染料敏化太阳能电池中染料分子共轭π桥的扩展

以染料分子D5为原型, 采用不同类型和数量的共轭桥单元来设计D-π-A 型有机分子. 采用密度泛函理论(DFT)和含时密度泛函理论(TDDFT)来模拟计算分子的形貌、分子轨道能级以及紫外-可见光谱, 为染料敏化太阳能电池(DSSCs)的敏化分子寻找适合的共轭桥. 采用“次甲基链”、“呋喃环”或“噻吩环”、“次甲基链和呋喃环”或“次甲基链和噻吩环”作为共轭桥单元, 使得分子的吸收光谱依次红移. 随着共轭桥单元的增加, 分子的吸收光谱有剧烈的红移, 但随着共轭桥单元数量的进一步增加, 分子吸收光谱的红移现象减弱. 分子的最低未占据分子轨道(LUMO)能级逐渐降低, 而最高占据分子轨道(HOMO)能级逐渐升高. 采用3个“次甲基链和呋喃环”或者“次甲基链和噻吩环”作为共轭桥时, HOMO能级已经高于氧化还原电解质的能级, 而在极性溶液中, 由2个“次甲基链和噻吩环”单元作为有机分子的共轭桥时, 分子的HOMO能级已经高于氧化还原电解质的能级了. 采用“次甲基链和呋喃环”或“次甲基链和噻吩环”单元作为有机分子的共轭桥时, 吸收光谱有明显的红移,但对于DSSCs的敏化分子, 这样的共轭桥单元只能有1-2个, 不宜过多.     

新手-熟手化学教师课堂教学基元系统有效性的比较研究

依据课堂教学系统CPUP模型理论和课堂教学基元系统有效评价量表,通过对24位新手教师和熟手教师的24节常态课堂中基元系统有效性进行对比分析。结果发现,新手教师与熟手教师的主要差别表现在“教学行为链实施质量”和“资源和技术的使用质量”2个维度上,熟手教师显著高于新手教师;而在“时间利用的合理性”“匹配度”和“基元内容的合理性”3个维度上,2者不存在显著差异。     

熵理论指导下的化学开放性教学模式探究

熵定律这一自然界的重要定律也被认为是“一种新的世界观”。熵是一个不断被深化与泛化的概念。教学过程也是不断从低级有序向高级有序转化的过程,即是从“高熵”走向“低熵”。用熵理论指导开放性教学模式,以“化学能转化为电能”为例进行课堂教学,从低级有序状态到非平衡态,输入新的教学手段、教学方式--涨落,通过非线性作用达到新的高级有序阶段。为学生的学习创造了一个广阔的思维空间和全方位、多层次、多渠道的学习环境。     

超支化聚酯的改性及其结晶性能的研究

用十六酰氯和十八异氰酸酯分别对端羟基的超支化聚酯Boltorn^TMH20改性,可获得粉末状超支化低聚物,具有无定形“内核”及可结晶“外壳”的分子结构.实验结果表明,采用十八异氰酸酯改性的丙烯酸化超支化聚酯的熔点高于十六酰氯改性聚合物.     

国际科学教育视角下1-9年级学生“物质”核心概念进阶维度研究

概念转变理论、认知架构理论、概念形成理论都验证了核心概念建构的重要性。基于核心概念建构的进阶路径,介绍了学生理解“物质”概念进阶表征框架、“物质”和学生能力水平进阶表征框架、“物质”结构的学习进阶表征框架、“物质”核心概念区块理论表征框架和“物质”概念描述理论表征框架,并以“水的认识”为例分析了其构造图和结果空间。基于美国、英国、澳大利亚、爱尔兰、新加坡、加拿大阿尔伯塔省、加拿大安大略省、中国台湾、中国大陆9个国家或地区1至9年级科学课程文件,梳理了学生“物质”核心概念,并从“成分与辨识”“性质与应用”“变化与转化”3个视角划分了学生“物质”核心概念进阶维度,介绍了“物质”核心概念进阶测量方法,以期对我国科学教育有所启示。     

科学探究能力的构成要素——基于国外科学课程文件的分析

科学探究能力构成要素的不明确使得对学生探究能力的培养和评价缺乏实效性。对国外科学课程文件中科学探究能力的构成要素进行频次统计,得出科学探究能力的构成体系：提出问题能力由“发现并建构明确的问题”等4个要素构成;猜想与假设能力由“基于观察和所学科学知识进行预测,建构可验证的假设”等4个要素构成;制定计划能力由“确定定性和定量方法”等6个要素构成;进行实验能力由“按照设计程序进行实验”等10个要素构成;收集证据能力由“用硬件）如计算机）和软件、电子资源收集和存储信息”等4个要素构成;解释与结论能力由“分析、推理证据的规律,通过归纳、演绎得出结论”等5个要素构成;反思与评价能力由“评价结论和观点正确性和局限性”等6个要素构成;表达与交流的能力由“口头进行探究实践报告,并准确地、有逻辑性地运用语言”等7个要素构成。     

硅胶表面上脂肪酸蒸气吸附膜

应用Gibbs方程由甲酸、乙酸和丙酸蒸气在硅胶上的吸附等温线计算了吸附膜的表面压力(π)与每个吸附分子所占面积(σ)间的关系(π～σ图).所得曲线与不溶物在溶液表面上的结果相似,均表现出有“液态扩张膜”“转变膜”和“液态凝聚膜”.不同的是,不溶物只能形成单分子层膜,而硅胶表面上的脂肪酸吸附膜则是多分子层的.蒸气吸附膜由单层向多层的转变,恰与π～σ图上的“液态扩张膜”向“转变膜”的转变相对应.吸附焓(△H)与吸附熵(△S)的计算结果表明,在此转变附近AH和AS发生急剧变化.     

“双一流”背景下化学本科人才培养创新路径探索*

人才培养是高校的核心使命和必然要求。在“双一流”建设背景下,国家对高校人才培养提出了新要求。西北大学化学与材料科学学院围绕“培养什么人”“怎样培养人”,对本科人才培养不断进行探索和创新,搭建 “以本科生导师制为核心”的科研训练体系,“以拓展学术视野为核心”的国际化培养体系,“以调动教师教学投入为核心”的评价激励体系,“以提升创新意识为核心”的实践育人体系等措施,实现高校理科人才培养的创新发展。     

十八烷基聚氧乙烯表面空间结构和蛋白质吸附行为研究

为探讨聚合物-水界面十八烷基聚氧乙烯链(SPEO)空间结构和白蛋白选择性吸附行为的内在联系,本文采用聚甲基丙烯酸甲酯接枝十八烷基聚氧乙烯(PMMA-g-SPEO),通过不同热处理方式获得了具有“环形链”(A)和“尾形链”(B)结构的两种模型表面.在A表面,水相接触角随水化时间的延长而迅速降低,最终亲水性的界面可同时有效阻抗白蛋白和纤维蛋白原的吸附,但不呈现对白蛋白的选择性吸附;而在B表面,水相接触角随水化时间的延长变化不大,最终疏水性的界面可在有效阻抗纤维蛋白原的吸附同时,有效诱导白蛋白的选择性吸附,具有聚氧乙烯(PEO)阻抗非特异性吸附和十八烷基选择性吸附协同作用的特点.     

新手熟手初中化学教师课堂教学行为特征的比较研究*——以“酸和碱”单元教学为例

通过对新手化学教师和熟手化学教师各4节“酸和碱”单元常态课堂中教师使用教学行为链、教学行为对在时间和频次等方面的特征进行对比分析发现,在教学行为链上,新、熟手化学教师都会在较高水平的教学行为链上花费更多的时间,熟手化学教师高水平教学行为链在频次上的占比要优于新手化学教师,在不同教学行为链时间安排上的合理性要更高一些;在教学行为对上,新、熟手化学教师都多以“问”和“讲”,学生多以“答”的方式来展开课堂活动,熟手化学教师在每一次“动”和“思”上所用时间要明显高于新手化学教师,学生参与课堂的水平上,熟手化学教师要优于新手化学教师。得出如下启示:与熟手化学教师相比,新手化学教师应有效地组织和安排课堂教学行为,注重对“酸和碱”学科内容本身及其教学的驾驭。无论是熟手还是新手化学教师均应进一步给予学生课堂参与的机会。     

A theory of polymer solutions without the mean-field approximation in Flory-Huggins theory

The concept of the volume fraction at chain end is proposed, which is the conditional probability for a site having been occupied, knowing that an adjacent site is occupied by polymer end. The overall entropy of polymer/solvent system is separated into two fundamentally different parts, i.e., the translational entropy and the conformational entropy. Based on these a theory of polymer solutions is established. When a mean-field approximation is introduced, Flory-Huggins (FH) theory is recovered. The FH interaction parameters and spinodal curves of the polystyrene/cyclohexane system are calculated and compared with the experimental data. The good prediction of them two is achieved.     

改进的聚合物溶液理论

在高分子溶液理论中引入Gibbs分布 ,用统计物理学方法重新推导出了聚合物溶液的热力学公式 .将高分子溶液的自由能和熵分三部分进行了计算 ,无热平动部分 ,无热构象部分和构象有热部分 .无热平动自由能和无热构象自由能分别等于Flory Huggins混合自由能公式的前两项 ,构象有热部分引入了Gibbs分布 ,考虑了链段 溶剂分子相互作用对高分子构象的影响 .在分子间的相互作用足够小时 ,又回到了FH公式     

Lattice cluster theory of associating polymers. II. Enthalpy and entropy of self-assembly and Flory-Huggins interaction parameter χ for solutions of telechelic molecules

The lattice cluster theory for solutions of telechelic polymer chains, developed in paper I, is applied to determine the enthalpy Δh(p) and entropy Δs(p) of self-assembly of linear telechelics and to evaluate the Flory-Huggins (FH) interaction parameter χ governing the phase behavior of these systems. Particular focus is placed on examining how these interaction variables depend on the composition of the solution, temperature, van der Waals and local "sticky" interaction energies, and the length of the individual telechelic chains. The FH interaction parameter χ is found to exhibit an entropy-enthalpy compensation effect between the "entropic" and "enthalpic" portions as either the composition or mass of the telechelic species is varied, providing unique theoretical insights into this commonly reported, yet, enigmatic phenomenon.     

Pressure Effects on Thermodynamics of Phase Behavior in Polystyrene/Methylcyclohexane Solutions

The calculations presented in this paper are based on the Sanchez-Lacombe(SL)lattice fluid theory.The interaction energy parameter,g12/k,required in this approach was obtained by fitting the cloud points of polystyrene(PS)/methylcyclohexane(MCH)polymer solutions under pressure.The SL lattice fluid theory was used to calculate the spinodals,the binodals,and the Flory-Huggins(FH)interaction parameter of the solutions.The calculated results show that the SL lattice fluid theory can describe the dependences of thermodynamics of PS/MCH solutions on temperature and pressure very well.However,the calculated enthalpy and the excess volume changes indicate that the Clausius-Clapeyron equation cannot be suitable to describe pressure effect on PS/MCH solutions.Further analysis on the thermodynamics of this system under pressure shows that the role of entropy is more important than the excess volume in the present case.     

The effect of polymer chain length on the thermodynamics of acrylate/cyanobiphenyl mixtures

The effect of polymer molecular mass on the phase behaviour and solubility limits of polymer/liquid crystal mixtures is studied for blends of poly(methyl methacrylate) (PMMA) and the small-molecule liquid crystal, 4'-octyl-4-biphenylcarbonitrile (8CB). The phase diagrams from optical microscopy show a limit to the effect of increasing polymer molecular mass. The Flory-Huggins theory (FH) for polymer solutions is used to extract the interaction parameter, χ, from the phase diagrams. The initial FH fits are performed with the assumption that χ is independent of polymer molecular mass, but result in poor correlation to the microscopy data. When χ is allowed to scale with M _w, however, the FH fits are consistent with the limiting molecular mass behaviour. This result represents, to our knowledge, the first time that this scaling behaviour has been observed in polymer/liquid crystal blends. The solubility limit, β, of 8CB in PMMA for each polymer molecular mass is also determined and, when compared with the results of previous studies, support the concept that β is independent of both polymer composition and molecular masses when the polymer molecular mass exceeds ca. 5×10⁵ g mol^-1.     

Communication: lateral phase separation of mixed polymer brushes physisorbed on planar substrates

Here, we present a new method to model lateral phase separation in mixed polymer brushes physisorbed to a planar surface with mobile grafting points. The model is based on a local mean field theory that combines a Flory-Huggins approximation for interaction enthalpies with an Alexander-de Gennes brush entropy contribution. Using Monte Carlo sampling, the application of these two interactions to a lattice model yields a range of phase behavior consistent with previous theoretical and experimental work. This model will be useful for predicting mixed polymer brush morphologies on planar surfaces and in principle can be extended to other geometries (e.g., spheres) and polymer systems.     

Thermodynamic model of gas permeability in polymer membranes

A new molecular thermodynamic model is developed of the gas permeability in polymer membranes on the basis of configurational entropy and Flory‐Huggins theory to predict permeability dependence on the concentration of penetrant. Three kinds of configurational entropy are taken into account by this model; that is, the disorientation entropy of polymer, the mixing entropy, and specific interaction entropy of polymer/gas. The validity of the mathematical model is examined against experimental gas permeability for polymer membranes. Agreement between experimental and predicted permeability is satisfactory. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 661–665, 2007     

Effect of attractions on the structure of polymer solutions confined between surfaces: a density functional approach

A density functional theory is presented to study the effect of attractions on the structure of polymer solutions confined between surfaces. The polymer molecules have been modeled as a pearl necklace of freely jointed hard spheres and the solvent as hard spheres, both having Yukawa-type attractions and the mixture being confined between attractive Yukawa-type surfaces. The present theory treats the ideal gas free energy functional exactly and uses weighted density approximation for the hard chain and hard sphere contributions to the excess free energy functional. The attractive interactions are calculated using the direct correlation function obtained from the polymer reference interaction site model theory along with the mean spherical approximation closure. The theoretical predictions on the density profiles of the polymer and the solvent molecules are found to agree quite well with the Monte Carlo simulation results for varying densities, chain lengths, wall separations, and different sets of interaction potentials.     

Density functional theory of realistic models of polyethylene liquids in slit pores: comparison with monte carlo simulations

Density functional theory is applied to study properties of fully detailed, realistic models of polyethylene liquids near surfaces and compared to results from Monte Carlo simulations. When the direct correlation functions from polymer reference interaction site model (PRISM) theory are used as input, the theory somewhat underpredicts the density oscillations near the surface. However, good agreement with simulation is obtained with empirical scaling of the PRISM-predicted direct correlation functions. Effects of attractive interactions are treated using the random-phase approximation. The results of theoretical predictions for the attractive system are also in reasonable agreement with simulation results. In general, the theory performs best when the wall-polymer interaction strength is comparable to polymer-polymer interactions.     

Phase equilibria and phase separation dynamics in a polymer composite containing a main-chain liquid crystalline polymer

Various topological phase diagrams of blends of main-chain liquid crystalline polymer (MCLCP) and flexible polymer have been established theoretically in the framework of Matsuyama–Kato theory by combining Flory–Huggins (FH) free energy for isotropic mixing, Maier–Saupe (MS) free energy for nematic ordering in the constituent MCLCP, and free energy pertaining to polymer chain-rigidity. As a scouting study, various phase diagrams of binary flexible polymer blends have been solved self-consistently that reveal a combined lower critical solution temperature (LCST) and upper critical solution temperature (UCST), including an hourglass phase diagram. The calculated phase diagrams exhibit liquidus and solidus lines along with a nematic–isotropic (NI) transition of the constituent MCLCP. Depending on the strengths of the FH interaction parameters and the anisotropic (nematic–nematic) interaction parameters, the self-consistent solution reveals an hourglass type phase diagram overlapping with the NI transition of the constituent MCLCP. Subsequently, thermodynamic parameters estimated from the phase diagrams hitherto established have been employed in the numerical computation to elucidate phase separation dynamics and morphology evolution accompanying thermal-quench induced phase separation of the MCLCP/polymer mixture. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3621-3630, 2006