Elementary Photoelectronic Processes at a Porphyrin Dye/Single‐Walled TiO2 Nanotube Hetero‐interface in Dye‐Sensitized Solar Cells: A First‐Principles Study

A unique one‐dimensional (1D) sandwich single‐walled TiO₂ nanotube (STNT) is proposed as a photoanode nanomaterial with perfect morphology and large specific surface area. We have thoroughly examined the elementary photoelectronic processes occurring at the porphyrin dye/STNT hetero‐interface in dye‐sensitized solar cells (DSSCs) by theoretical simulation. It is desirable to investigate the interfacial photoelectronic processes to elucidate the electron transfer and transport mechanism in 1D STNT‐based DSSCs. We have found that the photoexcitation and interfacial charge separation mechanism can be described as follows. A ground‐state electron of the dye molecule (localized around the electron donor) is first promoted to the excited state (distributed electron donor), and then undergoes ultrafast injection into the conduction band of the STNT, leaving a hole around the oxidized dye. Significantly, the injected electron in the conduction band is transported along the STNT by means of Ti 3d orbitals, offering a unidirectional electron pathway toward the electrode for massive collection without the observation of trap states. Our study not only provides theoretical guidelines for the modification of TiO₂ nanotubes as a photoanode material, but also opens a new perspective for the development of a novel class of TiO₂ nanotubes with high power‐generation efficiency.     

Influence of surface properties on the interfacial adhesion in carbon fiber/epoxy composites

A polyacrylonitrile‐based carbon fiber was electrochemically oxidized in an aqueous ammonium bicarbonate solution with current density of up to 2.76 A/m² at room temperature. X‐ray photoelectron spectroscopy revealed that the oxygen content increased with increasing current density before approaching saturation. The increase can be divided into two regions, the rapid increase region (0–1.78 A/m²) and a plateau region (1.78–2.76 A/m²). The surface chemistry analysis showed that the interlaminar shear strength (ILSS) value of the carbon fiber/epoxy composite could be improved by 24.7%. The carbon structure was examined using Raman spectroscopy in terms of order/disorder in the graphite structure and the results indicated that the relative percentage of graphite carbon in the form of sp² hybridization increased above a current density of 1.39 A/m². The increasing non‐polar graphite carbon on the carbon fiber surface decreased the surface energy. As a result, both the surface free energy () and its polar component () decreased when current density increased above 1.78 A/m². The ILSS value had no direct relationship with the nature and surface density of the oxygen‐containing functional groups nor with the carbon structure. It is the surface free energy (), especially the polar component (), which played a critical role in affecting the interfacial adhesion of carbon fiber/epoxy composites. The ILSS value changed with increasing current density and could be divided into three distinct regions, as chemical interaction region (I), anchor force region (II) and matrix damage region (III). Copyright © 2013 John Wiley & Sons, Ltd.     

A Happy Get-Together – Probing Electrochemical Interfaces by Non-Linear Vibrational Spectroscopy

Electrochemical interfaces are key structures in energy storage and catalysis. Hence, a molecular understanding of the active sites at these interfaces, their solvation, the structure of adsorbates, and the formation of solid-electrolyte interfaces are crucial for an in-depth mechanistic understanding of their function. Vibrational sum-frequency generation (VSFG) spectroscopy has emerged as an operando spectroscopic technique to monitor complex electrochemical interfaces due to its intrinsic interface sensitivity and chemical specificity. Thus, this review discusses the happy get-together between VSFG spectroscopy and electrochemical interfaces. Methodological approaches for answering core issues associated with the behavior of adsorbates on electrodes, the structure of solvent adlayers, the transient formation of reaction intermediates, and the emergence of solid electrolyte interphase in battery research are assessed to provide a critical inventory of highly promising avenues to bring optical spectroscopy to use in modern material research in energy conversion and storage.     

锂离子电池多孔电极理论的回顾与新思考

本文总结了Newman多孔电极理论的基本内容,提出若干改进思路. 提出基于离子-空穴耦合传输机制描述浓电解质中的离子输运过程,在此基础上引入离子-电子耦合转移反应的思想处理电极材料中的离子传输问题,并通过计算嵌锂材料的离子扩散系数验证其合理性. 总结了描述多孔电极多尺度结构的相关理论和技术,表明均质化方法和基于结构重建的介观模拟方法均能给出比较合理的有效输运参数,从而提高多孔电极理论模拟结果的准确性.     

A control volume finite element method for three-dimensional three-phase flows

A novel control volume finite element method with adaptive anisotropic unstructured meshes is presented for three-dimensional three-phase flows with interfacial tension. The numerical framework consists of a mixed control volume and finite element formulation with a new P₁DG-P₂ elements (linear discontinuous velocity between elements and quadratic continuous pressure between elements). A “volume of fluid” type method is used for the interface capturing, which is based on compressive control volume advection and second-order finite element methods. A force-balanced continuum surface force model is employed for the interfacial tension on unstructured meshes. The interfacial tension coefficient decomposition method is also used to deal with interfacial tension pairings between different phases. Numerical examples of benchmark tests and the dynamics of three-dimensional three-phase rising bubble, and droplet impact are presented. The results are compared with the analytical solutions and previously published experimental data, demonstrating the capability of the present method.     

New Approaches to Synthesizing Electroactive Polymers

The chemical oxidative polymerization of aniline in a heterophase system is studied. In the presence of a solid substrate, the aniline polymerization involves two kinetically and chemically independent processes, namely, the polymerization in the bulk solution and at the substrate surface. The growth of the polyaniline coating at the substrate surface includes three successive processes: interfacial polymerization, adsorptive polymerization, and destruction of the polymer chain. The interfacial oxidative polymerization of diphenylamine and phenothiazine is examined. The yield and chemical structure of polymers is shown to depend on the polymerization conditions.     

CTAB-Ti-Co-β沸石的制备、表征及其对环己烯水合催化性能

用十六烷基三甲基溴化铵（CTAB）对Ti-Co-β沸石表面进行修饰,制得了两亲性CTAB-Ti-Co-β沸石。通过XRD、IR、DRS-UV-Vis、TG-DTA、SEM和XPS等技术对样品进行了表征。结果表明：所制得的CTAB-Ti-Co-β沸石具有BEA拓扑结构,很高的结晶度,Ti和Co两种杂原子已进入沸石骨架。CTAB-Ti-Co-β沸石同时具有亲水和亲油性,对环己烯水合反应具有较高的催化活性,环己烯的转化率和环己醇的选择性分别高达20.6%和99.7%。     

原油乳状液稳定性和破乳研究进展

本文从控制乳状液稳定性的一些因素－界面膜、界面张力、双电层、空间位阻、固体粒子、液晶、油相溶解度、连续相粘度等方面综述了有关乳状液稳定性的一些研究进展。对国内外有关原油乳状液的破乳研究也做了综述。同时，介绍了应用于乳状液稳定性研究的新的实验技术和仪器。     

可控碳改性Pd/TiO2用于直接合成双氧水:非均相界面对催化性能的影响（英文）

双氧水(H2O2)是一种重要的绿色氧化剂,广泛应用于纺织、医疗、废水处理、军事等重要领域.目前, H2O2的工业生产以蒽醌法为主,该法设备投资大、运行成本高,同时工艺涉及大量的有机溶液,活性中间体蒽醌也会发生缓慢降解,产生有毒副产物.与蒽醌法相比,通过负载型贵金属催化剂催化H2与O2反应直接合成H2O2,过程绿色环保且生产工艺简单,引起了各界广泛关注.然而,从热力学上分析, H2和O2更容易反应生成H2O, H2O2只是该反应的中间产物,会继续发生加氢和直接分解反应生成H2O,导致H2和O2的低效利用,开发高H2O2选择性且高反应效率的催化剂已成为氢氧直接合成H2O2研究的重点与难点.目前大部分研究策略旨在通过调控或影响反应中心结构、价态来抑制H2O2的副反应,进而提升H2O2的选择性和反应效率;尽管已取得了良好的进展,但仍需发展新的调控策略来满足工业应用的要求.本课题组前期研究表明,促使H2O2从催化剂上脱附可以有效地提升H2O2的选择性和产率.相比于针对反应中心的调控,不稳定的H2O2从催化剂上快速脱附同样起到抑制H2O2参与副反应的作用.为此,本文提出一种炭量可控的非均一界面改性方法,以常规的Pd/TiO2作为研究对象,借助各种结构表征,发现炭物种在TiO2表面呈非均一分散状态,而且改性对于催化剂的几何结构影响较小;另外,催化剂表面的疏水性会随着碳含量的增加而增加,导致其与H2O2间的吸附能相应变小.反应结果显示,表面非均一的炭化改性技术可以显著提升Pd/TiO2催化剂的H2O2选择性和产率.通过构效关系分析,可知这种改性技术可以保持Pd颗粒与TiO2间相互作用的同时,还可以促进H2O2的快速脱附,进而提升改性Pd/TiO2催化剂的H2O2直接合成效率.该改性方法简单、易控,可拓展应用到其他类型催化剂的H2O2直接合成性能调控与改进.