一锅法合成四芳基吡咯并[3,2-b]吡咯空穴传输材料及其在无掺杂倒置钙钛矿太阳电池的应用（英文）

本文采用一锅法合成了四芳基吡咯并[3,2-b]吡咯有机空穴输运材料(D41、D42、D43和D44),制备出无掺杂的倒置型平面钙钛矿太阳电池.材料D41的芳环上含有甲基,具有供体-π-给体-π-供体结构;而D42、D43和D44具有受体-π-给体-π-受体结构,其中,芳环上分别含有氰基、氟和三氟甲基.研究表明,芳环上取代基对其分子表面电荷分布和空穴输运层薄膜形貌有显著影响,钙钛矿晶体颗粒的大小与空穴输运材料分子结构有关,含有氰基的材料D42最有利于形成较大的钙钛矿晶粒,这主要是由于吡咯并[3,2-b]吡咯结构具有丰富的电子性质的缘故.D42制备的倒置型平面钙钛矿太阳电池光电转换效率为17.3%,在黑暗条件下22天后,仍保留了初始效率的55%.吡咯并[3,2-b]吡咯结构具有良好的给电子特性,可作为高效钙钛矿薄膜的空穴传输材料.     

2-(2-苯并噁唑啉酮-3-甲基)-6-芳基-咪唑[2,1-b][1,3,4]噻二唑的NMR谱研究

许多文献已报道,含有咪唑[2,1-b][1,3,4]噻唑环的衍生物具有抗癌、抗结核、抗菌、抗真菌、抗惊厥、止痛等活性. 该文合成了一个新的在医药方面具有潜在应用价值的咪唑[2,1-b][1,3,4]噻二唑衍生物,即2-(2-苯噁唑啉酮-3-甲基)-6-苯基-咪唑[2,1-b][1,3,4]噻二唑,并利用2D NMR技术对其¹H NMR 和¹³C NMR谱进行了全归属.      

2,6-双(三甲基锡)-4,8-双(2-乙基己氧基)苯并[1,2-b∶4,5-b']二噻吩的合成与多核NMR研究

以苯并[1,2-b∶4,5-b´]二噻吩-4,8-二酮为原料合成了一种聚合物太阳能电池材料的单体2,6-双(三甲基锡)-4,8-双(2-乙基己氧基)苯并[1,2-b∶4,5-b´]二噻吩. 通过多核1D和2D NMR技术（包括1D ¹H、¹³C、¹¹⁹Sn、¹¹⁷Sn NMR、DEPT、选择性1D TOCSY及2D¹H-¹H COSY、gHSQC、gHMBC）表征了目标分子结构,完成了 ¹H、¹³C、¹¹⁹Sn 与¹¹⁷Sn NMR化学位移归属,并探讨了该化合物的NMR谱线特征.     

应用于钙钛矿太阳能电池中金属氧化物电子传输材料的研究进展

基于有机金属卤化铅钙钛矿材料作为光活性层的太阳能电池(PSCs)已经获得了25.2%的认证效率,是除硅基太阳能电池外被认为最有可能实现商业化的太阳能电池之一。电子传输层是PSCs器件结构的最基本组成之一,其构成材料与光活性层的成膜质量、界面电荷的快速提取以及能级匹配等密切相关。因而,电子传输材料在PSCs的光伏性能及稳定性调控方面发挥着重要作用。本文对应用在PSCs中的金属氧化物电子传输材料进行了回顾与总结,着重强调了材料的纳米结构与制备工艺、半导体特性与分类以及掺杂与界面修饰等方面的研究进展,并对其今后的发展进行了展望。     

New small organic molecules based on thieno[2,3-b]indole for efficient bulk heterojunction organic solar cells: a computational study

ABSTRACT

This study aims to evaluate the characteristics of novel organic D-π-A-π-D class small-molecules by using carefully the density functional theory, and time-dependent density functional theory calculations. Thedesigned sequence of (D-A) BHJ-1a to BHJ-4a in organic Bulk Heterojunction (BHJ) solar cells has been comprehensively analysed. Thiéno[2,3-b]indole (TI) has been used as donor, and Diketopyrrolopyrrole (DPP) as acceptor for all compounds. In order to improve the electronic, photovoltaic, and opticalproperties, we have substituted thiophene unit with furan, thieno[2,3-b]thiophene, thiazole and thiazolothiazole as π-bridge moieties. Thus, the result shows that the wise choice of the π-bridge units plays a significant role in improving E_gap, producing a high bathochromic shift, and increasing V_OC as well as a theoretical power conversion efficiency (PCE) over 7%. Interestingly, BHJ-4a with suitable π-bridge presents the optimal electronic properties with low band gap (1.870?eV) and high V_OC (1.534?eV). Furthermore, we have modelled a Bulk heterojunction organic photovoltaic cells based on donor-PCBM complex in order to achieve the optimum E_gap and V_OC. Consequently, the obtained results provide a new way to design BHJ small molecule donors with higher power conversion efficiency.     

基于4，8-二氢二呋咱[3，}4-b，e]吡嗪高能材料的设计与筛选

为了寻找高能量密度的材料,本文设计了一系列基于4,8-二氢二呋咱[3,4-b,e]吡嗪的含能材料. 利用密度泛函理论研究了它们结构与性质之间的关系. 结果表明,这些设计化合物的性质受到含能基团和杂环取代基的影响. -N₃含能基团是提高设计化合物生成热的最有效取代官能团,而四唑环/-C(NO₂)₃基团对炸药的爆轰性能有较大贡献. 键解离能分析表明,引入-NHNH₂,-NHNO₂,-CH(NO₂)₃和-C(NO₂)₃基团会显著降低键解离能. 由于化合物A8,B8,C8,D8,E8和F8具有良好的爆轰性能和热稳定性,最终被筛选为潜在的高能密度材料. 此外,还计算了这些筛选化合物的电子结构.     

菲并咪唑衍生物蓝光材料的合成、光物理性质及理论计算

合成了两个蓝光材料2-苯基-1H-[9,10-d]菲并咪唑(Phen-PI)和2-吡啶-1H-[9,10-d]菲并咪唑(PyriPI),光物理分析表明Phen-PI和Pyri-PI的最大发射峰分别位于371.5 nm,388.5 nm和403.5 nm,相对量子效率分别为0.383和0.528,激发态衰减寿命分别为3.87 ns和3.68 ns。通过密度泛函理论(DFT)对化合物的前线分子轨道成分和能级分布分析表明,当把Phen-PI中的苯基被吡啶环取代后,Pyri-PI的HOMO能级和LUMO能级分别下降0.09 e V和0.23 e V,同时Pyri-PI的HOMO轨道和LUMO轨道的能级差比Phen-PI减少0.14 e V,在理论层面上解释了Pyri-PI发射光谱的红移。     

二硫化钨纳米片制备及其钙钛矿太阳能电池空穴传输层应用

开发新型无机空穴传输层材料是钙钛矿电池实现商业应用的重要挑战之一。本文开展了二硫化钨纳米片制备及其钙钛矿太阳能电池空穴传输层应用研究。采用液相超声剥离法成功制备了WS₂纳米片,并将其引入钙钛矿太阳能电池中用作空穴传输层。结果表明,当WS₂纳米片溶液浓度为1 mg/mL时,制备的WS₂纳米片空穴传输层具有较合适的厚度,并且后续在其上生长的钙钛矿活性层成膜质量高、结晶性能好,电池取得6.3%的光电转换效率。结果证实WS₂纳米片可作为新型无机空穴传输层材料用于钙钛矿太阳能电池。     

染料敏化太阳能电池Sm~(3+)掺杂TiO_2下转换光阳极的制备及性能

用溶胶-水热法制备了Sm3+掺杂的Ti O2粉体(Ti O2∶Sm3+),将其按不同质量分数掺杂到P25基体中,制备了具有下转换功能的光阳极,并将其用于染料敏化太阳能电池中,提高了电池的光电性能。荧光光谱显示,Ti O2∶Sm3+粉体可以将紫外光转换为570~700 nm的可见光。当下转换光阳极中Ti O2∶Sm3+粉体的掺杂质量分数为80%时,短路电流密度达到13.12 m A/cm2,与纯P25光阳极相比,提高了26.5%,转换效率也提高了23.5%。     

染料敏化太阳能电池Eu~(3+),Sm~(3+)掺杂TiO_2下转换光阳极的制备及性能

用溶胶-凝胶法制备了Eu,Sm共掺TiO_2粉体,将其与P25复合,制备了下转换光阳极,用于染料敏化太阳能电池,利用其下转换特性提高电池的光电性能.用荧光光谱对粉体的发光性能进行表征,荧光光谱显示:Eu,Sm共掺TiO_2粉体受463nm光激发可以发射550~700nm的可见光,具有下转换功能.当Eu~(3+)的摩尔掺杂含量为1%,Sm~(3+)的摩尔含量为0.5%时,制备的Eu~(3+),Sm~(3+)共掺下转换光阳极,短路电流达到14.08mA/cm2,与使用Eu~(3+)掺杂TiO_2的下转换光阳极电池相比,提高了32.08%,转换效率也达到5.29%.     

Synthesis,Characterization and Antibacterial Activity of Some Transition Metal Complexes of 2-N-(isatinamino)-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene

Metal complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) with a Schiff base derived from isatin and 2-amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene were synthesised and characterised by elemental analysis, conductance measurements, magnetic susceptibility, UV-Vis, IR, ¹H NMR and EPR spectral studies. The spectral data revealed that the ligand acted as a neutral tridentate, coordinating to the metal ion through the azomethine nitrogen, ester carbonyl and carbonyl oxygen of the isatin moiety. The EPR spectral data indicated that metal-ligand bonds have considerable covalent character. The copper(II) complex was subjected to X-ray diffraction and cyclic voltammetric studies. The ligand and the metal complexes were screened for their antibacterial activity and it has been observed that the metal complexes are more potent bactericides than the ligand.     

A novel three-component reaction for the synthesis of 3-aryl-4H-benzo [1,4] oxazin-2-amine

A high yielding and fast method for the synthesis of 3-aryl-4H-benzo [1,4] oxazin-2-amine via one-pot, three component reaction of an aromatic aldehyde, isocyanide and o-aminophenol using p-toluene sulfonic acid as a catalyst is described.