Self-assembly and photoelectric properties of cerium complexes with 3, 4, 9, 10-perylenetetracarboxylic acid on nanocrystalline TiO2 films

Self-assembled (SA) films (PMP, M = Ce³⁺ or Ce⁴⁺) of 3,4,9,10-perylenetetracarboxylic acid (PTA) on nanocrystalline TiO₂ films with Ce³⁺ or Ce⁴⁺ as a bridge were fabricated and characterized with UV-Vis, IR, and XPS synchrotron radiation photoelectron spectroscopy (SRPES) which gave the HOMO energy levels for the SA films. It was shown that thin-layer sandwich-type solar cells based on these SA films possess good properties for photoelectric conversion. While PTA-loaded TiO₂ electrode (P) generated 26.9% of incident monochromatic photon-to-electron conversion efficiency (IPCE), PMP-sensitized TiO₂ electrodes yielded 55.8% and 39.1% for Ce⁴⁺ and Ce³⁺ respectively. PMP films can be considered as a kind of complexes whose HOMO energy levels were proved to be higher than that of film P, which is one of the major reasons for the increase in IPCE from film P to film PMP.     

Photosensitization of nanocrystalline TiO2 electrodes with II B group metal-ion-bridged self-assembled films of 3,4,9,10-perylenetetracarboxylic acid

Self-assembled films (SA films) of 3,4,9,10-perylenetetracarboxylic acid (PTA) (Film P) and II B group metal-ion-bridged PTA (Film PMP, M=Zn²⁺, Cd²⁺, or Hg²⁺) were fabricated on nanocrystalline TiO₂ electrodes and characterized with UV–VIS and IR spectra and XPS. Compared with Film P sensitized solar cell, Grätzel cells based on individual PMP electrodes are more efficient regarding photocurrent generation. Synchrotron radiation photoelectron spectroscopy (SRPES) study reveals that those HOMO energy levels of PMP films are greater than that of Film P. The higher HOMO energy levels will lead to higher excited state energy levels that benefit electron injection, and hence, increase efficiencies for photocurrent generation. In view of the invariable valence of Zn²⁺, Cd²⁺, and Hg²⁺ ions, electron injection should be attributed to ligand, but not to the central metal ions, like the case of Ru(II)–bipyridyl complex.     

TiO2纳米晶电极上半菁衍生物分子设计中空间位阻效应的研究

设计合成了具有不同空间位阻的吡啶盐类和喹啉盐类半菁染料 (E) N ( 4 磺酸根丙基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]吡啶盐 (EPS) ,(E) N ( 4 磺酸根丁基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]吡啶盐 (EPS4)和 (E) N ( 4 磺酸根丁基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]喹啉盐 (EQS4) ,研究了它们的光物理性质 ,并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池中 .研究发现 :对于吡啶类半菁染料而言 ,无论是以三个亚甲基或是以四个亚甲基来连接吸附基团RSO-3 和发色团时 ,单个的EPS和EPS4分子的光电响应行为一致 .但是由于以三个亚甲基来连接时 ,与EPS4相比 ,染料EPS的空间位阻相对较小 ,有利于其在多孔膜上的吸附 ,最终结果是染料EPS对TiO2 纳米晶电极的敏化作用好于EPS4.以喹啉环为受电子基团的染料EQS4与同样含有四个亚甲基的以吡啶环为受电子基团的EPS4相比 ,单个EQS4分子的光电响应行为虽然好于EPS4分子 ,但由于EQS4分子间的空间位阻较大 ,影响了它在多孔电极上的吸附 ,致使其敏化的太阳能电池的总光电转换效率有所下降     

In situ spectroelectrochemical behaviour of nanocrystalline TiO_2 thin films electrode fabricated by pulsed laser deposition

Nanocrystalline titanium oxide thin films have been successfully deposited on ITO coated glass by pulsed laser ablation of metallic Ti target in O_3/O_2 ambient gases. The intercalation of Li ions in the anatase TiO_2 film electrode is examined by cyclic vohammetry. The electrochromic behaviour of TiO_2 electrode is investigated by in-situ visible transmittance measurement, and two absorption bands at 420 and 650 nm are observed. The absorption falling and rising in color changing with excellent revisibility is relative to the insertion and deintercalation processes of Li ion. These resuits suggest that nanocrystalline titanium oxide films fabricated by pulsed laser deposition exhibit excellent spectroelectrochemical property.     

Enhancement of Overall Photovoltaic Efficiency by Changing the Position of the Attaching Group -RSO3- on the Hemicyanine Dye Molecules

A new photoresponsive D-π-A dye, mPS, has been designed and synthesized.Compared to the parent dye PS, IPCE values in the region from 400 nm to 560 nm was greatly improved upon changing the attaching group from the p- position to the o- position of the π-conjugation bridge. A solar cell based on mPS generated a remarkably high overall yield η of 5.4% under irradiation of 80.0 mW cm^-2 white light from a Xe lamp, Compared with PS, the overall yield η increased by 64%.     

葡萄皮色素敏化TiO_2的光电转换性能的研究

1991年,Gratzel[1]教授首次报道了染料敏化多孔TiO2纳米薄膜为光阳极的太阳能电池(Dye-sensitized Solar Cells,简写为DSSCs),其光电转化效率在AM1.5的模拟太阳光照射下可以达到7.1～7.9%,并且价格低廉,因而引起了全世界的关注.     

Preparation of TiO2 nanocrystalline films controlled by acetylacetone/polyethylene glycol and their photoelectric properties

TiO₂ nanocrystalline films were prepared from titanium tetra-n-butoxide modified with double hydrolysis inhibitors, acetylacetone and polyethylene glycol (PEG), in mixture of methanol and ethanol. The correlation among surface structure of the TiO₂ films, preparation conditions, and photovoltaic properties of the solar cells using the TiO₂ films was investigated. The particle size of the obtained TiO₂ films was decreased as the PEG content increased. The nanostructured films with the narrow distribution of particle size could be prepared. The amounts of adsorbed dyes for these TiO₂ films were larger than that without PEG. The performance of the solar cell fabricated using the TiO₂ film improved as the amount of the PEG increased, and the solar cell using the TiO₂ film prepared from the solution with 30 wt% PEG exhibited the highest performance.     

Electrochemical impedance spectra of CdSe quantume dots sensitized nanocrystalline TiO_2 solar cells

Quantum dots sensitized nanocrystalline TiO2 solar cells (QDSSCs) are promising third-generation photovoltaic devices.In comparison with conventional dye-sensitized solar cells (DSSCs),the efficiency of QDSSCs is still very low (about 3%).In this paper,the electrochemical impedance spectroscopy technology has been adopted to investigate the quasi-Fermi level and the carrier dynamics of the colloidal CdSe QDs sensitized TiO2 eletrode with S2-/Sxredox electrolytes and the series resistance of the QDSSCs.In co...     

Structure and photochromic properties of molybdenumphosphoric acid/TiO_2 composite films

TiO_2 sol-gel composite films with dropping molybdenumphosphoric acid(PMoA) have been prepared by sol-gel method.The structure and constitute of composite thin films were studied with Fourier transforms infrared spectroscopy(FT-IR),atomic force microscopy(AFM),and X-ray diffraction(XRD) patterns,respectively.The photochromic behavior and mechanism of composite thin films were inves-tigated with ultraviolet-visible spectra(UV-vis) and electron spin resonance(ESR).FT-IR results showed that the Keggin geometry...     

纳米结构TiO2/PS及TiO2空心球的自组装与表征

以TiCl₄的盐酸溶液配制的TiO₂溶胶为前驱体, 以聚苯乙烯微球为载体, 在表面活性剂存在下, 通过逐层自组装技术制备了纳米结构TiO₂/PS及TiO₂空心球. 利用XRD, SEM, TG-DTA等对复合颗粒进行了表征. 研究表明: 纳米结构TiO₂/PS的组成、结构、形貌和粒度可通过溶胶酸度、组装时水解反应温度、煅烧温度、硫酸根的加入量来控制.     

Structure and photoelectric properties of LB films of porphyrin bearing pyridinium with long-chain alkyl group

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Self-assembly properties of bile acid derivatives of l-cysteine,l-valine and l-serine alkyl esters

Comprehensive self-assembly studies for nine bile acid amides of amino acid esters are reported. The number of the hydroxyl groups attached to the steroidal skeleton and the character of the amino acid ester moiety were used as variables when examining the self-assembly properties of the compounds. Two of the compounds were shown to undergo self-assembly leading to organogelation. In addition, preliminary self-assembly studies in aqueous mixtures of polar organic solvents were conducted. Microscopic methods (optical microscopy and scanning electron microscopy) were utilised in order to gain a deeper insight into the self-assembled structures. Furthermore, single-crystal X-ray structures for three of the compounds were solved.     

Photocatalytic Characterization of TiO_2 Supported on Active Carbon

Photocatalysis on TiO2, with a promising application to the elimination of organic contaminants from air and water, has been a particularly active area1. For such application, it is important to improve the efficiency of TiO_2 photocatalysts. In the most cases, the concentration of organic contaminants in water is extremely dilute (ppm level or below) and TiO_2 itself has low adsorbabilities for them, it usually takes a long time to complete their decomposition. One of the effective ways to …     

Composite Electrode SnO2／TiO2 for Dye-Sensitized Solar Cells

Composite nanoporous electrode SnO2/TiO2 was fabricated for the dye sensitized solar cell (DSSC) with N3 (Cis-Ru). After introducing of TiO2, the open-circuit photovoltage (Voc) was higher than that of the pure SnO2 electrode, while short-circuit photocurrent (Isc) was varied with the ratio of the TiO2. Appropriate content of the TiO2 can be beneficial to the efficiency of the solar cell, and it gives negative impact on the composite electrode when the content of TiO2 is higher.     

高效光催化活性钠米农药制剂的制备

采用钛酸丁酯水解法制备出直径约为20 nm的纳米TiO2,并用钛酸丁酯对其进行改性。研究表明TiO2与硬脂酸事实上通过化学键键合,由亲水性变为亲油性。文中还提出了三种制备TiO2复合纳米农药制剂的方案,并探讨了几种TiO2复合纳米农药制剂在不同条件下的光催化降解率。结果表明,采用钛酸丁酯为原料直接在农药乳油中原位生成的TiO2复合纳米农药制剂与原农药性状保持基本一致,光催化降解率最大。     

Preparation and characterization of CoFe_2O_4/TiO_2 magnetic composite films

CoFe2O4/TiO2 magnetic composite films were prepared using the sol-gel method with tetrabutyltitanate and metallic chlorates as starting materials. The effects of heat treatment temperatures on micro- structures and on magnetic properties were studied. The microstructure and properties of the samples at different heat treatment temperatures were characterized by X-ray diffraction, Raman spectrum, scanning electron microscopy, polarized microscopy and vibrating sample magnetometry. The results show that crystals of different substances grow up independently. Cobalt ferrite is evenly embedded into the titanium dioxide matrix in the prepared composite films. The magnetism of the composite films is enhanced with an increase of the heat temperature.     

两种菁类染料复合敏化TiO_2纳米晶电极的光电化学研究

应用光电化学方法研究了两种菁类染料Cy3和Cy5复合敏化TiO2纳米晶电极的光电化学行为.结合两种染料的紫外-可见光谱和循环伏安曲线,确定了Cy3和Cy5的电子基态和激发态能级位置.结果表明两种染料的激发态能级位置能与TiO2纳米粒子导带边位置相匹配,复合敏化可以显著提高TiO2纳米晶的光电流,使TiO2纳米晶电极吸收波长由紫外光区红移至可见光区和近红外区.复合敏化降低了染料Cy3 在电极吸附时的聚集程度,使其单色光的转换效率(IPCE)提高了169%,复合敏化电极总的光电转换效率η为2.09%,分别是Cy3和Cy5单独敏化时光电转换效率的2.069 和1.229倍.     

纳米TiO_2的有机酸改性

纳米TiO2粉体独特的光催化作用、颜色效应以及紫外屏蔽等功能使其在汽车工业、防晒化妆品、环保等方面有着广阔的应用前景[1-3]。未经表面处理的纳米TiO2表面疏油,不易在有机介质中分散,直接影响到TiO2性能的发挥。锐钛矿型TiO2晶体中[4], Ti—O键距离短且不等长,分别为1·937A°和1·964A°,这种不平衡使TiO2分子极性很强,强极性使得TiO2表面易吸附水分子并使水分子极化而形成表面羟基。本文选用月桂酸和棕榈酸作为改性剂,让羧基与TiO2的羟基以化学吸附的形式连接起来,使纳米TiO2表面改性为亲油性。结果表明棕榈吸的改性效果较月桂…     

Preparation and characterization of highly photoactive nanocrystalline TiO_2 powders by solvent evaporation- induced crystallization method

Highly photoactive bi-phase nanocrystalline TiO2 photocatalyst was prepared by a solvent evaporation-induced crystallization (SEIC) method, and calcined at different temperatures. The obtained TiO2 photocatalyst was characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface areas. The photocatalytic activity was evaluated by the photocatalytic oxidation of acetone in air. The results show that solvent evaporation can promote the crystallization and phase transformation of TiO2 at 100℃. When calcination temperatures are below 600℃, the prepared TiO2 powders show bimodal pore size distributions in the mesoporous region. At 700℃, the pore size distributions exhibit monomodal distribution of the inter-aggregated pores due to the collapse of the intra-aggregated pores. At 100℃, the obtained TiO2 photocatalyst by this method shows good photocatalytic activity, and at 400℃, its photocatalytic activity exceeds that of Degussa P25. This may be attributed to the fact t     

SiW12、PbS对提高TiO2纳米管光电转换效率的协同效应研究

复合薄膜可以改善TiO2纳米管在光电转换时电子-空穴易复合和吸收光谱范围窄的缺陷。用电沉积法将多酸H4SiW12O40（SiW12）沉积在TiO2纳米管表面形成SiW12/TiO2纳米管复合薄膜,再用连续离子层吸附反应法（SILAR）将PbS吸附到SiW12 /TiO2纳米管复合薄膜表面,形成PbS/ SiW12/TiO2纳米管复合薄膜,所得薄膜的光电转换效率相较于TiO2纳米管提高了57倍。X射线衍射（XRD）和扫描电子显微镜（SEM）表征结果表明,用电沉积法和连续离子层吸附反应法实现了PbS/SiW12/TiO2纳米管复合薄膜的制备;紫外可见（UV-vis）吸收光谱测试表明,复合薄膜的光吸收带边扩展到了可见光区域,电化学阻抗测试（EIS）表明,复合薄膜具有更高的电子转移速率;荧光光谱（PL）测试表明,复合薄膜拥有更小的电子-空穴复合率。以上结果说明,SiW12、PbS与TiO2纳米管复合,很好地抑制了TiO2纳米管电子-空穴的复合,并拓宽了吸收光谱范围,能显著地提高TiO2纳米管的光电性能。本文探索了一种有效提高TiO2纳米管光电转换效率的方法,对TiO2纳米管复合薄膜的制备具有一定的参考意义。