酞菁和酞菁铜的电子结构与光谱

用ＩＮＤＯ／ＣＩ方法研究了酞菁和酞菁铜的电子结构和紫外－可见光谱。对酞菁采用共享氢模型。酞菁铜的一个单电子位于１１ｂ１ｇ（ｄｘ＾２－ｙ＾２）的ＭＯ上。从酞菁铜与酞菁，分子对称性由Ｄ４ｈ降低为Ｄ２ｈ，谱线发生分裂。计算结果基本与实验结果相符。     

Ce掺杂对SnO2薄膜电学及气敏性能的影响

以无机盐ＳｎＣｌ２．２Ｈ２Ｏ（Ｎ４）３Ｃｅ（ＮＯ３）６为原料，无水乙醇为溶剂，采用溶胶－凝胶工艺制备了纯ＳｎＯ２及ＳｎＯ２：Ｃｅ薄膜。研究了ＳｎＯ２：Ｃｅ薄膜的热分解晶化过程和Ｃｅ掺杂和ＳｎＯ２薄膜的及气敏性能的影响，发现ＳｎＯ２：Ｃｅ薄膜在常温下对Ｈ２Ｓ气体具有较妇的敢敏性能，对ＳｎＯ２：Ｃｅ薄膜的结构进行了表征。     

三环己基锡O，O＇－二（4－氯苯基）二硫代磷酸酯和二丁基锡双［O，O＇－二（4－甲基苯基）二硫代磷酸酯］的分子和晶体结构

三环己基锡Ｏ，Ｏ＇－二（４－氯苯基）二硫代磷酸酯（Ⅰ），Ｃ＿（３０）Ｈ＿（４１）Ｃｌ＿２Ｏ＿２ＰＳ＿２Ｓｎ，Ｍ＿ｒ＝７１８．３６，单斜晶系，Ｐ２＿１／ｎ，ａ＝１６．１５１（２），ｂ＝９．４１５（１），ｃ＝２２．９８７（３），β＝１０５．６９（１）°，Ｚ＝４，Ｄｃ＝１．４１８ｇ·ｃｍ￣（－３），Ｒ＝０．０６３；二丁基锡双［Ｏ，Ｏ＇－二（４－甲基苯基）二硫代磷酸酯］（Ⅱ），Ｃ＿（３６）Ｈ＿（４６）Ｏ＿４Ｐ＿２Ｓ＿４Ｓｎ，Ｍ＿ｒ＝８５１．６６，单斜晶系，Ｐ２＿１／ｃ，ａ＝１２．２８４（４），ｂ＝９．８０７（１），ｃ＝３４．４７１（８），β＝９９．０２（２）°，Ｚ＝４，Ｄ＿ｃ＝１．３７９ｇ·ｃｍ（－３），Ｒ＝０．０４２。化合物Ⅰ具有单分子的四配位变形四面体结构。其Ｓｎ－Ｓ（１）键长为２．５０１（２）；而Ｓｎ与Ｓ（２）的原子间距则为３．５９７；化合物Ⅱ具有单分子的六配位变形八面体结构，其Ｓｎ－Ｓ（１），Ｓｎ－Ｓ（２），Ｓｎ－Ｓ（３）和Ｓｎ－Ｓ（４）的键长分别为２．４９５（３），２．４９３（２），３．２４４（４）和３．２２８（３）。     

CuZSM-5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量、反应温度、反应时间及ｎ（ＰｈＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响．     

酞菁铜与四氰代二甲基苯醌电荷转移反应的测定

用红外光谱、紫外可见光谱、循环伏安法等研究了三．（２，４－二特戊基苯氧基）－８－喹淋氧基酞菁铜（简称酞菁铜）和２－十八烷基－７，７，８，８－四氰二甲基苯醌（简称Ｃ１８－ＴＣＮＱ）在Ｌａｎｇ－ｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）膜中的电荷转移。实验结果表明，在交替和混合ＬＢ膜中，酞菁铜和Ｃ１８－ＴＣ－ＮＱ分子之间均发生了电荷转移，其中酞菁铜为给体分子，ＴＣＮＱ为受体分子。在混合ＬＢ膜中，电荷转移程度较大。电导率测量表明荷移反应使ＬＢ膜的电导率较纯酞菁铜ＬＢ膜提高了３个数量级。     

CuZSM—5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量，反应温度，反应时间及ｎ（ＰｂＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响。     

质子化和脱质子化对酞菁光谱的影响

系统地研究四异丙氧基酞菁的子化和脱质子化对吸收和发射光谱的影响，研究表明，三氟乙酸可对酞菁分子连续质子化，分别生成（Ｈ２Ｐｃ（Ｏ＾ｉＰｒ）４．Ｈ＾＋）＾和（Ｈ２Ｐｃ（Ｏ＾ｉＰｒ）４．２Ｈ＾＋）＾２＋，而硫酸可使酞菁形成（Ｈ２Ｐｃ（Ｏ＾ｉＰｒ）４．４Ｈ＾＋＾４＋此外，ＮａＯＨ／ＥｔＯＨ可使酞菁分子脱质子化生成（Ｐｃ（Ｏ＾ｉＰｒ）４）＾２－反应一步完成，表明分子中的两个吡咯－ＮＨ－同步酸解，质子化可使     

含硅二硫代磷酸酯的合成及生物活性

硅基甲硫醇Ｒ＾１Ｒ＾２ＣＨ３ＳｉＣＨ２ＳＨ与Ｏ，Ｏ－二烷基二硫代磷酸酯（ＲＯ）２Ｐ（Ｓ）ＳＨ及甲醛可顺利地发生类Ｍａｎｎｉｃｈ缩合反应，利用此反应和硅基甲硫醇与Ｏ，Ｏ－二乙基－Ｓ（２－溴乙基）二硫代磷酸酯的取代反应合成了３７种新的含硅二硫代到酯化合物（ＲＯ）２Ｐ（Ｓ）Ｓ（ＣＨ２）ｎＳＣＨ２ＳｉＣＨ３Ｒ＾１Ｒ＾２（ｎ＝１，２），在初筛浓度下，该类化合物具有一定的杀虫，杀螨活性。     

SnF2的性质及其制备

ＳｎＦ＿２的性质及其制备陈荣，周杰，沈玉华（北京大学化学系１００８７１）（安庆师范学院）ＳｎＦ＿２是介于离子型和分子型之间的化合物，有α、β和γ三种变体，室温下是α－ＳｎＦ＿２，属单斜晶系，单位晶胞中含有４个环状四聚物Ｓｎ＿４Ｏ＿８，这种结构中有两种...     

SO_2－4／TiO_2┐Al_2O_3－SnO_2催化剂的研制及其催化合成己二酸二辛酯

ＳＯ２－４／ＴｉＯ２┐Ａｌ２Ｏ３┐ＳｎＯ２催化剂的研制及其催化合成己二酸二辛酯高根之（曲阜师范大学化学系，曲阜２７３１６５）于世涛杨锦宗＊（大连理工大学精细化工系，大连１１６０１２）关键词固体超强酸，ＳＯ２－４／ＴｉＯ２－Ａｌ２Ｏ３－ＳｎＯ２催化剂，...     

Electrophoretic deposition of phthalocyanine in organic solutions containing trifluoroacetic acid

The absorption spectra of copper phthalocyanine (CuPc) 1,2-dichloroethane (DCE) solutions containing trifluoroacetic acid (TFAA) shows that the number of protons coordinating to the CuPc molecule was 1 and 2 for the first and second proton adducts, respectively, which indicates the formations of CuPcH(+) and CuPcH(2)(2+). This CuPc molecule may act as a catalyst to dissociate TFAA into trifluoroacetate anion (A(-)) and H(+) and form the proton adducts. The electrical conductivity dependence of the solution on CuPc concentration also supports this mechanism. A dense film of CuPc was deposited on an indium tin oxide cathode plate by electrophoresis of the solution. Similar dense films of a wide variety of phthalocyanines (MPc; M = Cu, H(2), Fe, Ni, Zn, Pb, VO) were also deposited using this method. Similar films of CuPc were also formed using dichloromethane (DCM) and 1,1,1-trichloroethane (TCE) in place of DCE. Depositions are ascribed to the migration of positively charged monomers (i.e., protonated MPc). Scanning electron microscopy revealed that these films are composed of fibrous crystallites, size of which was found to increase with the electrophoresis time, the strength of the applied electrical field and the concentration of CuPc in the bath. The influence of the dielectric constant of the organic solvent on the film growth is discussed.     

Thickness-dependent structural transitions in fluorinated copper-phthalocyanine (F16CuPc) films

The detailed structure of F16CuPc films on SiO2 has been determined by means of in situ grazing incidence X-ray diffraction from the first monolayer to thicker films. In contrast to films of the homologous H16CuPc molecule, the F16CuPc films exhibit the same structure independently from the deposition temperature. The films show a thickness-dependent polymorphism manifested in the in-plane crystal structure, which implies large differences in the molecular tilt within the cofacial stacking of the molecules.     

酞菁铜溶解性研究及其电沉积薄膜的制备

通过测定α-酞菁铜(α-CuPc)在4种不同的有机溶剂中的紫外可见光吸收光谱,研究了不同溶剂以及加入不同量的三氟乙酸(TFAA)对酞菁铜溶解性和质子化的影响.以溶解性研究为基础,探讨了在电化学沉积法制备酞菁铜薄膜时不同工艺条件对其形貌的影响.实验结果表明:加入TFAA后,酞菁铜在硝基甲烷和氯仿中溶解良好,而且在氯仿中更容易质子化;使用扫描电镜(SEM)表征,结果表明TFAA及酞菁铜摩尔含量对薄膜制备的影响最为明显.     

CO gas sensing by ultrathin tin oxide films grown by atomic layer deposition using transmission FTIR spectroscopy

Ultrathin tin oxide films were deposited on SiO2 nanoparticles using atomic layer deposition (ALD) techniques with SnCl4 and H2O2 as the reactants. These SnO(x) films were then exposed to O2 and CO gas pressure at 300 degrees C to measure and understand their ability to serve as CO gas sensors. In situ transmission Fourier transform infrared (FTIR) spectroscopy was used to monitor both the charge conduction in the SnO(x) films and the gas-phase species. The background infrared absorbance measured the electrical conductivity of the SnO(x) films based on Drude-Zener theory. O2 pressure was observed to decrease the SnO(x) film conductivity. Addition of CO pressure then increased the SnO(x) film conductivity. Static experiments also monitored the buildup of gas-phase CO2 reaction products as the CO reacted with oxygen species. These results were consistent with both ionosorption and oxygen-vacancy models for chemiresistant semiconductor gas sensors. Additional experiments demonstrated that O2 pressure was not necessary for the SnO(x) films to detect CO pressure. The background infrared absorbance increased with CO pressure in the absence of O2 pressure. These results indicate that CO can produce oxygen vacancies on the SnO(x) surface that ionize and release electrons that increase the SnO(x) film conductivity, as suggested by the oxygen-vacancy model. The time scale of the response of the SnO(x) films to O2 and CO pressure was also measured by using transient experiments. The ultrathin SnO(x) ALD films with a thickness of approximately 10 A were able to respond to O2 within approximately 100 s and to CO within approximately 10 s. These in situ transmission FTIR spectroscopy help confirm the mechanisms for chemiresistant semiconductor gas sensors.     

气相合成SnO2超微粒薄膜研究

用直流气体放电活化反应蒸发法在玻璃基片上沉积的SnO2超微粒薄膜,研究其过程中各工艺参数对薄膜结构的影响及作用机理.结果表明, SnO2超微粒薄膜粒径随氧分压增加而增大;蒸镀时间的延长有助于SnO2的生成,也使薄膜发生晶化;而增加放电电压,则薄膜出现外延单晶生长趋势.     

一维带状SnO2的电子传输性能

采用水辅助化学气相沉积法制备了结晶性好的一维带状SnO₂. 分别以小粒径锡粉和金修饰的小粒径锡粉作为反应原料制得带宽度不同的带状SnO₂, 小粒径锡粉作为反应原料能提高带状SnO₂的产率. 将所得SnO₂带和SnO₂纳米颗粒按不同比例混合配制成胶体, 采用刮涂法制备含不同比例纳米颗粒和纳米带的复合SnO₂薄膜并组装染料敏化太阳能电池(DSSCs)来评价带状SnO₂的电子输运性能. 组装的太阳能电池表现出与复合纳晶薄膜中一维SnO₂带的带宽度和所含比例密切相关的光电性能. 通过强度调制光电流谱的测量确定复合SnO₂薄膜的电子传输速率, 并进一步分析一维材料所具有的良好电子传输性能对光电流增加的贡献. 因为一维SnO₂带在复合纳晶薄膜中作为电子输运的快速通道可以加快电子的输运速度, 所以以适宜的比例添加具有合适宽度的一维SnO₂带可以明显提高太阳能电池的光电性能.     

Role of coordinated metal ions on the orientation of phthalocyanine based coatings

In the present work, we have investigated the molecular orientation of phthalocyanine films deposited on polycrystalline gold. Three films built from the following molecules are investigated: phthalocyanine (H(2)Pc), cobalt phthalocyanine (CoPc) and copper phthalocyanine (CuPc). The films are prepared by spin coating and drop casting methods. Orientation analysis has been performed using polarization dependent Fourier transform infrared (FTIR) spectroscopy using transmission and grazing angle reflectance mode. The FTIR study suggests that each phthalocyanine film contains both alpha- and beta-phases. H(2)Pc based films demonstrate deposition method dependence on the molecular orientation, while the CuPc and CoPc films preserve their molecular orientation independent of deposition method. Grazing angle analysis also suggests that CoPc films show negligible preferred orientation irrespective of film deposition methods. In literature, the band at 878cm(-1) in CuPc has been assigned to out-of-plane bending of C-H. Our grazing angle experiments suggest that this band cannot be assigned to out-of-plane bending vibrations of C-H. Accurate band assignments are also described here for the phthalocyanine system.     

基于p-6P异质诱导生长酞菁铜薄膜的NO2传感器

为实现室温下低浓度NO₂气体检测,制作了p-六联苯(p-6P)诱导层的酞菁铜有机薄膜传感器。利用原子力显微镜(AFM)研究了不同沉积速率下p-6P薄膜的生长规律,慢速沉积提供足够的分子扩散时间,利于薄膜横向生长,形成高度低、尺寸大的晶畴。在p-6P薄膜上生长了酞菁铜薄膜,可以清晰看到晶畴上酞菁铜薄膜的有序排列。利用X射线衍射(XRD)仪,阐明了p-6P对酞菁铜薄膜具有很好的诱导效应。通过对比不同沉积速率p-6P薄膜诱导的酞菁铜传感器性能,发现慢速沉积诱导层的酞菁铜器件有高的响应强度和低的回复时间。异质诱导生长的酞菁铜传感器响应强度是直接生长在二氧化硅上的酞菁铜传感器的2倍,回复时间是3.2 min,对浓度为1.0 × 10^-5的NO₂气体灵敏。     

Physicochemical aspects of novel surfactantless, self-templated mesoporous SnO2 thin films

A novel method of synthesis consisting of the production of ordered arrangements of tubular pores distributed inside SnO2 annealed thin films, which are prepared from a rotating disk process carried out at 2000-3500 rpm, is herein described. The main novelty is that no surfactant molecules are required in order to create these ordered pore structures; the templating entities are supramolecular assemblies of oligomeric chains formed during the extra-long aging allowed to the sol-gel processing of tin(IV) tetra-tert-amiloxide, Sn(OAm(t))4, chelated with acetylacetone molecules. Low angle X-ray diffraction peaks of SnO2 thin films calcined at 500 degrees C clearly certify the existence of ordered mesostructures when employing the right H2O/Sn(OAm(t))4 molar ratio during the SnO2 sol-gel synthesis. The final SnO2 ordered mesostructures are reminiscent of those linked to MCM-41 and SBA-15 substrates. Pore-size distribution analyses proceeding from N2 sorption isotherms at 76 K on the SnO2 thin films calcined at 500 degrees C unequivocally confirm the presence of tubular mesopores (mode pore sizes ranging from 5 to 7 nm). The thicknesses of the SnO2 films range from 80 to 150 nm after performing a drying process at 100 degrees C and from 70 to 125 nm after calcining in air at 500 degrees C; these film thicknesses show, in general, decreasing trends when either the spinning rate or the H2O/(Sn(OAm(t))4 ratio is increased.