1-丁基-3-甲基咪唑碘对染料敏化太阳电池的影响

采用季铵化反应合成了1-丁基-3-甲基咪唑碘([Bmim]I).以此制备了DSCs用液体电解质.通过对比不同浓度的1-丁基-3-甲基咪唑碘、碘化钾、碘,研究其对电池性能的影响.经过优化后,当c_IL=0.9 mol·L^-1、c_KI=0.5 mol·L^-1、c_I2=0.12 mol·L^-1时,所组装的离子液体DSCs在AM1.5,100 mW·cm^-2下,DSCs的短路电流密度为15.97 mA·cm^-2、开路电压为0.71 V、填充因子为0.55、光电转换效率可达6.34%.     

白光及紫外光辐照下甲氨碘化铅基钙钛矿太阳能电池降解机制差异

本工作实验对比了可见光以及紫外光辐照下甲氨碘化铅(CH₃NH₃PbI₃即MAPbI₃)基钙钛矿太阳能电池器件性能及微结构演变特征差异. 结果表明可见光辐照下钙钛矿太阳能电池器件中MAPbI₃层发生降解的同时, 伴随着Au元素从金属电极一侧向MAPbI₃和电子传输层SnO₂的界面处迁移现象. 但相较于紫外光, 可见光辐照下器件中Au元素的迁移速率慢30倍左右. 这是由于器件电子传输层SnO₂具有较低的价带顶位置(–8.4 eV), 它吸收紫外光激发出强氧化性的空穴h⁺, 氧化碘离子I^–生成I原子. 而I原子会对金属电极层产生较大的破坏作用, 促进Au⁺离子的形成. 因此可见光辐照下, 尽管器件开路电压V_oc一直保持较高的数值, 但是Au元素的迁移以及钙钛矿层的分解, 会引起短路电流密度J_sc的快速降低. 本文为钙钛矿太阳能电池光照不稳定性的机理解释, 提供了全新的理论依据.     

哌啶型离子液体混合电解液在Li/LiCoO2电池中的性能研究

合成并考察了N-甲基-N-乙（丙,丁）基哌啶-二( 三氟甲基磺酰) 亚胺三种离子液体( PP12（3,4）TFSI )作为电解液添加剂的影响. 使用热分析和电化学技术研究了离子液体混合电解液的热稳定性和电化学性能.实验表明,哌啶型离子液体可以提高有机电解液的热稳定性,并且侧链的长短对 LiCoO₂ 电极的电化学性能有重要的影响.当以PP13TFSI配成的混合电解液,在3.0~4.35 V之间、电流密度为150 mA•g^-1时, LiCoO₂ 电极的首次放电容量为156.6 mAh•g^-1,200周循环后容量为133.9mAh•g^-1,容量保持率为85.5%,远远优于在传统有机电解液中的循环性能.     

1-甲基-3-己基咪唑碘在染料敏化太阳电池中的应用研究

利用超微铂电极和循环伏安法, 以及电化学阻抗谱研究了在1-甲基-3-己基咪唑碘(HMII)的3-甲氧基丙腈(MePN)溶液中I₃^－和I^－的氧化还原行为, 并对比了由不同浓度的I₂和HMII组成的电解质溶液对染料敏化纳米薄膜太阳电池(DSCs)光伏性能的影响. 发现以MePN为溶剂, 含1.0 mol•dm^－3 HMII, 0.12 mol•dm^－3 I₂, 0.10 mol•dm^－3 LiI和0.50 mol•dm^－3 4-叔丁基吡啶的电解质溶液, 其DSCs的短路光电流密度为14.06 mA•cm^－2, 开路电压为0.71 V, 填充因子为0.69, 光电转换效率达6.81%.     

基于P掺杂TiO2/C纳米管负极的高性能锂离子电容器

以磷酸二氢钠(NaH₂PO₄)为磷源, 通过溶剂热法制备了P掺杂的TiO₂/C (P-TiO₂/C)纳米管以改善TiO₂的储锂性能. 电化学测试表明: P-TiO₂/C负极具有高的比容量(在0.1 A•g^-1的电流密度下达到335 mAh•g^-1)、优异的倍率性能(在2.0 A•g^-1的电流密度下为92 mAh•g^-1)及循环性能(在1.0 A•g^-1的电流密度下经过1000次循环后放电比容量仍维持在135 mAh•g^-1). 并且, P-TiO₂/C在2 mV•s^-1时的赝电容贡献约为96%. 由P-TiO₂/C负极和活性炭正极组装的锂离子电容器在250 W•kg^-1的功率密度下能量密度能够达到74.7 Wh•kg^-1. 此外, 该锂离子电容器在10000次循环后比电容保持率约为43%. 此外, 该器件在1.0 A•g^-1下循环10000次后充满电仍可点亮18只红色的LED灯组成的“LIC”字样. 该工作为高性能锂离子电容器TiO₂负极材料的设计提供了思路.     

高压静电纺丝法制备P(VDF-HFP)聚合物电解质

以高压静电纺丝法制备了具有微孔结构的偏氟乙烯-六氟丙烯共聚物[P(VDF-HFP)]无纺布膜, 吸附离子液体3-乙基-1-甲基咪唑鎓四氟硼酸盐(EMIBF₄)后成为凝胶聚合物电解质, 其室温离子电导率达到8.43 mS•cm^－1, 初始热失重温度超过300 ℃. 以其为聚合物电解质的活性碳电极双电层电容器具有较好的电化学性能, 1.0 mA•cm^－2恒流充放电500次循环后仍保持 90.67 F•g^－1的比容量, 容量保持率为96.86%.     

基于ZIFs合成的中空双金属(Zn,Co)S纳米晶及其赝电容性质研究

通过两步法设计合成了具有中空结构的双金属硫化物（Zn,Co）S纳米晶,并研究了其电化学性质.首先在室温下,以水为溶剂,十六烷基三甲基溴化铵为表面活性剂,利用Zn²⁺,Co²⁺与2-甲基咪唑的配位作用形成了ZIF-Zn,Co.然后以ZIF-Zn,Co为自牺牲模板剂,加入硫代乙酰胺,在微波辐射下快速合成了具有中空结构的（Zn,Co）S纳米晶.电化学测试结果表明,在电流密度为3 mA/cm²时,（Zn,Co）S纳米晶比电容为423.3 F/g,在电流密度为10 mA/cm²时,充放电2000次,仍能保持59%的初始电容.所制备的中空纳米结构具有较高的比表面积和较好的电化学性能,可作为超级电容器的电极材料.     

粉末活性炭基复合材料制备及净化含油污水的性能和机制

针对粉末活性炭对亲水小分子有机物吸附效率低和固液分离速度慢的问题, 本研究以粉末活性炭(PAC)、腐植酸盐(HS)、聚合氯化铝(PACl)为原料, 通过融合法成功制备了粉末活性炭基复合材料PACMC (powdered activated carbon matrix composites), 将其作为含油污水的净化吸附剂. 扫描电子显微镜-X射线能量色散谱仪(SEM-EDS)和傅里叶红外光谱(FT-IR)等表征分析确认了PACMC的微观形貌和化学组成, 证实了PAC、HS和PACl是通过化学反应生成了PACMC. PACMC具有层状多孔结构和活性官能团, 有利于含油污水分子的传输扩散和化学吸附. 通过静态吸附实验研究了PACl、PAC和PACMC对含油污水中有机物的吸附性能, 结果表明: PACMC对含油污水中有机污染物的吸附能力是PAC和PACl的2~3倍(q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1); 当吸附时间达到120 min 时, PACMC上的活性位点与含油污水中有机污染物的结合已基本达到饱和(q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1). 溶液pH值对PACMC吸附去除含油污水中有机物的影响显著, pH=3时, 吸附效果最好(q_e=27.6 mg•g^‒1, C₀=300 mg•L^‒1); 伪二级动力学方程能很好地描述含油污水中有机物在PACMC上的吸附行为, 动力学拟合结果表明其吸附过程分多步进行, 化学吸附和内扩散均具有重要作用. 等温吸附数据符合Dubinin-Radushkevich模型, 证明其吸附机理为化学吸附. 因此, PACMC吸附含油污水的机理包括化学结合/螯合作用、疏水力作用和静电吸附作用.     

P(VDF-HFP)基凝胶电解质染料敏化纳米TiO2薄膜太阳电池

采用循环伏安法(CV)研究了凝胶电解质中I₃-/I-氧化还原行为,凝胶电解质中I₃-/I-的表观扩散系数和相应的稳态扩散电流明显低于液体电解质.通过对阴/阳离子的结合能和孔穴阻塞作用的研究解释了凝胶电解质电导率较液体电解质发生变化的原因.制备的凝胶电解质电池具有较高的光电转换效率(6.6%),其短路电流密度(Jsc)仅比液体电解质电池低0.3-0.4 mA/cm²,电池效率也仅低约0.6%.     

离子液体辅助条件下由稻壳合成超级电容器用多孔炭

本文以稻壳为碳源,以离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF₆)为模板和辅助活化剂制备了多孔炭材料（PCs）. 多孔炭的比表面积达1438 m²·g^-1,总孔容达0.75 cm³·g^-1. 以PCs为超级电容器电极材料,6 mol·L^-1的KOH溶液为电解液组装成扣式电池,在0.05 A·g^-1的电流密度下,比电容高达256 F·g^-1;当电流密度增大至10 A·g^-1,其比电容仍保持在211 F·g^-1,展现出好的倍率性能. 所得的多孔炭电极均表现出优异的循环稳定性. 这一工作以BMIMPF₆作为模板和辅助活化剂,为合成生物质基超级电容器用多孔炭提供了一种新方法.     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.