类水滑石材料主客体插层结构的构筑及特性的理论研究

因主体层板和层间客体具有丰富的可调性, 类水滑石材料(LDHs)在催化、 吸附、 生物医药及光、 电、 磁等方面展现出了广阔的应用前景. 近年来理论研究已成为揭示LDHs微观结构和性质的重要手段, 本文系统综述了LDHs材料主体结构、 客体结构以及主客体相互作用3个方面的理论研究工作进展, 及其在作为光驱动催化剂方面应用的理论研究. 从主体元素构成、 元素比例、 电荷分布、 拓扑结构转变、 能带结构、 态密度、 层间阴离子组成、 离子交换性能、 主客体作用力、 能量性质及光催化性能等方面, 在原子、 电子尺度上揭示了LDHs材料结构-性能之间的构效关系, 为以其为材料平台构筑一系列基于超分子插层结构主客体间相互作用的新型功能材料、 扩展材料的功能性提供了丰富的理论信息和有益指导.     

硼酸根插层水滑石层间组成及取向结构的控制

以Mg0 .67Al0 .3 3 (OH) 2 (CO3 ) 0 .165·0 .62H2 OLDHs为前体 ,以水为分散介质 ,由离子交换法组装了硼酸根插层LDHs ,并用XRD ,FT IR ,TG DTA ,ICP ,11BMASNMR等手段对样品进行了分析和表征 .结果表明 ,通过控制离子交换时的pH ,可使硼酸根取代Mg Al CO3 LDHs前体层间的CO2 -3 ,且可控制离子交换程度及客体的取向 ,从而控制插层结构 .对硼酸根插层LDHs的结构进行研究发现 ,控制pH =4.5 ,层间阴离子主要是一硼酸根和离子平面与LDHs层板平行的三硼酸根 ,出于结构稳定的需要 ,CO2 -3 不能完全被置换 ;控制pH =3 .5 ,层间阴离子是一硼酸根和离子平面与LDHs层板垂直的三硼酸根     

基于层状前驱体制备活性位高分散催化材料

综述了近年来以层状双金属氢氧化物(LDHs)为前躯体制备高分散催化剂的研究进展,基于LDHs层板金属阳离子以原子水平高度分散及层间阴离子以一定方式有序排布的结构特点,以LDHs材料作为单一前驱体,经层板剥离、晶格限域、插层组装及阵列化等途径制备催化活性位高度分散的多相催化材料具有显著的优势.     

ZnAl-LDHs热致拓扑转变的理论及实验研究

层状复合金属氢氧化物(LDHs)材料具有纳米尺度的二维层状结构.其晶体结构在煅烧的条件下可发生热致拓扑转变,利用此性质可以LDHs为前驱体制备高分散催化剂.本文采用基于密度泛函的第一性原理分子动力学模拟方法并结合热重分析(TG-DTA)研究了ZnAl-LDHs在升温过程的拓扑转变机理.通过TG-DTA数据明确了发生分解反应的两个关键性温度273和800℃,并在这两个温度进行模拟.在273℃,模拟了LDHs层间阴离子分解及层板脱羟基过程中金属离子的迁移机理,结果表明,层间阴离子CO_3~(2-)通过与主体层板作用形成单齿配体进行分解,产物水分子先于CO_2释放到层间区域内.此时LDHs层板结构已经坍塌,金属离子在层板方向及垂直层板方向都发生了显著的迁移,拓扑不变量(层板方向迁移度)变化明显.因此,ZnAl-LDHs不存在记忆效应.在800℃,模拟发现LDHs结构已经完全坍塌,生成了多孔性的混合金属氧化物,与文献实验结果相符合.本文从原子水平上理解了LDHs整个结构从分解的起始阶段到完全脱水的演变过程,并解释了ZnAl-LDHs没有记忆效应的原因,为认识LDHs热致拓扑转变机理,设计高分散催化剂提供了有益的理论信息和指导.     

LDHs薄膜基纳米荧光传感器的制备及其研究进展

层状复合氢氧化物(LDHs)是一种层板金属元素和层间离子可调的无机层状材料,利用其独特的插层组装特性,基于静电、氢键、范德华力等相互作用力,功能性荧光客体分子可与LDHs纳米片复合构筑多功能荧光薄膜材料.LDHs薄膜基荧光材料用于荧光传感器,在有机挥发性气体(VOCs)、温度、压力、重要生物分子等的检测中显示了良好性能.本文总结了LDHs复合薄膜的制备方法以及近年来其在纳米荧光传感领域的进展,并对其未来发展做出了展望.     

二元类水滑石层板组成、结构与性能的理论研究

采用晶体学理论建立二元类水滑石(LDHs)微观结构模型与静电势能模型，将层板金属离子间距、层板电荷密度、层间阴离子间距等微观结构参数定量化，并将层间阴离子的静电势能表示成层板金属离子半径和物质的量之比、插层阴离子尺寸和电荷的函数。研究结果表明：LDHs层板金属离子间距应用离子紧密堆积来估算和孔径按阴离子平面六方点阵分布来计算是可行的；调变层板金属离子种类与物质的量之比影响层间阴离子的稳定性，势能计算值与文献报道的LDHs热稳定性次序一致。所以该模型可用于预测LDHs的微观结构参数以及热稳定性，为新型层状双羟基材料的定向合成提供思路。     

层状双金属氢氧化物微观结构与性质的理论研究进展

总结了近年来理论计算方法在研究层状双金属氢氧化物(LDHs)结构与功能方面的应用现状. 结合LDHs材料的结构特点, 归纳了量子力学、分子力学、几何建模及物理静电模型相结合对LDHs材料进行结构模拟的思路, 比较了各种方法在LDHs结构模拟上的优势及存在的不足. 量子力学方法能够精确获得水滑石材料的层板构成及作用机制、简单阴离子插层水滑石主客体间的超分子作用实质以及电子性质、反应机理等方面的信息. 与量子力学相比较, 分子力学方法可以快速得到插层水滑石材料的层间阴离子排布及取向、水合膨胀特性及宏观力学性质等. 几何模型和物理静电模型能构建直观、形象的数学模型, 大大简化了计算量,因此能计算接近实际LDHs尺寸的体系, 为推测LDHs结构信息提供了可能性. 随着理论方法和计算机硬件水平的发展, 使得计算机模拟技术逐渐成为获得LDHs材料微观结构参数、电子性质和动力学性质的一种有效手段.     

层状双金属氢氧化物基光催化剂的研究进展

层状双金属氢氧化物(LDHs)具有组分可调、层板金属离子高度分散、层间阴离子可交换、拓扑转变等特性,使其可作为理想的光催化剂、催化剂载体或前驱体。作为一种新型多功能材料,LDHs基光催化剂在环境净化、能源储备、工业催化和生物医学等多个领域广泛应用。但是,选择合适的路径进一步优化LDHs基光催化剂的性能,以实现太阳能的高效利用及催化反应过程的高转化率和高选择性仍然具有很大的挑战性。本文依据LDHs的结构特点及活性组分引入方式,将LDHs基光催化剂的制备方法总结归纳为主体层板构筑法、客体插层敏化法、剥离层层组装法、复合材料杂化法四类,详细介绍了不同制备方法对光催化性能的影响,综述其最新研究进展;并结合LDHs基光催化材料的应用,介绍其光催化行为和机理;最后,对LDHs基光催化剂的应用前景进行分析和展望。     

层状双金属氢氧化物基光催化剂研究进展

层状双金属氢氧化物(LDHs)具有组分可调、层板金属离子高度分散、层间阴离子可交换、拓扑转变等特性,使其可作为理想的光催化剂、催化剂载体或前驱体。作为一种新型多功能材料,LDHs基光催化剂在环境净化、能源储备、工业催化和生物医学等多个领域广泛应用。但是,选择合适的路径进一步优化LDHs基光催化剂的性能,以实现太阳能的高效利用及催化反应过程的高转化率和高选择性仍然具有很大的挑战性。本文依据LDHs的结构特点及活性组分引入方式,将LDHs基光催化剂的制备方法总结归纳为主体层板构筑法、客体插层敏化法、剥离层层组装法、复合材料杂化法四类,详细介绍了不同制备方法对光催化性能的影响,综述其最新研究进展;并结合LDHs基光催化材料的应用,介绍其光催化行为和机理;最后,对LDHs基光催化剂的应用前景进行分析和展望。     

类水滑石主体层板与客体CO2-3、H2O间的超分子作用

通过构建类水滑石双层计算模型,采用混合密度泛函B3LYP/6-31G(d)//B3LYP/3-21G方法计算类水滑石(LDHs-CO3-yH2O)的结构与能量,探讨LDHs限域空间中客体阴离子及水分子的分布形态以及主客体超分子作用.计算结果表明,客体阴离子与水分子以平行层板的方式存在于水滑石层间.主客体发生作用时,CO2-3的HOMO轨道向层板的LUMO轨道转移电子.所形成的LDHs-CO3主客体作用要强于LDHs-F以及LDHs-Cl.与其离子交换性能相一致.水滑石去水结构(LDHs-CO3)水合过程,氢键作用较静电作用更占优势,并且layer-water型氢键要强于anion-water型氢键.此外,水合能计算表明LDHs水合具有一定的饱和量.     

有机复合光电导材料及器件研究进展

有机光电导复合材料已经成为当前国际上有机光电材料科学研究的前沿与热点之一。复合化是大幅度提高有机半导体材料光电导性能的有效手段,本文主要从有机光电导材料的复合化角度,综述了新型高效的多种有机复合光电导材料体系的制备及其光电导性能,初步解释了其相应的复合原理和光电导机理,并介绍了其在单层型光电导器件中的研究进展。最后提出了制备高性能有机光电导复合材料及单层型光电导器件的几点建议。     

Nanostructured Carbonaceous Materials from Molecular Precursors

Nanostructured carbonaceous materials, that is, carbon materials with a feature size on the nanometer scale and, in some cases, functionalized surfaces, already play an important role in a wide range of emerging fields, such as the search for novel energy sources, efficient energy storage, sustainable chemical technology, as well as organic electronic materials. Furthermore, such materials might offer solutions to the challenges associated with the on‐going depletion of nonrenewable energy resources or climate change, and they may promote further breakthroughs in the field of microelectronics. However, novel methods for their preparation will be required that afford functional carbon materials with controlled surface chemistry, mesoscopic morphology, and microstructure. A highly promising approach for the synthesis of such materials is based on the use of well‐defined molecular precursors.     

Synthesis of 3D printing materials and their electrochemical applications

Three-dimensional (3D) printing, also known as additive manufacturing, has the advantages of low cost, easy structure operation, rapid prototyping, and easy customization. In the past few years, materials with different structures, compositions, and properties have been widely studied as prospects in the field of 3D printing. This paper reviews the synthesis methods and morphologies of one-, two- and three-dimensional micro/nano materials and their composites, as well as their applications in electrochemistry, such as supercapacitors, batteries and electrocatalysis. The latest progress and breakthroughs in the synthesis and application of different structural materials in 3D-printing materials, as well as the challenges and prospects of electrochemical applications, are discussed.     

Sorption on eggshell waste—A review on ultrastructure,biomineralization and other applications

The structure, adsorption behavior and applications of eggshell waste materials have been reviewed. The ultrastructure of eggshell particles has been discussed to understand the pore structure as well as the surface geometry of the materials leading to its multifarious applicability. Besides, the ultrastructure studies give full information regarding the chemical constituents of egghell particles as well as eggshell membranes. The process of biomineralization in living organisms, their consequent effect of controlling the formation of inorganic–organic composites propelling their application in biomimetic designing of advanced composites with optimized novel properties leading to advances in materials design have been discussed. Utilization of eggshell waste materials for the removal of organic dyes and heavy inorganic ions has been reviewed with suitable models for understanding their adsorption quality and capacity. The applications of these materials in various fields of research have been extensively discussed.     

Luminescent Surface-Tethered Polymer Brush Materials

Surface-tethered polymers are unique molecular architectures that have been recently used in advanced sensors, electronics and biomedical applications. However, techniques for characterizing these materials in their surface-tethered form remain limited. The incorporation of luminescent functionality into these materials has enabled new characterization methods, while also unlocking new applications in optoelectronics, stenography and sensing. Micron-scale photolithography techniques have recently enabled the preparation of high-resolution patterns, as well as architectures with unique photophysical properties. Herein, we provide an overview of the techniques used to prepare luminescent polymer brush materials and their applications in stimuli-responsive sensors, cell adhesion materials, and optoelectronics. We also provide our perspective on the promising future uses of surface-tethered polymers, as well as the short-term challenges and opportunities in the field.     

Chiral biointerface materials

Chiral phenomena are ubiquitous in nature from macroscopic to microscopic, including the high chirality preference of small biomolecules, special steric conformations of biomacromolecules induced by it, as well as chirality-triggered biological and physiological processes. The introduction of chirality into the study of interface interactions between materials and biological systems leads to the generation of chiral biointerface materials, which provides a new platform for understanding the chiral phenomena in biological system, as well as the development of novel biomaterials and devices. This critical review gives a brief introduction to the recent advances in this field. We start from the fabrication of chiral biointerface materials, and further investigate the stereo-selective interaction between biological systems and chiral interface materials to find out key factors governing the performance of such materials in given conditions, then introduce some special functionalities and potential applications of chiral biointerface materials, and finally present our own thinking about the future development of this area (108 references).     

Preparation and application of cellular and nanoporous carbides

A tutorial review on cellular as well as nanoporous carbides covering their structure, synthesis and potential applications. Especially new carbide materials with a hierarchical pore structure are in focus. As a central theme silicon carbide based materials are picked out, but also titanium, tungsten and boron carbides, as well as carbide-derived carbons, are part of this review.     

Polymer microfabrication technologies for microfluidic systems

Polymers have assumed the leading role as substrate materials for microfluidic devices in recent years. They offer a broad range of material parameters as well as material and surface chemical properties which enable microscopic design features that cannot be realised by any other class of materials. A similar range of fabrication technologies exist to generate microfluidic devices from these materials. This review will introduce the currently relevant microfabrication technologies such as replication methods like hot embossing, injection molding, microthermoforming and casting as well as photodefining methods like lithography and laser ablation for microfluidic systems and discuss academic and industrial considerations for their use. A section on back-end processing completes the overview.     

From coordination complexes to coordination polymers through self-assembly

Metal ion coordination in metallo-supramolecular assemblies offers the opportunity to fabricate and study devices and materials that are equally important for fundamental research and new technologies. Metal ions embedded in a specific ligand field offer diverse thermodynamic, kinetic, chemical, physical and structural properties that make these systems promising candidates for active components in functional materials. In particular, dynamic coordination polymers offer exciting opportunities to provide materials with responsive properties. In addition, this approach allows to incorporate the well known properties of metal complexes in polymeric architectures. This review highlights the improvements and the possible applications based on metallo-supramolecular systems with an emphasis on materials science. Examples for new materials such as molecular magnets, coordination polymers as carrier package as well as molecular electronics are featured in this article.