基于吡嗪空穴传输层的合成及在p-i-n型钙钛矿太阳能电池中的应用

钙钛矿太阳能电池由于具有高的光电转换效率,简单的溶液加工工艺,较低的成本等优势因而拥有广阔的应用前景。有机小分子空穴传输层材料在钙钛矿太阳能电池中扮演着极其重要的角色。在本工作中,我们设计和合成了基于吡嗪为分子中心核,三苯胺为分枝的X型空穴传输层材料PT-TPA。与Si-OMeTPA对比,吡嗪的引入不仅不会影响其结晶性,并且能够改善其电荷转移特性和分子中心共平面性,从而显著提升了PT-TPA的空穴迁移率。在非掺杂的情况之下,基于PT-TPA空穴传输层的p-i-n型钙钛矿太阳能电池展现出17.52%的光电转换效率,与相同条件下基于Si-OMeTPA空穴传输层的器件相比,效率提高了近15%。     

Surface-Degenerate Semiconductor Photocatalysis for Efficient Water Splitting without Sacrificial Agents via a Reticular Chemistry Approach

The production of green hydrogen through photocatalytic water splitting is crucial for a sustainable hydrogen economy and chemical manufacturing. However, current approaches suffer from slow hydrogen production (<70 μmol ⋅ g_cat⁻¹ ⋅ h⁻¹) due to the sluggish four-electrons oxygen evolution reaction (OER) and limited catalyst activity. Herein, we achieve efficient photocatalytic water splitting by exploiting a multifunctional interface between a nano-photocatalyst and metal–organic framework (MOF) layer. The functional interface plays two critical roles: (1) enriching electron density directly on photocatalyst surface to promote catalytic activity, and (2) delocalizing photogenerated holes into MOF to enhance OER. Our photocatalytic ensemble boosts hydrogen evolution by ≈100-fold over pristine photocatalyst and concurrently produces oxygen at ideal stoichiometric ratio, even without using sacrificial agents. Notably, this unique design attains superior hydrogen production (519 μmol ⋅ g_cat⁻¹ ⋅ h⁻¹) and apparent quantum efficiency up to 13-fold and 8-fold better than emerging photocatalytic designs utilizing hole scavengers. Comprehensive investigations underscore the vital role of the interfacial design in generating high-energy photoelectrons on surface-degenerate photocatalyst to thermodynamically drive hydrogen evolution, while leveraging the nanoporous MOF scaffold as an effective photohole sink to enhance OER. Our interfacial approach creates vast opportunities for designing next-generation, multifunctional photocatalytic ensembles using reticular chemistry with diverse energy and environmental applications.     

有机过氧化物与N-甲基-N-2-羟乙基苯胺引发体系的研究

测定了有机过氧化物与N-甲基-N-2-羟乙基苯胺(HMA)体系引发MMA聚合的动力学方程和聚合表现活化能。由过氧化物/HMA/MNP的ESR波谱证实芳叔胺HMA中,与氮原子相连的亚甲基的氢被摘去形成相应的碳自由基,它能引发单体聚合成为聚合物的端基。这也由聚合物的UV光谱所证实,由实验结果提出这类体系的引发机理。     

有机-无机自由基盐(DBTTF)6PMo12O40·2H2O的合成、性质和晶体结构

用电解法制备了有机-无机自由基盐(DBTTF)6PMo12O40·2H2O.用红外光谱、电子光谱和电子自旋共振谱进行了表征,测定了其磁化率、导电性和单晶的晶体结构,该晶体属三斜晶系,P1空间群,晶胞参数为a=1.378 7(7)nm,b=1.420 4(2)nm,c=1.570 2(2)nm,α=104.570(8)°,β=103.41(2)°,γ=95.80(2)°,V=2.853(2)nm3,Z=1,Dc=2.142 Mg·m-3,R=0.072 7.     

有机化学进展(2011~2012)

本文综述了中国大陆地区有机化学研究人员2011至2012年两年内在合成方法学、有机合成化学、元素有机化学以及天然产物化学等领域获得的重要成果。文章中共引用参考文献355篇,其中110多篇手性金属配合物和有机小分子催化的不对称反应、金属催化的碳氢键活化等合成方法学论文和30余篇氟有机化学论文基本来源于德国《应用化学》(国际版)和《美国化学杂志》。本文汇集了中国有机化学家两年中合成的150多个具有生物活性和化学结构多样性的天然产物,其中不乏具有高度挑战性的复杂天然分子。在近两年中中国有机化学家从陆地和海洋的生物体内发现各种不同类型新天然产物90多个。     

含酯基Gemini表面活性剂在有机醇-水体系中的胶束热力学及聚集行为

采用电导法研究了不同温度下含酯基Gemini表面活性剂在纯水和在质量分数为10%的甲醇-水(MAWR),乙二醇-水(EG-WR),丙三醇-水(GL-WR)四种体系中的集聚行为和胶束热力学;聚集行为参数包括临界胶束浓度(cmc)和抗衡离子的解离程度(α)以及胶束的热力学参数,包括标准吉布斯自由能(ΔG_m~o)、吉布斯迁移自由能(ΔG_(trans)~o)、吉布斯烷基链胶束化自由能(ΔG_(tail)~o)、标准焓变(ΔH_m~o)和标准熵变(ΔS_m~o),均被计算和讨论。研究表明在所有的研究体系中,cmc值随着疏水链的增加而减小,随着加入的醇结构中羟基数目的增加而增大,随温度的升高先变小,后变大呈U字形;胶束化过程都是自发进行的,并且在293.15 K下,胶束化过程是吸热的,在293.15 K上,胶束化过程是放热的;通过稳态荧光光谱法研究了表面活性剂在纯水、有机醇-水混合溶液中的微极性,结果表明,在相同溶剂中,随着烷基链长度的增加,溶液微环境的疏水性越强;对于相同的Gemini表面活性剂,随着加入含羟基数目越多的醇,其微环境的疏水性越强。并研究了Gemini表面活性剂在混合体系中形成胶束过程的焓-熵补偿曲线。     

芴基张力半导体结构和光电性质的理论研究

[4]Cyclo-9, 9-dimethyl-2, 7-fluorenylene ([4]CF) was used as a model compound to explore the steric strain effect on the structures and photoelectrical properties of materials. A series of strained cyclic polyfluorene materials, [n]CFs (n=3-8), was designed. It was found that the strain energy decreased and the energy gap increased as the number of n and ring diameter increased. The ionization potential and electronic affinity tended to increase and decrease as the strain energy decreased at the same number of [n]CFs, respectively. With a balance between hole and electron reorganization energies in the system, these compounds demonstrated great potential as ambipolar materials. It was also found that [n]CFs showed an obvious blue shift in their emission spectra wavelengths (λ_em2) as the strain energy decreased. Steric strain provides a powerful tool for the design of multifunctional semiconductors in organic optoelectronics.     

Carbonyl polymeric electrode materials for metal-ion batteries

This review presents the recent progress in carbonyl polymeric electrode materials for lithium-ion batteries, sodium-ion batteries and magnesiumion batteries. This comprehensive review is expected to be helpful for arousing more interest of organic materials for metal-ion batteries and designing novel battery materials with high performance.     

Quantitative studies on furfural and organic acid formation during hydrothermal,acidic and alkaline degradation ofD-xylose

Summary Chromatographic analysis of the degradation ofD-xylose either in plain water or aqueous sulfuric acid at temperatures ranging from 180 – 220°C gave up to 50 mol% of furfural. Activation energies did not differ significantly between reactions in plain water (E _a =119.4 kJ/mol), 0.001M H₂SO₄ (E _a =120.6 kJ/mol), 0.01M H₂SO₄ (E _a =130.8 kJ/mol), and 0.1M H₂SO₄ (E _a =120.7 kJ/mol). However, under alkaline conditions the activation energy was only 63.7 kJ/mol, indicating a different reaction mechanism. Isotachophoretic analyses revealed the formation of pyruvic, formic, glycolic, lactic, and acetic acid. While the relative yields of these acids ranged from 0.8 to 7% under hydrothermal and acidic conditions, 10 – 23% were obtained in alkaline degradation.

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Quantitative Studien zur Bildung von Furfural und organischen Säuren während des hydrothermalen, sauren und alkalischen Abbaues vonD-Xylose

Zusammenfassung Die chromatographische Analyse des Abbaues vonD-Xylose in reinem Wasser und Schwefelsäure bei Temperaturen von 180 – 220°C ergab die Bildung von bis zu 50 mol% Furfural. In bezug auf die Aktivierungsenergie zeigten sich keine signifikanten Unterschiede zwischen dem Abbau vonD-Xylose in reinem Wasser (E _a =119.4 kJ/mol), 0.001M H₂SO₄ (E _a =120.6 kJ/mol), 0.01M H₂SO₄ (E _a =130.8 kJ/mol), and 0.1M H₂SO₄ (E _a =120.7 kJ/mol). Unter alkalischen Bedingungen hingegen betrug die Aktivierungsenergie nur 63.7 kJ/mol. Dies weist auf einen unterschiedlichen Reaktionsmechanismus hin. Ferner konnte mittels Isotachophorese die Bildung von Brenztraubensäure, Ameisensäure, Glycolsäure, Milchsäure und Essigsäure nachgewiesen werden. Während sich die relativen Ausbeuten in Wasser und Schwefelsäure zwischen 0.8 und 7% bewegten, betrugen sie unter alkalischen Bedingungen 10 bis 23%.

     

吸附/一级热解吸/气相色谱联用测定室内空气中的挥发性有机物

本文以高聚物TenaxTA动态吸附,一级热解吸/毛细管气相色谱法联用测定室内空气中的挥发性有机物。优化了热解吸温度和热解吸时间,建立了苯、甲苯、乙酸正丁酯、乙苯、对二甲苯、苯乙烯、邻二甲苯、正十一烷等8种典型有机污染物的外标定量曲线,各化合物线性范围为103,相关系数R为0.9983～0.9999,最低检出浓度可达2×10-4mg/m3;考察了方法的重复性、热解吸率和残留率,并分析了实际空气样品。