含中氮茚有机太阳能电池染料敏化剂的分子设计

采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)方法研究了9个新的中氮茚[3, 4, 5-ab]异吲哚(INI)为给体的染料敏化剂性质.对影响电池效率的光捕获效率、电子注入、染料再生和电荷复合等重要因素与D5和D9染料进行了对比.计算表明,设计的INI系列敏化剂在440-500 nm内有最大吸收峰,表现出明显的电荷分离特征, INI2具有比D9染料更高的最大理论短路电流. Fukui反应指数计算指出INI2的亲核加成最易实现.染料分子在二氧化钛(101)面吸附计算表明,染料INI2以间接注入途径实现电子注入.综合计算结果,中氮茚INI染料有希望作为性能优良的染料敏化剂而得到应用.     

有机锡修饰的双吡唑甲烷及其与W(CO)5THF的反应

通过双吡唑甲基锂(LiCHPz₂)与有机锡卤化物(R₃SnX)的反应合成了一系列有机锡修饰的双吡唑甲烷配体(R₃SnCHPz₂).由于锡上取代基的不同,这些配体与W(CO)₅THF反应时表现出了不同的反应方式.三芳基锡修饰的双吡唑甲烷与W(CO)₅THF反应发生Sn-C(sp₃)键对W(0)中心的氧化加成;而三苄基锡修饰的双吡唑甲烷与其反应时仅给出羰基取代产物[Bz₃SnCHPz₂W(CO)₄].另外,二苯基苄基锡以及三(2-苯基-2-甲基丙基)锡修饰的双吡唑甲烷配体类似的反应导致配体的分解,产生单吡唑配体取代的羰基钨衍生物[W(CO)₅PzH]以及脱有机锡的双吡唑甲烷四羰基钨衍生物[CH₂Pz₂W(CO)₄].     

Cu/Zn/TiO2负载型催化剂上CO2加氢合成甲醇

采用溶胶-凝胶法和浸渍法制备Cu/Zn/TiO2负载型催化剂,研究了不同Cu、Zn负载量对催化剂性能的影响,采用BET、XRD、TPR对催化剂进行了表征.考察了反应温度、压力和催化剂组成对CO2加H2催化合成甲醇的影响.     

二噁英、多溴联苯醚和多氯联苯同时测定方法的研究

本实验以美国环保署1613B、1614和1668A等标准方法为基础,建立了同一样品中二噁英、多溴联苯醚和多氯联苯的同位素稀释-多层色谱柱净化-高分辨气质联用-高通量同时分析方法.该方法利用弗罗里土对二噁英组分吸附能力强的特点,采用不同极性的溶剂淋洗,先实现二噁英组分和其它两个组分的分离,再利用多溴联苯醚更易保留在硝酸银硅胶(10%)柱上的特点,实现了多溴联苯醚和多氯联苯两类化合物的分离.实验优化了样品前处理过程,纯化过程中去除了大量干扰物质,同时将三类化合物在前处理中进行分离,消除了相互干扰,实现了准确定量.纯化效果和检测限均符合美国环保署相关标准的要求.通过标准参考物的比对和实际样品的分析验证了方法的可靠性和结果的准确性.     

Pt/Cu双金属纳米颗粒的制备及其催化制氢活性

采用化学共还原法合成了聚乙烯吡咯烷酮保护的Pt/Cu双金属纳米颗粒(BNPs),并采用紫外可见吸收光谱、透射电子显微镜、高分辨透射电子显微镜等对所合成的Pt/Cu BNPs进行了表征。研究了化学组成对Pt/Cu BNPs催化Na BH4水解制氢性能的影响。结果表明,所制备的Pt/Cu BNPs平均粒径为1.8~2.3nm,其催化活性远高于单金属Pt和Cu NPs的活性,其中Pt90Cu10BNP的催化活性最高,其在30℃的条件下,催化Na BH4制氢的活性可达6570mol-H2·mol-cat-1·h-1,约为相同粒径的Pt单金属NP的1.6倍。密度泛函理论的计算结果表明,Pt/Cu BNPs优异的催化性能可归因于电荷转移效应,Pt原子与Cu原子之间发生的电子转移使得Pt原子带负电而Cu原子带正电,荷电的Pt和Cu原子成为催化反应的活性中心。     

碘化1-甲基-2-异丙基(或丙基)-3-苯磺酰基咪唑啉的合成及基团转移反应

合成了新的四氢叶酸辅酶(THF)模型化合物碘化1-甲基-2-异丙基-3-苯磺酰基咪唑啉(5a)和碘化1-甲基-2-丙基-3-苯磺酰基咪唑啉(5b),研究了其反应性能.结果表明,化合物5与双官能团亲核体邻苯二胺或邻氨基苯酚反应,完全转移了4个碳的异丁基和正丁基单元,基于此探索了合成2-取代苯并咪唑及2-取代苯并唑的新方法;化合物5a与单官能团亲核体胺类反应部分转移了4个碳的异丁基单元,生成不同基团取代的N,N,N'-三取代乙二胺盐;化合物5a在Na BH4作用下可发生还原反应,在Na OH水溶液中可发生水解反应,也可与碳负离子基团(硝基甲基负离子或二腈基甲基负离子)发生亲核加成反应,生成了3类不同基团取代的N,N,N'-三取代乙二胺衍生物,探索了此类化合物的简易合成方法.这些反应模拟了四氢叶酸辅酶在生物体内转移一碳单元的功能,并将其扩展到4个碳原子单元,获得了可应用于有机合成的新方法和新试剂.     

Potential energy curves for the X1∑ g, B1△g and B''''1∑ g states of C2 using MRCI and approximate CI methods

The potential energy curves for the X1∑ g, B1△g and B′1∑ g states of C2 have been studied by using MRCI and approximate CI methods, and are benchmarked against the calculations of full configuration interaction (FCI). The results obtained by MRCI method agree with the FCI very well, and even are accurate enough to compare other approximate methods as benchmark, when the calculations of FCI are not feasible. The approximate CI methods mentioned in this paper are reliable for treating chemical problems.     

Synthesis of air-stable mixed bis-carboxylate titanocene complexes and their catalytic behaviors in cross-aldol and Mannich reactions

Tunable organometallic Lewis acid catalysts were developed by combining salicylic acid (H₂-Sal) with benzoic acid (H-Ben), 4-fluorobenzoic acid (H-BenF) and 3-thiophenic acid (H-Th), as coligands for mixed bis-carboxylate titanocene complexes. Three air-stable complexes [Cp₂Ti(η¹-HSal)(η¹-Ben)] (1), [Cp₂Ti(η¹-HSal)(η¹-BenF)] (2) and [Cp₂Ti[η¹-HSal][(η¹-Th)] (3) were prepared in high yields by the reaction of salicylato titanocene chelate with carboxylate ligands. The mixed bis-carboxylate titanocene complexes were fully characterized by physicochemical and spectroscopic methods. Single-crystal X-ray diffraction studies revealed Ti–O_(H-Sal) bond distances in 1, 2 and 3 of 1.972(3), 1.9245(18) and 1.912(5) Å, respectively, while the bond distances involving the coligands of 1, 2 and 3 are 1.908(3) Å (Ti–O_Ben), 1.9296(19) Å (Ti–O_BenF) and 1.945(5) Å (Ti–O_Th), respectively. These bis-carboxylate titanocene complexes showed satisfactory activities and selectivities in Mannich and cross-aldol reactions. Notably, complex 3 bearing the labile thiophene carboxylate ligand gave high yields with a diastereomer ratio (d.r.) as high as 1:99 for the direct Mannich reactions of benzaldehyde, cyclohexanone and aniline. In cross-aldol reaction of benzaldehyde and cyclohexanone, 1 and 2 successfully catalyzed the formation of double-aldol products in up to 99 % yield.     

Cu-Fe-PILC催化C3H6选择性还原NO的性能

采用羟基铁离子柱撑Na-Mont制备出1.0Fe-PILC,通过超声浸渍法合成不同铜负载量的nCu-Fe-PILC,并测试了其在富氧条件下催化C_3H_6选择性催化还原NO的性能。通过N_2吸附脱附、XRD、UV-Vis、H_2-TPR、Py-FTIR等技术手段表征催化剂的微观结构和物化性质,进一步解释其催化反应机理。结果表明,Cu的引入提高了1.0Fe-PILC的中低温活性和抗水硫能力。其中9Cu-Fe-PILC在300℃时NO转化率可达69.8%以上,400℃后NO转化率保持在99%以上且水硫影响较小。XRD、N_2吸附脱附结果表明,催化剂的SCR活性与所负载的活性组分和催化剂的吸附能力有关。UV-Vis结果表明,9Cu-Fe-PILC具有较强的中低温活性,与其含有较多的游离态Cu~(2+)有关。H_2-TPR结果表明,与1.0Fe-PILC相比,经Cu修饰的nCu-Fe-PILC获得了中低温还原能力。Py-FTIR结果表明,nCu-Fe-PILC表面同时含有Lewis酸和Br?nsted酸,Lewis酸是影响催化剂SCR活性的主要因素。     

Self-assembly of a thymine quartet and quadruplex via an organic template

The synthesis of two hydrophobic cavitands bearing four (1) and eight (2) thymidine residues covalently linked with triazole moieties is reported. Spectral evidence indicates the adoption of a hydrogen-bonded T-quartet assembly by 1 in chloroform at low temperature and a π-stacked quadruplex by 2 in DMSO under ambient conditions.