Targeted Management of Perovskite Film by Co(II) Sulfophenyl Porphyrin for Efficient and Stable Solar Cells†

In the lead halide perovskite solar cells (PSCs), the redox reaction of I^– and Pb²⁺ ions in perovskite materials under the fabrication and operation processes causes the formation of defects to destroy the cell efficiency and long-term stability. Herein, we have employed a Co(II) sulfophenyl porphyrin (CoTPPS) to modify the perovskite film. The sulfonic group could coordinate with Pb²⁺ to efficiently passivate the uncoordinated Pb²⁺. Additionally, Co²⁺ ions in CoTPPS could react with I₂ generated under the thermal and light stress to yield the Co³⁺ and I^–, thus achieving the regeneration of I^– in perovskite film. Therefore, the CoTPPS could realize the targeted management of the imperfections in perovskite film. As a result, the modified PSCs reveal the remarkably enhanced cell performance. More importantly, the CoTPPS modified device retains 75% of its initial efficiency value storing at 85°C for 2000 h and about 70% of its efficiency when being continuously illuminated at a simulated sunlight for 1200 h. This strategy tackles the chemical reaction and inhibits the defect generation, thus improving the operational stability and efficiency of PSCs.      

两亲性季铵盐对钙钛矿太阳能电池效率和稳定性的影响

将廉价易得的两亲性季铵盐十六烷基三甲基溴化铵（CTMAB）加入到钙钛矿前驱体溶液中,通过调节添加量研究了CTMAB对钙钛矿太阳能电池效率和稳定性的影响.结果表明,加入CTMAB后制备的钙钛矿薄膜更加致密均匀,表面缺陷更少,钙钛矿晶体结晶性得到显著提高,从而提高了电池的光电转换效率及电池稳定性;含有CTMAB的钙钛矿太阳能电池的光电转换效率（PCE）为18.03%,明显高于未添加CTMAB的电池效率（17.05%）;含有CTMAB的电池稳定性有较大的提高,在一定湿度环境中保存40 d后效率仍达初始效率的95%,而未添加CTMAB的器件效率只有初始效率的70%.     

金属有机骨架及其复合材料在分离领域中的应用进展

金属有机骨架（MOFs）是一类由无机金属离子与有机配体自组装形成的新型有机-无机杂化多孔材料,因具有比表面积超高、结构多样、热稳定性良好、孔道尺寸和性质可调等优势,在分离领域表现出重要的应用价值。然而,采用传统方法制备的MOFs多为粒径在微米或亚微米尺度的晶体,且颗粒形貌不规则,因此限制了MOFs在样品前处理和色谱固定相等领域的应用和发展。构建基于MOFs的复合材料是弥补MOFs应用缺陷的一项有效措施,有望在保留MOFs优越的分离特性的同时,引入基体材料的特定性能。该文简要综述了近年来MOFs及其复合材料在吸附、样品前处理和色谱固定相等分离领域中的应用进展,并对MOFs在分离科学中的应用前景做出展望。     

A mesoscale study of thermal expansion behaviors of epoxy resin and carbon fiber/epoxy unidirectional composites based on periodic temperature and displacement boundary conditions

The thermal expansion behaviors of neat epoxy resin and carbon fiber/epoxy unidirectional (UD) composites were experimentally and numerically studied in this paper. The dynamic mechanical analysis (DMA), thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and thermal conductivity measurement were used to measure the thermo-mechanical properties of epoxy resin at different temperatures. The dilatometer was used to measure the thermal strains and linear CTEs of neat epoxy resin and UD composites. In addition, a mesoscale finite element model based on the periodic temperature and displacement boundary conditions was presented to analyze the thermal expansion behaviors of UD composites. The resin-voids representative volume element (RVE) was used to calculate the thermo-mechanical properties of several kinds of resin-voids mixed matrix. From the results it can be found that the glass transition temperature of epoxy resin, porosity and fiber orientation angle have significant effects on the thermal expansion behaviors of UD composites. The mesoscale finite element analyses (FEA) have obvious advantages than various existing analysis models by comparing their predictive results. The distributions of thermal displacement, thermal stress and thermal strain were extracted between the carbon fiber, resin-voids mixed matrix and their interface, and also between the front and back surfaces of the loading direction, to further investigate thermal expansion structure effects of UD composites. This paper revealed that the mesoscale FEA based on periodic temperature and displacement boundary conditions can be also used for thermal expansion researches of other complex structure composites.     

Preparation of high performance composites based on aluminum nitride/poly(ether-ether-ketone) and their properties

Novel high performance aluminum nitride (AlN)/poly(ether-ether-ketone) (PEEK) composites containing 0-50 wt.% fractions of AlN were prepared by solution blending method followed by hot pressing to evaluate their density, melting temperature, crystallization, thermal stability, morphological behavior and Vickers hardness by using different characterization techniques. Differential scanning calorimetry results indicated that the AlN particles are very effective nucleating agent, which results in increase in melting point, hot crystallization temperature and crystallinity of composites as the AlN content increases. Thermogravimetric analysis showed enhanced thermal stability of the composites with respect to PEEK. Density and X-ray diffraction techniques showed that crystallinity of the composites increases as the wt.% of AlN content increases in polymer matrix. Scanning electron microscopy revealed that AlN particles were well dispersed with no porosity in composites. Vickers hardness of the samples increased from 24 kg/mm² for the pure PEEK to 35 kg/mm² for AlN/PEEK composites.     

Effect of weighting materials on carbonation of oil well cement-based composites under high temperature and CO2-rich environment

As an indispensable part of cement slurry for high temperature and high pressure oil and gas wells, weighting materials have a significant impact on the carbon dioxide corrosion of oil well cement-based composites.This paper studied the carbonation process of cement with three weighting agents, and evaluated the compressive strength and carbonation depth of cement at 150 ℃. XRD, SEM and MIP were used to study the carbonation mechanism of cement. When 21 days of carbonation, the carbonation depth growth rate of hausmannite cement was 0.21 mm/d, hematite cement was 0.24 mm/d, and barite cement was 0.31 mm/d. The compressive strength of cement decreased after carbonation,and the carbonation had a minor influence on the compressive strength of hausmannite cement and the most significant impact on barite cement. The carbonation product of oil well cement was mainly calcite. Unstable vaterite mainly existed in the barite cement sample, indicating that the barite cement sample was the most serious corrosion. In the carbonation zone, the number of pores smaller than 10 nm increased the most in the hausmannite cement sample. Pores with a diameter greater than 100 nm accounted for 1.9 % in the hausmannite cement, 3.0 % in hematite cement, and 4.8 % in barite cement. The result shows that hausmannite is the most conducive to the corrosion resistance of oil well cement.     

Copper(I)-Catalyzed Cycloaddition of Methyl O-Propargylpodocarpate and Azides at Room Temperature

Copper iodide was employed as an efficient catalyst for the synthesis of 1,2,3-triazole derivatives of podocarpic acid at room temperature through “click” chemistry cycloaddition reactions of methyl O-propargylpodocarpate and propargyl O-propargylpodocarpate with azides.

Fe_3O_4/RGO复合材料的制备及其电化学性能研究

以改进Hummers法合成的氧化石墨烯(GO)为前驱体,通过水热法结合烧结工艺制备了四氧化三铁/还原氧化石墨烯(Fe_3O_4/RGO)复合材料。利用X射线衍射(XRD)、拉曼光谱(Raman)、扫描电镜(SEM)、透射电镜(TEM)等手段对复合材料的理化性能进行表征;通过充放电测试、循环伏安(CV)和电化学阻抗谱(EIS)等技术,综合考察了材料的储锂性能及电化学性能增强机制。结果表明,在200和600 m A/g电流密度下,Fe_3O_4/RGO复合负极循环60次后的放电比容量分别保持在709和479 mAh/g,表现出良好的倍率性能;相较于纯Fe_3O_4负极,复合负极呈现出更优异的锂电性能,其电化学性能的改善得益于RGO能增强材料的电导性和结构稳定性。     

Preparation and properties of composites made from rice straw and poly(vinyl chloride) (PVC)

Rice straw was employed for the preparation of lignocellulosic‐poly(vinyl chloride) (PVC) composites. The effect of pretreatment of rice straw, concentration of PVC, pressure as well as pressing temperature on the mechanical properties and water absorption was studied. Also, the effect of lignin as coupling agent on the mechanical properties and water absorption of composite was studied. Composites of rice straw comprising both PVC and a coupling agent offer superior properties compared to those made from only rice straw and PVC. The extent of improvement in the mechanical properties and dimensional stability of composites depended not only on the pretreatment of rice straw, concentration of PVC and lignin but also on pressure and pressing temperature. Copyright © 2004 John Wiley & Sons, Ltd.     

Fe(II) Spin Crossover/Polymer Hybrid Materials: Investigation of the SCO Behavior via Temperature-Dependent Raman Spectroscopy,Physicochemical Characterization and Migration Release Study

Polymeric composites constitute an appealing class of materials with applications in various fields. Spin crossover (SCO) coordination complexes are switchable materials with potential use in data storage and sensors. Their incorporation into polymers can be considered an effective method for their wider practical application. In this study, Fe(II) SCO/polylactic acid hybrid polymeric composites have been prepared by film casting. The mononuclear coordination complex [Fe{N(CN)₂}₂(abpt)₂] was incorporated into polylactic acid. The morphological, structural and thermoanalytical characterization of the composite films were performed via scanning electron microscopy (SEM), attenuated total reflectance (ATR/FTIR), Raman spectroscopy and differential scanning calorimetry (DSC). In addition, the migration release study (MRS) of the SCO compound from the polymeric matrix into the food simulant 50% v/v water/ethanol solution was also examined via UV/Vis absorption. Of particular interest was the investigation of the SCO behavior of the coordination complex after its incorporation into the polymer matrix; it was accomplished by temperature-dependent micro-Raman spectroscopy. The described attempt could be considered a preparatory step toward the development of SCO-based temperature sensors integrated into food packaging materials.     

Morphology,crystalline structure,and properties of poly(vinylidene fluoride)/silica hybrid composites

Poly(vinylidene fluoride)/silica (PVDF/SiO₂) hybrid composite films were prepared via sol–gel reactions from mixtures of PVDF and tetraethoxysilane in dimethylacetamide. Their morphology, crystalline structure, and thermal, mechanical, and electrical properties were examined. For morphology measurements, scanning electron microscopy and optical microscopy were applied. X‐ray diffraction and infrared analyses showed that the crystalline structure of PVDF was not changed much by the addition of SiO₂, indicating that there was no interaction between PVDF and SiO₂. With increasing SiO₂ content, the melting temperature rarely changed, the degree of crystallinity and the dielectric constant decreased, and the decomposition temperature slightly increased. A PVDF/SiO₂ hybrid composite film with 5 wt % SiO₂ exhibited balanced mechanical properties without a severe change in the crystalline structure of PVDF, whereas for the hybrid composites with higher SiO₂ contents (>10 wt %), the mechanical properties were reduced, and the spherulite texture of PVDF was significantly disrupted by the presence of SiO₂ particles. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 19–30, 2002     

Nonisothermal melting and crystallization of polypropylene in model composites: Kinetic analysis

The kinetics of nonisothermal melting and the crystallization of polypropylene (PP) in polypropylene/carbon‐fiber (C/PP) composites were studied by differential scanning calorimetry with the Nedkov and Atanasov method. Characteristic parameters such as the lamellar thickness, the transport energy through the phase boundary, and the surface free energy were determined and analyzed. In nonisothermal melting, the nucleation effect of carbon fibers was confirmed by decreasing transport energy (79 and 41 kJ/mol for PP and C/PP, respectively) and surface free energy (8 × 10^?4 and 7.9 × 10^?5 J/m² for PP and C/PP, respectively). Depending on the carbon‐fiber content, the lamellar thickness changed from 6.7 × 10^?9 m to 9.05 × 10^?9 m. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 66–73, 2005     

Fabrication and properties of poly(propylene carbonate)/calcium carbonate composites

Composites of poly(propylene carbonate) (PPC) reinforced with micrometric and nanometric calcium carbonate particles were prepared via melt mixing followed by compression molding. The morphology and mechanical and thermal behaviors of the composites were investigated. Static tensile tests showed that the tensile strength, stiffness, and ductility of the composites tended to increase with increasing contents of micrometric calcium carbonate particles. This improvement in the tensile properties was attributed to good interfacial adhesion between the fillers and matrix, as evidenced by scanning electron microscopy examination. However, because of the agglomeration of calcium carbonate nanoparticles during blending, those composites with nanoparticles exhibited the lowest tensile strength. Thermogravimetric measurements revealed that the incorporation of calcium carbonate into PPC resulted in a slight improvement in its thermooxidative stability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1806–1813, 2003     

Annealing induced electrical conductivity jump of multi‐walled carbon nanotube/polypropylene composites and influence of molecular weight of polypropylene

Multi‐walled carbon nanotube (MWCNT)/polypropylene (PP) composites were prepared by a micro melt mixing process. As‐prepared composites had relatively low electrical conductivity due to the disruption of MWCNT network by strong shear. The electrical conductivity jumped to high values throughout an annealing process above the melting temperature of PP. The significant enhancement of electrical conductivity was influenced by annealing time, temperature, and content of MWCNTs. In particular, molecular weight of PP played an important role in affecting the conductivity enhancement. The molecular weight of PP was varied from 190,000 to 340,000 to examine its effect on the electrical conductivity. By comparing the conductivity enhancement behavior of composites with different molecular weight PPs and observing the morphology evolution during annealing, it was found that reaggregation of MWCNTs and the subsequent formation of MWCNT network during annealing are the main reasons for the jump of electrical conductivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Preparation of conducting poly(vinyl chloride)/polyindole composites and freestanding films via chemical polymerization

This study covers the synthesis of conducting polyindole (PIN) homopolymer, poly(vinyl chloride)/polyindole (PVC/PIN) composites, and preparation of their freestanding films. PIN and composites were synthesized chemically by radicalic mechanism using FeCl₃ as an initiator. Films of PVC and PVC/PIN composites were prepared by casting on glass Petri dishes. Mechanical properties of films were examined by stress–strain experiments. From FTIR spectra of polymers, it was revealed that polymerization reaction occurred by 2–3 mechanism. The conductivities of polymers at different temperatures were also measured by four‐probe technique and found in the range 10^?4 to 10^?5 S cm^?1. Magnetic properties of the polymers were analyzed by Gouy scale measurements and were found that their conducting mechanisms are of polaron and bipolaron natures. Thermal properties of polymers were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) and found that they had shown adequate thermal stability. X‐ray diffraction (XRD) spectra showed the amorphous nature of the polymers. Scanning electron microscopy (SEM) was used for microstructural analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1290–1298, 2010     

Pt-ZnO/C复合材料的合成及对醇类催化活性的研究

采用溶胶-凝胶法制备了ZnO微米颗粒,电沉积Pt合成了Pt-ZnO/C复合材料。利用X射线衍射仪（XRD）和扫描电子显微镜（SEM）对产物的晶型和形貌进行了表征,并利用循环伏安法（CV）研究了所得复合材料对甲醇和乙醇的电催化活性。实验结果表明,该催化剂在ZnO的质量分数为50%时对甲醇和乙醇氧化的电催化活性最好。
     

Thermal and volumetric property analysis of polymer networks and composites using elevated temperature digital image correlation

Digital Image Correlation (DIC), which exploits non-contact advantages and full-field analysis, provides more data in-situ that are not possible with traditional techniques. In this work, elevated temperature digital image correlation techniques were applied to a glassy polymer network via thermal expansion and contraction experiments to study volumetric behavior during the curing process. A glassy epoxy network was tested in both cured and under-cured states and heated to the ultimate cure temperature. Matrix volume changes due to both thermal expansion and cure shrinkage were quantified. Concurrently, the thermal expansion of aerospace-grade composite laminates was also observed in matrix and fiber-dominant directions. Additionally, the strain-free temperature of a non-symmetric composite laminate was identified through thermal compensation of process-induced curvatures. Finally, laminate dimension changes were related to the strain-free temperature as means to probe process-induced strains within composite laminates. Thermal properties of the neat matrix and composite laminates were compared to traditional techniques, validating the benefit of elevated temperature digital image correlation for composite matrix qualification.     

钙钛矿型LaFexCu（1-x）O3固相芬顿催化剂制备及其降解亚甲基蓝性能研究

采用共沉淀法制备系列钙钛矿型催化剂LaFexCu(1-x)O3(x=0.2,0.4,0.6,0.8),通过XRD、FT-IR、SEM、BET和XPS进行表征。以亚甲基蓝(Methylene Blue, MB)为模型污染物,将LaFexCu(1-x)O3的催化性能与LaFeO3和LaCuO3进行比较,确定最佳掺杂比例。考察不同因素对催化反应的影响,确定最佳反应条件,并研究催化反应机理和催化剂的稳定性。结果表明：LaFexCu(1-x)O3呈钙钛矿晶型结构,颗粒空间分布松散,孔道丰富,比表面积和平均孔径较大,从而有利于亚甲基蓝的吸附降解。当x=0.6时,LaFe0.6Cu0.4O3具有最高的比表面积,同时催化活性最高。最佳条件：亚甲基蓝初始浓度为1000 mg·L-1,温度55 ℃、初始pH为4、双氧水投加量2.5 mL·L-1、LaFe0.6Cu0.4O3投加量60 mg·L-1。在最佳条件下,亚甲基蓝在20分钟内催化降解完全脱色,50分钟内COD去除率和TOC去除率分别达到94.2%和84.3%。ESR测试表明亚甲基蓝降解是在羟基自由基(·OH)和超氧自由基(·HO2)共同作用下完成的。10次循环后脱色率、COD去除率和TOC去除率仍能分别达到90.2%、84.2%和80.2%,证实LaFe0.6Cu0.4O3是一种高效稳定的非均相催化剂。     

Molecular composites of poly(p‐phenylene terephthalamide) anion and poly(ethylene oxide): Thermal behavior and morphology

Molecular composites, in which a small concentration of ionically modified poly(p‐phenylene terephthalamide) (PPTA) is dispersed in a poly(ethylene oxide) matrix, have been prepared. With the content of PPTA anion increasing to about 5 wt %, the glass‐transition temperature rises and the melting temperature decreases. From the equilibrium‐melting‐temperature depression data that were obtained from Hoffman–Weeks plots, the Flory–Huggins interaction parameter was determined to be negative (−1.10). These indications of enhanced miscibility between the components are attributed to intermolecular ion–dipole interactions. The presence of rigid PPTA‐anion reinforcement alters the morphology; for example, the spherulite size is reduced, and the degree of crystallinity is lowered. Possible models of how the reinforcement is incorporated into the composite are presented. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1369–1376, 2000     

氨丙基官能化HMS介孔分子筛的合成及表征

沿S0I0路径,以十六胺为模板剂,以3-氨丙基三乙氧基硅烷为有机硅源,通过与TEOS共水解沉淀合成了氨丙基官能化HMS介孔分子筛.采用粉末X-射线衍射分析、N2吸/脱附、扫描电镜分析、高分辨透射电镜分析、傅立叶变换红外分析以及元素分析等表征手段,对所合成的材料进行表征.氨丙基官能化HMS介孔分子筛具有worm-like孔道结构,且较为均一的孔径分布.研究了前体硅源中3-氨丙基三乙氧基硅烷含量的变化对氨丙基官能化HMS介孔分子筛的相结构及织构性能的影响.傅立叶变换红外分析表明,NH2-CH2-CH2-CH2有机基团分布在杂化HMS介孔孔道中.