钙钛矿材料组分调控策略及其光电器件性能研究进展

近年来，钙钛矿太阳电池的光电转换效率取得了爆发式增长，这与电池中钙钛矿薄膜的制备工艺和材料组分密切相关.关于钙钛矿薄膜的制备方法，相关的研究报道及综述较多，然而钙钛矿材料组分调控方面的研究梳理工作相对缺乏.本综述总结了近年来不同组分体系钙钛矿材料的研究进展，包括有机无机铅卤钙钛矿、全无机铅卤钙钛矿、少铅钙钛矿以及无铅钙钛矿.重点介绍了不同体系中具有代表性的材料组分及其对器件性能的影响，旨在梳理通过组分调控提高钙钛矿电池的效率及稳定性的研究思路，最终实现商业化应用.     

钙钛矿太阳电池吸光层材料研究进展

近年来,有机-无机卤化铅钙钛矿太阳电池的研究取得了突破性进展,公证记录电池效率22.1%,与CdTe薄膜电池（认证记录电池效率22.1%）和CuInGaSn（CIGS）（认证记录电池效率22.3%）薄膜电池技术相媲美,已经接近于市场上主导地位的晶体硅太阳电池（约25%）。有机卤化铅钙钛矿太阳电池器件的长期效率输出稳定性和含毒性Pb严重制约其实际应用。本文将讨论有机卤化铅钙钛矿太阳电池不稳定性因素和相应的解决方案,并对钙钛矿材料中Pb元素的取代工作和无机非铅钙钛矿材料及其太阳电池的研究进行了阐述与展望。     

钙钛矿太阳电池研究进展:薄膜形貌控制与界面工程

有机-无机杂化钙钛矿太阳电池因兼具低成本溶液加工和优异的光电转换性能在国际上倍受关注. 基于其吸收强、迁移率高、载流子寿命长、可调控带隙以及可采用多种方式加工等优势, 钙钛矿太阳电池在短短5年时间里, 实验室小面积器件的能量转换效率已经从低于5%提高到近20%, 模块器件的能量转换效率可达8.7%, 其效率超过了很多其他类型太阳电池, 接近可以商业化的水平. 借助于相关材料性质理解和电池设计优化, 钙钛矿太阳电池效率的进一步提升存在很大的潜力空间. 本文通过文献综述, 在回顾国内外钙钛矿太阳电池发展情况的基础上, 着重讨论影响钙钛矿太阳电池性能的其中两个重要因素: 薄膜形貌控制与界面工程, 并分析了钙钛矿太阳电池面临的基础科学问题以及展望该技术的未来前景.     

反式锡基钙钛矿光伏电池的制备及稳定性策略

近年来,钙钛矿光伏电池（PSCs）取得了突飞猛进的发展,迄今最高认证光电转换效率达到25.7%,但是钙钛矿材料常使用有毒的重金属元素铅,对环境和人体都有极大的危害,不利于其实际应用,因此发展无铅PSCs受到越来越多的关注。锡基钙钛矿材料具有优异的光电性质,特别是带隙窄、载流子迁移率高和激子复合能低,是无铅钙钛矿中最具有潜力的材料。反式（p-i-n型）锡基PSCs由于低迟滞效应、可低温制备及低成本等优点获得普遍关注,取得了一系列重要突破,目前最高效率已经突破14%,具有巨大的发展潜力。鉴于反式锡基钙钛矿太阳能的迅速发展,本文系统综述了反式锡基PSCs制备及稳定性研究进展,尤其关注反式锡基PSCs的界面修饰、锡基钙钛矿材料性能、构筑高质量锡基钙钛矿薄膜的方法以及提高稳定性的策略,并讨论了锡基PSCs的前景展望。     

全无机钙钛矿太阳电池的制备及稳定性

全无机钙钛矿太阳电池因其热稳定性好、载流子迁移率高,可用于制备叠层电池等优点备受关注。随着人们对全无机钙钛矿太阳电池的深入研究和制备工艺的持续优化,全无机钙钛矿太阳电池的光电转换效率已经突破19%。然而,全无机钙钛矿材料相稳定性较差,这使得实现全无机钙钛矿太阳电池在空气环境下制备和长期使用面临巨大挑战。众多科研工作者通过分析全无机钙钛矿材料的相变机制,有针对性地提出了包括添加剂工程、界面工程和开发全无机钙钛矿量子点电池等多种方式来改善全无机钙钛矿太阳电池的长期稳定性。本综述从全无机钙钛矿材料与电池的结构、活性层制备方法和稳定性研究三个方面总结了近年来关于全无机钙钛矿太阳电池的研究进展。     

钙钛矿型太阳电池研究进展

自从2009年钙钛矿材料被应用到太阳电池领域,到现在仅6年的时间里,钙钛矿型太阳电池的光伏转换效率从约3%提高到20.1%,受到全球瞩目。 本文对近年来钙钛矿型太阳电池的发展进行了综述,介绍了钙钛矿吸光材料的性能及其制备,总结了钙钛矿型太阳电池器件结构及其内在机理,探讨了该类型电池待突破的方向和可能的解决途径,阐述了钙钛矿型太阳电池的进展历程,展望了未来发展方向。     

Sn类钙钛矿太阳电池薄膜的掺杂改性研究

采用一步法分别制备了Sn类CH3NH3Sn I3和Pb类CH3NH3Pb I3钙钛矿太阳电池薄膜材料,并对其表面形貌、微观结构、吸收光谱和电池器件性能进行了表征和测试。研究结果表明:Sn类钙钛矿材料的吸收光谱相对于Pb类钙钛矿材料发生了明显的红移,吸收截止波长从800 nm上升到950 nm左右,光学带隙由1.45 e V降低至1.21 e V左右;Sn类钙钛矿材料的光谱吸收范围明显扩大,但吸收强度有所降低,相应太阳电池器件的光电转换效率也明显低于Pb类钙钛矿太阳电池,分别为2.05%和6.71%。而Br的掺杂可使Sn类钙钛矿材料带隙变宽,吸收光子能量增大,电池器件的开路电压也相应提高。当Br含量由0增加至完全替代I时,Sn类钙钛矿材料逐渐由黑褐色转变为黄色,光学带隙增大至1.95 e V,但吸收截止波长由950 nm降低至650nm。值得提及的是当Br含量为0.5时,电池器件的光电转换效率可由最初的2.05%提升至2.94%。     

甲胺气体处理修复钙钛矿薄膜缺陷

正有机无机杂化钙钛矿由于其独特的光、电、磁性能以及制备工艺简单、成本低等特点,一直备受关注,特别是自2009年第一次将其应用于太阳能电池以来,钙钛矿太阳能电池的能量转换效率由3.8%迅速上升到目前的20.1%[1],并且钙钛矿在二极管和激光器件等领域也受到了广泛关注.在这些器件中,钙钛矿活性材料是其核心部分,钙钛矿膜的好坏是影响器件性能的关键因素,因此,对钙钛矿成膜性的研究具有     

环境友好型无铅卤化物钙钛矿太阳能电池研究进展

ABX_3(A为甲胺、甲脒等有机离子或铯离子,B为铅或锡等金属离子,X为溴、碘等卤化物离子)卤化物钙钛矿材料具有优异的光电特性,是当前太阳能电池研究的前沿和热点之一。然而,这类太阳能电池普遍面临含毒性元素铅和稳定性差等问题,极大地阻碍了钙钛矿太阳能电池商业化应用进程。因此,发展新型高效无铅钙钛矿太阳能电池势在必行。本文评述了环境友好型无铅卤化物钙钛矿太阳能电池的最新研究动态和进展,探讨了该类太阳能电池的制备、性能及其稳定性等问题,展望了其未来发展趋势。     

有机-无机杂化钙钛矿太阳电池中的钙钛矿层功能添加剂

有机-无机杂化钙钛矿太阳电池作为新一代薄膜太阳电池,自2009年Mayasaka等制备出第一块钙钛矿太阳电池后得到迅猛发展,截止目前,其认证转换效率由最初的3%达到22.1%。钙钛矿材料作为光吸收层,具有光吸收效率高、载流子迁移率高和电子扩散寿命长等特点,但是其本身对水和氧气敏感,在环境氛围中不稳定。研究表明,在钙钛矿材料中添加一些功能添加剂,通过调节钙钛矿晶体结构、结晶过程和晶体缺陷等方法,可以提高钙钛矿太阳电池的光伏性能或者环境稳定性。本文主要评述了钙钛矿太阳电池中各类功能添加剂的应用研究进展。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.