固体表面分子的自组装结构与调控机制

固体表面有机分子自组装是合成低维超分子材料和对固体表面进行功能化的重要途径.本文主要介绍了利用理论计算与扫描隧道显微镜实验相结合的手段研究固体表面分子自组装机制及结构与物性调控的相关工作.主要聚焦于几种由弱相互作用主导的分子自组装过程,从影响固体表面功能分子自组装过程的基本要素出发,如固体表面性质、功能分子的结构、功能分子间相互作用的类型和强度以及有卤族元素增原子参与的组装等,介绍了这些要素在构筑并调控分子自组装结构中的作用,理解固体表面功能分子自组装结构的调控机制,最后对如何实现分子自组装结构及物性的可控调制进行了展望,为设计新型低维超分子网格结构提供思路.     

二维光催化材料电子结构和性能调控策略研究进展

二维光催化材料具有丰富的表面活性位点、独特的几何结构、可调的电子结构和良好的光催化活性,在环境净化和能源转化等领域具有潜在的应用价值。鉴于此,二维光催化材料的合成方法和性能调控策略得到了快速发展。以往的策略主要集中在形貌和几何结构特征的调节上,实际上并不能完全满足高效稳定的光催化剂的设计需求。通过表面设计构建丰富的活性位点和调整电子结构,可以提高光催化性能及其稳定性。本文从光吸收、电荷分离和活性位点三个方面综述了二维光催化材料的表面设计和电子结构调控策略的研究进展,包括元素掺杂、异质结设计、缺陷构造、单原子修饰、等离子体金属负载等方法,总结了电子结构调控对二维光催化材料净化典型空气污染物反应机理的影响机制。最后,对二维光催化材料研究中存在的问题和挑战进行了分析和展望。     

低聚乙烯链在碳纳米管侧壁上的图案化吸附

碳纳米管（CNTs）自1991年被发现以来,已经在各个领域,尤其是在材料领域被深入研究．CNT作为添加剂与高分子形成的复合材料已被大量的制备并报道．实验室制备的CNTs中,含有5-7缺陷对的CNTs占很大一部分．Chico等引入5-7缺陷对将不同的CNTs连接起来形成类二极管的异质结．目前,对含有异质结的CNTs的研究大都停留在CNTs本身的结构与电学性质的研究上．而在材料领域对其与高分子形成复合材料的研究非常少．用理论的方法从原子角度来研究含有异质结的CNTs／高分子复合材料具有实际意义．     

石墨烯在复合热电材料中的应用

热电材料是一种可以实现热能与电能之间直接相互转换的功能材料,在温差发电和热电制冷方面具有广阔的应用空间。石墨烯是一种单原子层厚度的二维碳材料,具有特殊的晶体结构和优异的物理化学性质。大量研究表明石墨烯优异的电学性能、超大的比表面积以及多样的边界结构有利于材料电、热性能的协同调控,使其在热电领域有较大的应用潜力。本文结合热电材料的性能特点,从石墨烯的结构与性能入手,综述了石墨烯自身作为热电材料时结构与性能的优化关系,并总结归纳了石墨烯与Bi₂Te₃、CoSb₃等传统无机热电材料以及与导电高分子热电材料构成纳米复合块体和薄膜时,对材料结构与热电性能的影响,并结合现存的问题对石墨烯在热电领域中的应用进行了展望。     

表面合成异质原子掺杂的石墨烯纳米带

超高真空环境下,通过自下而上的方法原子级精确合成石墨烯纳米带是打开石墨烯带隙的重要方法。合理地设计带有异质原子(如硼、氮、氧等)的前驱体分子可以合成异质原子掺杂的石墨烯纳米带。掺杂的异质原子可以显著地调制石墨烯纳米带的电学、磁学等物理化学性质,并且调控的效果与异质原子的种类、位置、密度等密切相关。本文综述了近些年来利用分子束外延方法,在表面上合成异质原子掺杂的石墨烯纳米带的研究进展,同时对掺杂石墨烯纳米带的应用前景进行了展望。     

有机光催化剂用于太阳能水分解：分子水平和聚集体水平改性

利用太阳能光解水产氢是实现氢能开发最绿色且可持续的理想技术。为了提高太阳能的转换效率，设计和发展高效、稳定、宽/全光谱响应光催化产氢体系成为关键研究课题。相比于无机半导体，有机半导体具有丰富的π电子和结构可修饰性，使其光学吸收和能带结构易剪裁，光催化路径多样。但低的介电常数造成其载流子迁移率低及迁移距离短。通过有目的地改变有机分子结构，可以轻松地设计和调控有机半导体的能带位置、增加摩尔吸光系数，改善材料对于整个太阳光谱中可见光或红外光的利用；通过功能分子微纳组装或集成，可进一步获得不同组分、维度(0维、1维、2维、3维)、尺寸、晶体学取向的有机光催化剂。有机微纳/复合结构的优异的比表面积、分子排布结构或能级排列结构可进一步提高太阳能的利用率和光生电荷的传输/分离效率，从而提高整体光电转换效率和产氢效率。然而，由于复杂的反应过程和设计困难，整个有机半导体的光催化物理化学过程仍不清楚。在这里，光催化的基本原理从光捕获、光激发电荷分离、表面反应的角度进行了讨论。随后详细总结了有机半导体纳米结构的制备方法包括超分子自组装、再沉淀法、气相沉积法以及其他方法。描述了典型的有机半导体材料，包括苝二酰...     

二维材料“遇见”生物大分子:机遇与挑战

二维材料的超薄原子层结构使其具有独特的力学性能、导热导电性以及巨大的比表面积,在能源存储、催化、传感和生物医学等领域引起了国内外学者的广泛关注。将二维材料与具有生物活性的生物大分子相结合可以为开发具有优异电学、力学和生物学功能的特种功能材料提供新的方法和途径。近年来,科研工作者针对这一方向展开了广泛的研究,取得了一系列重要的成果,使二维材料与生物大分子的结合与应用成为了新的研究热点。本文综述了近年来二维材料和生物大分子之间的相互作用及应用的研究进展,重点介绍了二维材料与生物大分子在分子水平上的相互作用机理,还总结了基于二维材料与生物大分子之间的相互作用在工程、疾病治疗和抗菌中的应用,并对其未来的研究趋势提出了展望。     

二维有机-无机杂化钙钛矿铁电材料的研究进展

铁电性通常是指电介质材料的自发极化取向随着外加电场发生变化的性能. 以自发极化为核心, 铁电材料表现出优异的介电响应、热释电性、压电性、电光效应和非线性光学效应等, 是一类具有广阔应用前景的功能材料. 近年来, 二维有机-无机杂化钙钛矿化合物在铁电研究领域崭露头角, 逐渐发展为铁电材料的重要组成部分. 此类材料具有独特的结构兼容性与可调控性, 能够实现多种功能的共存或耦合, 是发展新型多功能材料的理想体系. 本综述基于居里原理的对称性方法, 以铁电材料的结构相变为基础, 阐述了铁电体的晶体学对称性破缺现象. 具体结合二维有机-无机杂化钙钛矿铁电体的典型实例, 揭示材料铁电性能的结构来源及光电性能调控的潜在途径, 最后对该铁电材料体系的发展趋势和应用前景提出了展望.     

异质中空结构微纳材料的构建

异质中空结构是指壳层由不同成分组成的空心微纳结构. 通过对异质中空结构的表面性质和传质过程进行调控, 可以调控经过中空结构的物质及能量. 目前, 异质中空结构在太阳能转化、 气体传感、 电化学储能和药物运输等领域展示出了优异的性能, 对异质中空结构的设计与构建已成为新型多功能先进材料研究的前沿领域. 本文总结了异质中空结构的种类、 特征和性能优势, 重点描述了各类异质中空结构的制备方法, 并探讨了异质中空结构微纳材料面临的挑战及发展趋势.     

外界刺激调控的表面引发原子转移自由基聚合

聚合物刷被广泛用于调控表/界面的物理化学性质,表面引发聚合(SIP)是制备聚合物刷的有效手段,该方法已广泛地用于合成具有各种结构以及功能的聚合物以及无机/有机杂化材料。表面引发原子转移自由基聚合(SI-ATRP)方法是表面接枝聚合刷最为常用的方法,但是目前的方法存在很多问题,例如:单体利用率低、反应条件苛刻、可控性较差等。近年来,一些研究组发展了一系列通过外界刺激来调控聚合过程的新方法,旨在克服以上缺陷。本文首先详细介绍了SI-ATRP的机理,在此基础上讨论通过一系列外界刺激(电化学、光、化学试剂等)灵活调控表面引发-原子转移自由基聚合来制备聚合物刷的最新研究进展,同时展望利用新的聚合方法调控聚合物刷结构、界面性质以及应用。     

Hybrid Organic–Inorganic Thermoelectric Materials and Devices

Hybrid organic–inorganic materials have been considered as a new candidate in the field of thermoelectric materials since the last decade owing to their great potential to enhance the thermoelectric performance by utilizing the low thermal conductivity of organic materials and the high Seebeck coefficient, and high electrical conductivity of inorganic materials. Herein, we provide an overview of interfacial engineering in the synthesis of various organic–inorganic thermoelectric hybrid materials, along with the dimensional design for tuning their thermoelectric properties. Interfacial effects are examined in terms of nanostructures, physical properties, and chemical doping between the inorganic and organic components. Several key factors which dictate the thermoelectric efficiency and performance of various electronic devices are also discussed, such as the thermal conductivity, electric transportation, electronic band structures, and band convergence of the hybrid materials.     

Smooth and flexible filler-nanocellulose composite structure for printed electronics applications

A new type of micro/nanocomposite was made by using only micro fibrillated cellulose and inorganic fillers. This composite structure can contain up to 90% fillers being still mechanically stable and flexible. Calendering can be used to produce dense structures with extremely smooth surface. To study the effect of filler shape and type, both kaolin and precipitated calcium carbonate (PCC) based sheets were examined. Microscopy (cross-sectional and surface SEM images) and mechanical and morphological properties, including strength properties, surface roughness and dimensional stability as a function of moisture were analysed. After calendering the surface of the PCC containing sheets was smoother than that of photopaper and in the same level as reference plastic film Mylar A. The dimensional stability of the sheets was clearly better than that of paper sheets. The combination of a good dimensional stability with low surface roughness makes these structures potential for printed electronics applications, in which they could replace oil-based plastic substrates. Suitability for printed electronic applications was tested by inkjet printing conductors with silver nanoparticle ink. The sheet resistances of conductors printed on kaolin based sheets were close to those printed on plastic Mylar A film.     

From Two‐ to Three‐Dimensional Structures of a Supertetrahedral Boran Using Density Functional Calculations

With help of the DFT calculations and imposing of periodic boundary conditions the geometrical and electronic structures were investigated of two‐ and three‐dimensional boron systems designed on the basis of graphane and diamond lattices in which carbons were replaced with boron tetrahedrons. The consequent studies of two‐ and three‐layer systems resulted in the construction of a three‐dimensional supertetrahedral borane crystal structure. The two‐dimensional supertetrahedral borane structures with less than seven layers are dynamically unstable. At the same time the three‐dimensional superborane systems were found to be dynamically stable. Lack of the forbidden electronic zone for the studied boron systems testifies that these structures can behave as good conductors. The low density of the supertetrahedral borane crystal structures (0.9 g cm⁻³) is close to that of water, which offers the perspective for their application as aerospace and cosmic materials.     

稀土无机发光材料:电子结构、光学性能和生物应用

目前,稀土无机发光材料在激光、光通讯、平板显示、荧光生物标记和纳米光电子器件等领域具有广泛的应用前景.稀土离子(从Ce到Yb)是一类性能优异的结构和光谱探针,其在不同介质材料中的光学性能主要取决于其局域态的电子结构和激发态动力学.对稀土发光材料开展深入的光学和光电子学基础研究有助于发现新颖的光学性能或开辟新的应用领域.依托研制的低温高分辨激光光谱和上转换量子产率等仪器,本课题组致力于稀土无机发光材料电子结构与性能研究,近年来在发光材料的控制合成、电子结构、光学性能及生物应用等方面取得了系列重要结果.这些研究有望加快实现稀土无机发光材料在生物应用的突破,实现稀土资源的高值利用.     

Quantitative investigations of aggregate systems

Nanomaterials with disordered, ramified structure are increasingly being used for applications where low cost and enhanced performance are desired. A particular example is the use in printed electronics of inorganic conducting and semiconducting nanoparticles. The electrical, as well as other physical properties depend on the arrangement and connectivity of the particles in such aggregate systems. Quantification of aggregate structure and development of structure∕property relationships is difficult and progress in the application of these materials in electronics has mainly been empirical. In this paper, a scaling model is used to parameterize the structure of printed electronic layers. This model has chiefly been applied to polymers but surprisingly it shows applicability to these nanolayers. Disordered structures of silicon nanoparticles forming aggregates are investigated using small angle x-ray scattering coupled with the scaling model. It is expected that predictions using these structural parameters can be made for electrical properties. The approach may have wide use in understanding and designing nano-aggregates for electronic devices.     

Effect of Two‐Dimensional Crystal Orbitals on Fermi Surfaces and Electron Transport in Three‐Dimensional Perovskite Oxides

Perovskite oxides are candidate materials in catalysis, fuel cells, thermoelectrics, and electronics, where electronic transport is vital to their use. While the fundamental transport properties of these materials have been heavily studied, there are still key features that are not well understood, including the temperature‐squared behavior of their resistivities. Standard transport models fail to account for this atypical property because Fermi surfaces of many perovskite oxides are low‐dimensional and distinct from traditional semiconductors. In this work, the low‐dimensional Fermi surfaces of perovskite oxides are chemically interpreted in terms of two‐dimensional crystal orbitals that form the conduction bands. Using SrTiO₃ as a case study, the d/p‐hybridization that creates these low‐dimensional electronic structures is reviewed and connected to its fundamentally different electronic properties. A low‐dimensional band model explains several experimental transport properties, including the temperature and carrier‐density dependence of the effective mass, the carrier‐density dependence of scattering, and the temperature dependence of resistivity. This work highlights how chemical bonding influences semiconductor transport.     

纳米技术在高效温差电材料中的应用

介绍了传统的热电材料，论述了热电材料的工作原理以及热电材料的应用。随着电子器件向小型化、微型化发展，迫切要求具有低功率和高输出电压的微型供电装置，低维热电材料因为小尺寸效应，表现出优异的热电性能，成为研制微温差电池的首选材料，受到了科研工作者的广泛关注。     

Low-cost Cu-based inorganic hole transporting materials in perovskite solar cells: Recent progress and state-of-art developments

Perovskite solar cells (PSCs) are rapidly approaching as promising processes toward efficient energy harvesting technologies. High cost and low environmentally stable organic hole transporting materials (HTMs) are the main hurdles in their commercial realization. Perovskite community is actively looking for inorganic HTMs which will potentially yield into a pragmatic solution. Cu-based materials, e.g. Cu-based oxides, halides, and chalcogenides exhibit features like low production cost, suitable band alignment, and high hole mobility Due to these properties, Cu-based materials are being explored as potential HTMs in PSCs. Significant efforts are contributed toward using low-cost Cu-based materials because of high chemical stability, high carrier mobility, low-cost and the possibility of developing a very simple technique. The photo-physical properties, e.g. optical electronic structure, valence band engineering, and carrier mobility are briefly discussed. Detailed insights toward understanding the development of Cu-based HTMs along with their possible pragmatic commercialization aspects are presented. This article highlights the utilization of Cu-based chalcogenide HTM and role of ternary Cu-based chalcopyrite, Pnma ternary chalcogenides, sulvanite and oxychalcogenides in the field of PSC with a brief idea about tailoring their optoelectronic properties. This article will significantly help the community toward the engineering of novel Cu-based HTMs for possible commercialization of PSC technology.     

荧光纳米晶制备及其与聚合物的复合组装

纳米尺寸无机晶体(纳米晶)具有特殊的光、电和磁等性能, 但这类材料通常以胶体溶液或固体粉末的状态存在, 稳定性和分散性较差. 实现这类材料的应用, 需要将其与一些惰性介质复合, 从而提高稳定性和加工性. 聚合物材料作为一种有机惰性介质, 具有良好的材料兼容性和可加工性, 是稳定纳米晶材料的首选介质. 此外, 很多聚合物材料本身也具备特殊的性能, 可以对纳米晶性能进行有益的补充和调节. 因此, 功能纳米晶材料与聚合物复合, 将成为开启材料性能宝库的钥匙. 我们研究组结合自己的相关研究, 系统总结了荧光纳米晶材料与聚合物的复合组装方法, 着重阐述不同方法的优势及意义, 希望对从事这一前沿领域研究的人们有所启发.     

Sol–gel processing at increased temperatures: the formation of polyester nanocomposites

Polyester nanocomposites were prepared using sol–gel precursors, prehydrolyzed sols, or nanoparticles in polyester formulations. The different inorganic components were introduced in the early stages of the esterification reaction and a typical polymerization temperature program was applied leading to temperatures up to 240 °C at low pressures. The structural and physical properties of the final materials depend on the applied method for the introduction of the sol–gel materials. Silicon atoms were incorporated into the polyester chain if silicon tetraalkoxide was used as precursor. The silicon atoms represent branching points in the polymer structure. Prehydrolyzed sols that were prepared under acidic conditions were another source of silicon and formed larger inorganic aggregates in the polymer matrix. Nanoparticles prepared via the Stöber process were the third inorganic species in polyester formation. All three processing pathways produced different kinds of materials depending on the type of silica incorporated in the polyester networks but also with regard to the nanoscale structure of the materials. Both, composition and structure have a major influence on the final polyester nanocomposite properties. Model reactions between silicon tetraalkoxides and diols or diacids using the temperature program for the polyester formation showed that exchange reactions of the alkoxides and the alcohols or acids can occur and the obtained products can carry out side reactions in the polyester formation. The final materials show a homogeneous distribution of the silicon containing moieties in the polyester matrix. The viscosities and the branching degrees of the polymers changed dramatically compared to the pristine polymers by incorporation of the sol–gel precursors.