高效率变色WO3多聚体/1,10-DAD自组装薄膜的制备

新型复合材料能够将多种特异性能结合在一种材料上,为未来的光电材料提供了广阔的应用前景[1,2].无机光电致变色材料因其在信息显示、传感器、调光器件和高密度存储等领域有显著的应用前景而倍受人们的关注[3－6].一般常规方法(物理沉积方法和化学沉积方法等)制备的半导体氧化物光电致变色材料存在着结构无定形、变色响应较慢、变色可逆疲劳等问题,限制了其进一步的应用.分子沉积膜（MolecularDeposition）技术[7,8]能有效构建纳米量级上高度有序的介观结构复合材料,能为新型无机变色材料的设计和构建提供技术支持.　　本研究组已成功地…     

自组装超薄膜: 从纳米层状构筑到功能组装

总结了一种新型的超薄膜自组装技术－交替沉积组装技术的发展现状,着重对成膜推动力、生物分子的层状组装、无机／有机杂化结构、有机小分子化合物的层状组装、超薄膜化学修饰电极、层间化学反应及非平衡基底上的层状构筑等几个方面的问题进行了讨论。     

光致变色WO3/4,4'-BPPOBp超晶格薄膜的制备

具有光致变色和电致变色特性的三氧化钨薄膜因其巨大的应用前景而倍受人们关注[1-4].其制备方法一般为物理沉积方法和化学沉积方法等.其中化学方法包括喷射裂解法[5],化学气相沉积法[6,7],电化学沉积法[8]和溶胶凝胶法[9]等.利用超分子化学自组装技术构建用有机组分调控的光致变色纳米超晶格薄膜材料,是研制光致变色功能薄膜材料的新方法.本文采用溶液中相反电荷聚电解质超分子自组装的方法(ＰＥｓ法)[10],制备了ＷＯ3/4,4′ＢＰＰＯＢｐ超晶格薄膜.采用紫外可见吸收光谱和小角Ｘ射线衍射谱对薄膜的结构和分子的排列方式进行了研究.1　实验…     

染料敏化TiO2/WO3薄膜电池的光电变色

The light-to-electricity conversion process of the TiO2 nanostructured electrode sensitized by a dye was investigated using the photoelectrochemical method in this paper. At the same time, the WO3 thin film was electrodeposited on conducting glass. The results showed that the dye-sensitized nanoporous TiO2 film has the properties of energy conversion, along with good electrochromic properties of electrodeposited MoO3 thin film. A self-powered smart window was achieved by combining a dye-sensitized nanoporous TiO2 film as the photovoltaic layer and an electrodeposited WO3 film as the electrochromic layer. This window changed from being almost transparent to blue spontaneously under illumination, and thus could modulate light transmittance.     

光致变色WO3/4,4′-BPPOBp超晶格薄膜的制备

Layered WO3/4,4′-BPPOBp self-assemble mulitlayers (SAMs) films have been fabricated by polyelectrolytes (PEs) approach.The SAMs films with well-ordered superlattice structure and d-space of 0.695nm and good photochromic property have been studied by employing UV- visible,small angle XRD and XPS.     

壳聚糖辅助制备WO_3薄膜材料及其电致变色性能

以壳聚糖(CS)为辅助材料,利用层层自组装方法(LbL)制备了WO3复合薄膜材料(CS/WO3).采用紫外-可见吸收光谱(UV-Vis)、扫描电子显微镜(SEM)和循环伏安扫描(CV)等手段对CS/WO3纳米复合材料的形貌和电化学性能进行了表征.利用电化学和UV-Vis联机技术研究了复合材料的电致变色性能.结果表明,该复合材料呈现出从无色到蓝色的颜色调变,其光反差可达48.0%,着色效率为58.5cm2/C,着色与褪色时间分别为9.5和1.8s.     

LBL自组装技术及自组装生物功能膜结构

主要介绍近几年发展的用于生物大分子自组装功能膜的三种逐层（LBL）自组装技术与制备方法,酰胺化反应自组装技术、生物分子的特异识别自组装技术、分子沉积自组装技术;同时总结了自组装功能膜的结构、特性的表征方法,主要有AFM、TEM、循环伏安法、石英晶体微天平（QCM）技术、UV/VIS、XPS方法等。     

阳极氧化膜WO3（Ⅰ）：电显色和自褪色

用循环伏安法、交流阻抗技术和光电流谱技术研究了阳极氧化膜WO_3电显色和自褪色过程的机理,电显色时,氢原子先在WO_3表面吸附,其后从WO_3表面向晶格内部传输,电褪色时,H_xWO_3晶格中填隙H原子先传输到W表面脱附生成填隙H~+,然后再在电场驱动下在膜中迁移,自褪色过程可能是由膜中所含的少量水和部分填隙H原子的羟基化作用引起的。     

乙二胺改性的玻璃基片上C60自组装薄膜的制备及光致发光

利用Ｃ６０与乙二胺改性的普通玻璃表面进行加成反应,得到一种新的Ｃ６０自组装单层膜;在自组装单层膜的基础上,利用Ｃ６０与乙二胺反应形成自组装双层膜。通过Ｘ光电子能谱、激光解吸电离飞行时间质说等手段证实在乙二胺改性的普通玻璃表面上存在通过化学键合的Ｃ６０自且装单层和双层膜。并对共光致发光性质进行了初步研究,发现在６８０ｎｍ附近存在一个与Ｃ６０不同的宽的光致发光峰。     

树形大分子的自组装

非共价的分子间作用力或超分子相互作用，可用于树枝直接自组装，或将树枝环绕在以某一中心核作模板的分子周围，最终形成树形大分子。另外，树形大分子自组装，可得到高度有序的液晶聚集体和单层膜，也可增加其它有机物的溶解性。综述了树形大分子的自组装研究进展、研究结果及其应用前景。     

聚合物前驱体法制备立方相WO_3薄膜的光电化学性质

以(NH4)6W7O24·6H2O为钨源,聚乙二醇1000(PEG 1000)为配位聚合物,采用聚合物前驱体法制备了WO3薄膜,利用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见(UV-Vis)吸收光谱等手段对其结构进行表征.采用循环伏安法、Mott-Schottky测试、瞬态光和稳态光电流谱等方法研究了WO3薄膜电极的光电化学性能.结果表明,制备的WO3薄膜为立方晶系,禁带宽度约为2.7eV.当热处理温度为450℃时,载流子浓度达到最大2.44×1022cm-3,平带电位为0.06V,在500W氙灯光源照射和1.2V偏压下,光电流密度为2.70mA·cm-2.进一步探讨了热处理温度对其光电性质的影响及其机理.     

NH0-1+2-3离解能等的高级ab initio计算与评价

A recent experimental determination[1] of the dissociation energies (D0) for H2N-H, H2N+-H and H2N-H+, the ionization energies for NH3 and NH2 resulted in large deviations when compared with those of the earlier values and the QCISD(T)/6-311+G(3df,2p) ab initio calculations. We have performed some higher level ab initio calculations on these data by utilizing the Gaussian 92/DFT and Gaussian 94 pakages of programs and have assessed the available experimental values. Our calculations were carried out at the QCISD (TQ)/aug-cc-pVDZ, G2(QCI), QCISD(T)/6-311 ++G(3df,3pd) and QCISD(T)/aug-cc-pVTZ levels of theory. Geometries were optimized at both of the MP2(full)/6-31G(d) and the MP2(full)/6-31(d,p) levels, and were compared with those of the experiments if available. The MP2(full)/6-31G(d,p) tight-optimized geometries for the neutrals are closer to those of the experiments than those of the MP2 (full)/6-31G(d), and are in excellent agreement with the experimental results as shown in Table 1. In this case, we assumed that the optimized geometries for the cations would be better if p polarization functions are added to the hydrogen atoms. We firstly noted that the symmetry of the NH3+ cation was D3h, other than Cs. as reported in ref.[1]. All of the zero-point energies and the final geometries are calculated at the MP2(full)/6-31G(d,p) level of theory. We have also repeated the QCISD(T )/6-311 + G(3df,2p) calculations of ref. [1], because we could not identify their level of goemetry optimization. It is found that the total energy, -55.244 19 Hartrees, for NH2+(1A1 ) in ref.[1] might be in error. Our result is -55.336 29 Hartrees at the same level of theory. At our highest level [QCISD(T)/aug-cc-pVTZ] of calculations as shown in Table 3, the D0 (temperature at zero Kelvin) values of H2N-H, H2N+-H(3B1for NH2+ ) and H2N- H+ are 4.51, 5.49 and 8.00 eV, respectively. These data reported in re f.[1] were 4.97, 5.59 and 8.41 eV, respectively. Our result on D0(H2N-H) supports the work of ref.[2,3,5,6]. The ionization energies (IE) for NH3 and NH2 (3B1 for NH2+) at our highest level are 10.11 and 11.09 eV while in ref.[1] were 10.16 and 10.78 eV, respectively. For the latter, our result supports the experiment of ref.[3]. Our predicted D0 for HN2+-H and IE for NH2 (1A1 for each NH2+) are 6.80 and 12.39 eV, respectively. These values differ greatly from the predicted values (9.29 and 14.88 eV) of ref.[1] where the total energy of NH2+(1A1) might be in error. The D0 value for HN-H has not been found in ref.[1]. Our result supports the work of ref.[3]. We have also derived all of these values at the temperature of 298K and under the pressure of 101kPa at several levels of thoery as shown in Table 3. On examining the experiment of ref.[1] in detail, it is easy to find that all of the larger deviations might be from a too high value of the appearance potential of proton AP(H+). Indeed, ref.[1] has mentioned that the determintion of AP(H+), due to kinetic shift, would lead to a hihger value for the dissociation energy as has been pointed out by Berkowitz and Ruscic. In this work, we concluded that, besides some mistakes in the theoretical calculations of ref.[1], the dissociation energies for H2N-H and H2N-H+,the IE for NH2 (3B1 for NH2+) might also be unreliable and need to be re-examined.
     

ZrO2表面B2O3的分散及其作用状态

用XPS、FT IR和FT Raman等技术研究了ZrO2表面B2O3的分散及其作用状态,测定了B2O3在ZrO2表面的分散阈值.结果表明：B2O3在ZrO2表面可以三配位BO3和四配位BO4结构单元存在;载体ZrO2的预焙烧温度和硼含量对B2O3的分散及作用状态有较大影响,并改变BO3与BO4结构单元之间的比例.实验测得B2O3在ZrO2载体上的单层分散阈值为0.05 gB2O3/gZrO2（或B2O3的质量分数w=4.76％）,处在此单层中的硼原子以BO4为结构单元直接与ZrO2表面相作用.只有当B2O3的负载量超过此（单层）分散阈值时, BO3结构单元才会形成.     

基于TiO2纳米管阵列的高效正面透光型染料敏化太阳能电池的制备及其光电性能

报道了一种基于TiO2纳米管(TNT)阵列正面透光型光阳极的高效染料敏化太阳能电池.将TNTs在450°C烧结后能避免其有序结构在HF处理过程中被破坏,使膜内高速电子传输通道被保留,有利于染料敏化太阳能电池(DSSC)实现高速电荷传输.再用HF、TiCl4、HF和TiCl4混合等溶剂对TNTs进行处理,提高其表面粗糙度以吸附更多染料.染料吸附量的增加能提高光阳极在300-570 nm波段光子捕获效率,该波段是染料吸收光子的主要区域.然而,在染料吸收光子较弱的长波段区域(570-800 nm)光子捕获效率的增加主要源于光阳极光散射率的提高.光阳极光子捕获效率的提高使DSSC的内外量子效率在全波段(300-800 nm)均有所增加,从而使短路电流明显提高.从电化学阻抗数据可知,与电子传输性能密切相关的电化学参数如电荷传输电阻、界面电荷复合电阻、电容、电子寿命、电子扩散长度和电子收集效率等在含处理过的TNTs光阳极DSSC中均有所改善,从而提高电池光电转换效率.含HF和TiCl4混合溶剂处理TNTs光阳极的DSSC最高光电转换效率能达到7.30%,比未处理的DSSC(5.38%)提高35.69%.     

微波辅助溶剂热合成In-Si共改性TiO2的增强光催化性能

利用微波辅助溶剂热法合成了In-Si 共改性的TiO₂ 光催化剂. 粉末X 射线衍射（XRD）、激光拉曼（Raman）光谱、N₂吸脱附（BET）、X射线光电子能谱（XPS）、光致发光（PL）光谱和紫外-可见漫反射光谱（UV-VisDRS）等实验表明,尽管掺杂和改性后TiO₂结晶度略有降低,但不影响光催化剂锐钛相的形成. Si 掺杂入TiO₂晶格使颗粒变小,比表面积变大. In 不能进入TiO₂晶格,在TiO₂表面形成了In₂O₃. 罗丹明B（RhB）降解实验显示,In-Si 共改性TiO₂表现出很高的紫外和可见光催化活性,Si：In：Ti 的摩尔比为0.03：0.02：1 的样品（IST-2）光催化活性最高,紫外光下3 min 即可将RhB降解完全,可见光下120 min RhB降解率为97%,这是由材料的高表面积,In₂O₃-TiO₂复合半导体之间高效电荷转移及染料敏化等共同作用所致. 对于苯酚,光催化降解则相对缓慢,700 min内尚不能降解完全.     

内嵌复合物X@C60中相互作用的变化规律与键本质

系统地研究了内嵌复合物Ｘ＠Ｃ６０（Ｘ＝第ＩＡ簇或第ＶＩＩＡ族元素）形成过程的能量变化,以及其中笼环境下Ｘ与Ｃ６０间相互作用的变化特征与键本质。结果表明：（１）Ｃ６０笼环境力场具有球对称性;（２）各种分解与总相互作用与内嵌原子的原子序数或原子半径呈现出规则的递变规律;（３）除Ｉ外,其余元素原子与Ｃ６０间的作用对各自复合物的稳定性都有正效应的较大贡献;（４）Ｘ在Ｃ６０笼环境中居心或偏心的稳定位置是各种     

含O2高温高压CO2环境中3Cr钢腐蚀产物膜特征

采用高温高压反应釜分别开展3Cr钢在CO2和O2共存、单独CO2和单独O2三种气体条件下的腐蚀实验,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能量色散X射线能谱(EDS)和电化学方法研究了3Cr钢在高温高压含有O2的CO2环境中的腐蚀产物膜特征.结果表明,在含有O2的CO2的条件下,3Cr钢表面腐蚀产物膜疏松多孔,主要成分为FeCO3、Fe3O4和Fe2O3,腐蚀产物中未见明显Cr元素富集,3Cr钢表现出点蚀的腐蚀形态.3Cr钢在高温高压含O2的CO2腐蚀条件下内外膜层电阻(Rf1、Rf2)和电荷传递电阻Rt均比仅含有CO2腐蚀环境的低,双电层电容(Cdl)和内外膜层电容(Cf1、Cf2)均比仅含有CO2腐蚀环境的高.含有O2的CO2条件下,其保护性显著低于单一CO2条件下形成的腐蚀产物膜.提出了在含O2的CO2气体条件下,3Cr钢表面存在由多种物质组成的腐蚀产物,这导致腐蚀产物疏松多孔,不会形成单一CO2条件下存在的显著提高腐蚀产物膜保护性的Cr(OH)3层,从而促进了3Cr钢的析氢腐蚀和酸性介质中的吸氧腐蚀的机理.     

Al(2Pu)+H2(X1Σ+g)的分子反应动力学

基于多体展式方法所导出的ＡｌＨ２（Ｘ＾２Ａ１）分析势能函数,用准经典的Ｍｏｎｔｅ－Ｃａｒｌｏ轨迹法对Ａｌ（＾２Ｐｕ）＋Ｈ２（Ｘ＾１∑＾＋ｇ,ｕ＝ｊ＝０）的分子反应动力学过程进行了计算。结果表明,此反应的主产物为交换反应Ａｌ（＾２Ｐｕ）＋Ｈ２（Ｘ＾１∑＾＋ｇ,ｖ＝ｊ＝０）→ＡｌＨ（Ｘ＾１∑＾＋,Ｖ’,ｊ’）＋Ｈ（＾２Ｓｇ）的ＡｌＨ（Ｘ＾１∑＾＋,ｖ’,ｊ’）没有发现ＡｌＨ２（Ｘ＾２Ａ１）的络合物。而     

C60微电极伏安法研究

The microdisk electrode voltammetric behaviors of C_(60) are reported in this communication. This was accomplished by use of a mixed solvent system as Acetonotrile:Xylene=1:4 and a supporting electrolyte as 0.1 mol·L~(-1) Bu_4NPF_6. Au, Pt and Hg (Pt) were used as working electrode. In this new conditions, the successive six step reduction of C60 were obtained at below 15 ℃. It was found that the former five steps are all the single electron reversible reduction, but behaviors of the sixth steps are like EC' processes. Several electrochemical data were determined.     

制备方法对WO3/ZrO2结构的影响

WO3/ZrO2 catalysts prepared from Zr(OH)4 and crystallized ZrO2 have been characterized by means of XRD, LRS (qualitative and quantitative), and the specific sufrace area has been measured. The influence of the preparation method, the contents of WO3 in the samples and the calcination tempearture on the specific surface areas of the samples, the phase of support and the structural states of active component has been studied. The results show: (1) WO3 can disperse on ZrO2 as a monolayer; (2) WO3 dispersed on Zr(OH)4 as a monolayer retards the crystalline growth of the support on calcination, makes it crystallizing into a metastable tetragonal modification, and prevents the inter- crystalline sintering between the crystallites of ZrO2. These factors would result in an increase in the specific surface area of WO3／ZrO2 prepared from Zr(OH)4. As the content of WO3 in the sample comes up to its monolayer capacity, this effect is displayed most fully. A chemical reaction can occur between WO3 and Zr(OH)4 (or the tetragonal ZrO2) at a high temperature(800℃),producing some superacid sites on the surface. By these views, the main experimental facts published in the literatures can been interpreted satisfactotily.