested that the black color can be ascribed to surface disorder, other reports have suggested that it is caused by the "oxygen vacancy" states associated with Ti3+ within the bandgap of the Ti O2. The chemical nature and potential use of the bandgap states responsible for the black color of increased visible absorption is not yet well understood and subject of strong interest. Here we briefly review current understanding of the possible mechanisms behind the black color of hydrogen-treated Ti O2 nanowires and its relevance to photocatalysis and solar water splitting for hydrogen generation. One important conclusion to date is that while hydrogen treatment enhances photocurrent of Ti O2 with UV excitation, no noticeable photocurrent can be detected with visible light, which seems to be due to the very short lifetimes of the bandgap oxygen vacancy states arising from hydrogen treatment.     

高介电常数TiO2纳米晶的表面态研究

将钛酸四丁酯和硬脂酸在熔融状态下混合均匀后置于冷水浴中,使其凝固成凝胶,通过控制烧结过程中氧气的含量,成功地制备出粒度均匀、介电性能好的纳米晶TiO2.通过采用X射线光电子能谱和表面光电压谱对纳米晶TiO2表面状态的分析发现,材料表面存在大量的氧空位缺陷,暴露在粒子表面上的主要是一些金属Ti4+.纳米材料的这种表面状态对其极化性质具有重要的影响,使其在接近静态条件下的低频介电常数远大于常规材料的介电常数.     

Surface Engineering of Titania Boosts Electroassisted Propane Dehydrogenation at Low Temperature

Electric field catalysis using surface proton conduction, in which proton hopping and collision on the reactant are promoted by external electricity, is a promising approach to break the thermodynamic equilibrium limitation in endothermic propane dehydrogenation (PDH). This study proposes a catalyst design concept for more efficient electroassisted PDH at low temperature. Sm was doped into the anatase TiO₂ surface to increase surface proton density by charge compensation. Pt−In alloy was deposited on the Sm-doped TiO₂ for more favorable proton collision and selective propylene formation. The catalytic activity in electroassisted PDH drastically increased by doping an appropriate amount of Sm (1 mol % to Ti) where the highest propylene yield of 19.3 % was obtained at 300 °C where the thermodynamic equilibrium yield was only 0.5 %. Results show that surface proton enrichment boosts alkane dehydrogenation at low temperature.     

氢原子在Ti(0001)表面吸附的密度泛函理论研究

用密度泛函理论研究了氢原子的污染对于Ti(0001)表面结构的影响. 通过PAW总能计算研究了p(1×1)、p(1×2)、3^1/2×3^1/2R30[deg]和p(2×2)等几种氢原子覆盖度下的吸附结构, 以及在上述结构下Ti(0001)面fcc格点和hcp格点的氢原子吸附. 结果表明, 在p(1×1)-H、p(1×2)-H、3^1/2×3^1/2R30[deg]-H和p(2×2)-H几种H原子覆盖度下, 以p(1×1)-H结构的单个氢原子吸附能为最大. 在p(1×1)-H吸附结构下, 由于氢原子吸附导致的Ti(0001)表面Ti原子层收缩的理论计算数值分别为-2.85%(hcp吸附)和-4.31%(fcc吸附), 因此实际上最有可能的情况是两种吸附方式都有一定的几率. 而实验中观察到的所谓“清洁”Ti(0001)表面实际上是有少量氢原子污染的表面. 不同覆盖度和氢分压下, 氢原子吸附的污染对Ti(0001)表面结构有极大的影响, 其表面的各种特性都会随覆盖度的不同而产生相应的变化.     

电沉积二氧化钛纳米微粒膜的光电化学性能和表面形貌研究

采用光电流谱、透射光谱和扫描微探针显微镜技术对电沉积法制备的二氧化钛纳米微粒膜的光电化学性能和表面形貌进行了研究.结果表明,不同制备条件下的二氧化钛纳米微粒膜具有与紧密的半导体电极不同的光电化学性质,并探讨了其光电化学性能与表面形貌的关系.     

Effect of solution viscosity on dynamic surface tension detection

A dynamic surface tension detector (DSTD) was used to examine the molecular diffusion and surface adsorption characteristics of surface-active analytes as a function of solution viscosity. Dynamic surface tension is determined by measuring the differential pressure across the air/liquid interface of repeatedly growing and detaching drops. Continuous surface tension measurement throughout the entire drop growth is achieved for each eluting drop (at a rate of 30 drops/min for 2 μl drops), providing insight into the kinetic behavior of molecular diffusion and orientation processes at the air/liquid interface. Three-dimensional data are obtained through a calibration procedure previously developed, but extended herein for viscous solutions, with surface tension first converted to surface pressure, which is plotted as a function of elution time axis versus drop time axis. Thus, an analyte that lowers the surface tension results in an increase in surface pressure. The calibration procedure derived for the pressure-based DSTD was successfully extended and implemented in this report to experimentally determine standard surface pressures in solutions of varied viscosity. Analysis of analytes in viscous solution was performed at low analyte concentration, where the observed analyte surface activity indicates that the surface concentration is at or near equilibrium when in a water mobile phase (viscosity of 1.0 Cp). Two surface-active analytes, sodium dodecyl sulfate (SDS) and polyethylene glycol (MW 1470 g/mol, PEG 1470), were analyzed in solutions ranging from 0 to 60% (v/v) glycerol in water, corresponding to a viscosity range of 1.0-15.0 Cp. Finally, the diffusion-limited surface activity of SDS and PEG 1470 were observed in viscous solution, whereby an increase in viscosity resulted in a decreased surface pressure early in drop growth. The dynamic surface pressure results reported for SDS and PEG 1470 are found to correlate with solution viscosity and analyte diffusion coefficient via the Stokes-Einstein equation.