有机或金属-有机二维纳米材料的制备与应用（英文）

对石墨烯等二维材料的研究进一步引发了人们对相似结构的其他有机、金属-有机二维层状纳米材料的浓厚兴趣.这些二维材料由于其优异的化学可剪裁性而受到关注,预期未来在电子器件、催化和小分子分离等方面具有广泛的用途.这篇综述系统地介绍了目前制备有机基二维材料的自上而下和自下而上的两大类方法,总结了有机基二维材料在生物识别、小分子分离和纯化以及电学方面的应用,最后讨论了有机基二维材料目前在制备和性质改进方面面临的问题和未来可能发展的研究方向.     

超薄二维MOF纳米材料的制备和应用

超薄二维金属有机框架材料(MOF)纳米材料是MOF材料中的一类,不同于传统体相MOF材料,超薄片状结构赋予了它高比表面积、丰富的配位不饱和的金属位点等独特性质,能够有效改善MOF在催化、分离和传感等领域中的性能。本文综述了近年来国内外在超薄二维MOF纳米材料的构建及制备方法的研究进展,其中包括自上而下法、自下而上法以及独立于二者的二维氧化物模板牺牲法等。同时,本文详细讨论了超薄二维MOF纳米材料在气体吸附与气体分离、催化、能量储存和传感平台等领域的应用前景,并对未来超薄二维MOF纳米材料的研究面临的挑战和机遇做了进一步的分析。     

有机光伏材料与器件研究的新进展

近几年有机光伏电池应用研究发展迅猛。本文综述了有机光伏薄膜电池在材料(包括有机小分子材料与聚合物材料)、器件构造方面的最新进展，分析了有机聚合物光伏电池目前效率低的主要原因，并探讨了该领域进一步研究的方向和前景。     

二维分子晶体的研究进展

二维分子晶体具有超薄、长程有序、无晶界和缺陷密度低等优点,是构建多种高性能光电器件的理想材料.实现二维分子晶体的低成本、大面积制备是二维分子晶体走向应用的关键.目前,人们开发了多种方法,在气相和液相中实现了二维分子晶体的可控制备,并揭示了这类二维有机体系独特的光电性能.本文综述了二维分子晶体的制备方法及其在有机场效应晶体管和光探测器等器件中的应用.     

一维有机微纳米光功能材料研究进展

近年来,一维有机小分子微纳材料因为其新颖的光学性能和在未来小型化器件中的广泛应用,受到了人们越来越多的关注.相比于传统无机半导体材料,有机小分子材料具有结构多样性、功能可设计性、易大量制备、易机械加工等显著优势.本文将从一维有机小分子纳米材料的制备方法、形貌调控、光学性能(如光波导、受激发射、电致发光等),及其在光学器件上的应用出发,对近十年来的相关研究进展及成果进行总结和介绍.     

共价有机骨架材料设计及其在分离领域的应用

共价有机骨架(COFs)材料是由有机小分子单体通过共价键连接形成的结晶多孔聚合物。与传统的线性聚合物不同的是,COFs可以在二维和三维空间上对其骨架结构进行控制,从而合成具有高度有序的刚性多孔结构,并且能够调节骨架的化学和物理性质。这种由COF形成的纳米级孔道和空间为分子存储、释放和分离提供了理想的环境。因此它在能量储存、分离、催化等领域有着广泛的应用前景。本文综述了近年来COFs材料的研究进展,主要包括材料的合成策略及其在分离领域的应用,并对COFs材料未来的发展方向进行了展望。     

金属有机骨架薄膜用于小分子和离子的高效分离

综述了近几年金属有机骨架（MOF）薄膜在小分子和离子高效分离应用中的研究进展.MOF膜材料因具有结晶度良好、结构可设计、孔径可调和可功能化等特点,在分离领域展现出极大的潜在应用价值而受到广泛关注.鉴于近年来MOF膜材料在分离领域取得的巨大进展,对这一领域的前沿进展进行及时系统的总结,并对未来的发展趋势进行展望,具有重要的学术价值,也为科研工作者对MOF膜材料的研究提供了参考.本文首先总结了MOF膜的4种制备方法,包括LBL自组装法（液相外延和Langmuir-Blodgett沉积）、真空制备法（化学气相沉积和原子层沉积）、电化学沉积法和粉末沉积法;而后,详述了MOF膜在气体分离、液体分离及离子/质子传导等方面的应用;最后,总结了MOF膜材料领域当前存在的挑战及潜在解决途径,并对该领域的未来发展方向进行了展望.     

高结晶性小分子给体材料应用于全小分子有机太阳能电池中的研究进展

随着新型小分子给体材料和非富勒烯小分子受体材料的开发和应用, 非富勒烯全小分子有机太阳能电池(NF-ASM OSCs)的光电转换效率已经突破15%, 并逐渐接近聚合物太阳能电池的效率. 相比于聚合物电子给体材料, 小分子电子给体材料拥有其独特的优势, 例如合成批次性差异小、分子量明确和易于提纯等; 但是, 对小分子给体材料的结晶性难于精确调控, 使获得合适的纳米级结构的混合膜仍然是一个挑战. 本综述以给体小分子中心共轭单元的扩展为主线, 从分子设计的角度汇总了近年来对苯并二噻吩、萘并二噻吩和二噻并苯并二噻吩类小分子给体材料的结晶性研究, 并为进一步改善电池活性层形貌和获得更高的光伏性能提供了未来发展的建议.     

基于共价有机框架的电化学生物传感器在生物样品检测中的应用

共价有机框架材料(Covalent Organic Frameworks, COFs)是一种具有纳米级结构有序性的二维或三维有机结晶材料, 具有高度周期性和可修饰性等结构优点. 基于COFs制备的电化学生物传感器具有灵敏度高、特异性强、重复性好等特点, 在检测生物样品方面具有广阔前景. 本综述简要概述了COFs的合成方法与策略、电化学生物传感器的介绍与分类以及COFs在电化学生物传感检测生物样品领域的应用. 最后本综述对COFs材料在生物传感领域的技术瓶颈与未来的发展方向进行了总结与讨论.     

有机太阳能电池材料研究新进展

介绍了有机太阳能电池研究的背景、基本原理、分类,并对有机太阳能电池材料进行了全面综述,包括小分子太阳能电池材料、大分子太阳能电池材料、D-A体系材料和有机无机杂化体系材料.     

卟啉框架材料在光催化领域的应用

卟啉分子对可见光具有较强吸收能力,被广泛应用于光催化和光敏化材料的设计开发。 基于卟啉单元设计构筑框架结构材料,可以借助框架结构的大比表面积和可调控孔结构,实现对卟啉单元光物理化学性质的修饰和调控,达到提高材料光催化量子产率和光催化选择性的目的。 本文综述了卟啉基金属有机框架材料(MOFs)、卟啉基共价有机框架材料(COFs)、以及卟啉基多孔共价有机聚合物(COPs)在光催化领域的研究进展,通过归纳需要解决的关键问题,对卟啉框架材料的未来发展进行了展望。     

网状框架中的机械互锁结构

网状框架具有结晶而延伸的多孔结构，不仅能将多种构筑模块按预期的方式有序组织形成介观材料，也因其可调控的精确结构成为研究基础科学问题的良好平台.机械互锁结构是利用分子间的机械作用将多种分子结合起来以协同实现复杂功能的分子集合体.将网状框架与机械互锁结构结合不仅能实现机械互锁结构的高维度有序组装以协同实现更复杂的分子机器的功能，也有望对更有应用前景的固相中机械互锁结构间的相互作用和微观机理有更深入的认识.本综述介绍了网状框架与机械互锁结构结合的研究领域的重要进展，第一部分在分别简要介绍网状框架和机械互锁结构的基础上阐述了两个领域结合的意义和策略；第二部分主要介绍了机械互锁结构作为构筑模块参与网状框架构建的系统性和代表性工作，包括含轮烷和索烃的构筑模块；第三部分则是介绍由机械互锁作用为主要相互作用构筑的网状框架，包括弹性编织框架和机械互锁框架，最后对全文进行总结并对该领域的后续发展方向予以探讨.     

离子液体功能化金属/共价-有机框架材料在催化反应中应用

离子液体（ILs）功能化的金属有机框架（MOFs）和共价有机框架（COFs）材料兼具离子液体和MOFs/COFs的优点，是一种极具潜力的复合催化材料。MOFs和COFs材料固定的孔结构及较大的比表面积为负载高分散催化中心提供了天然的物理空间；多孔结构促使催化剂与反应物充分接触；丰富的孔道有利于运输催化反应底物和产物，进而实现催化反应的高效进行。特别是离子液体片段的引入，可以作为催化活性中心的配体（稳定剂）或分散剂，同时能够有效改善MOFs和COFs材料孔道和活性中心周围的微环境。此外，还可以充分利用离子液体片段在适当的反应条件下转化为氮杂环卡宾配体的特点，在MOFs和COFs材料中引入氮杂环卡宾有机金属配合物。因此，我们对近几年来离子液体功能化的MOFs或COFs催化体系在CO2环加成、CO2还原、C-C偶联、羰基化以及其它有机转化反应中的研究应用进行简要综述。并对复合材料在催化领域的发展进行总结和展望。     

Recent advances in metal‐organic frameworks and covalent organic frameworks for sample preparation and chromatographic analysis

In the field of analytical chemistry, sample preparation and chromatographic separation are two core procedures. The means by which to improve the sensitivity, selectivity and detection limit of a method have become a topic of great interest. Recently, porous organic frameworks, such as metal‐organic frameworks (MOFs) and covalent organic frameworks (COFs), have been widely used in this research area because of their special features, and different methods have been developed. This review summarizes the applications of MOFs and COFs in sample preparation and chromatographic stationary phases. The MOF‐ or COF‐based solid‐phase extraction (SPE), solid‐phase microextraction (SPME), gas chromatography (GC), high‐performance liquid chromatography (HPLC) and capillary electrochromatography (CEC) methods are described. The excellent properties of MOFs and COFs have resulted in intense interest in exploring their performance and mechanisms for sample preparation and chromatographic separation.     

Recent strategies to enhance the performance of polymer monoliths for analytical separations

This review summarizes recent developments made in the incorporation of functional materials into organic polymer monoliths, together with new monolithic forms and formats, which enhance their application as supports and stationary phase materials for sample preparation and chromatographic separations. While polymer monoliths are well‐known supports for the separation of large molecules, recent developments have been made to improve their features for the separation of small molecules. The selectivity and performance of organic polymer monoliths has been improved by the incorporation of different materials, such as metal‐organic frameworks, covalent organic frameworks, or other types of nanostructured materials (carbon nanohorns, nanodiamonds, polyoxometalates, layered double hydroxides, or attapulgite). The surface area of polymer monoliths has been significantly increased by polymer hypercrosslinking, resulting in increased efficiency when applied to the separation of small molecules. In addition, recent exploration of less conventional supports for casting polymer monoliths, including photonic fibres and 3D printed materials, has opened new avenues for the applications of polymer monoliths in the field of separation science. Recent developments made in these topics are covered, focusing on the strategies followed by the authors to prepare the polymer monoliths and the effect of these modifications on the developed analytical applications.     

A Facile Grinding Method for the Synthesis of 3D Ag Metal–Organic Frameworks (MOFs) Containing Ag6Mo7O24 for High-Performance Supercapacitors

Successful synthesis of three kinds of dynamically stable compounds by a simple grinding method is reported, giving Ag₆Mo₇O₂₄, Ag-BTC (Ag-MOF, BTC=benzene-1,3,5-tricarboxylic acid), and {Ag₆Mo₇O₂₄}@Ag-MOF metal–organic frameworks (MOFs). According to the electrochemical dynamic analysis, these materials have pseudocapacitor behavior and high capacitance. The unique nanorod structure of {Ag₆Mo₇O₂₄}@Ag-MOF provides more active sites, faster ion/electron transfer, and electrolyte diffusion pathways, resulting in excellent specific capacitance (971 F g⁻¹) higher than the other compounds. {Ag₆Mo₇O₂₄}@Ag-MOF (glassy carbon electrode) also has an excellent rate ability (60.1 %) and long cycle stability (98 % retention after 5000 cycles). In addition, the fully symmetrical button battery (with nickel foam as the current collector) fabricated with {Ag₆Mo₇O₂₄}@Ag-MOF delivers an energy density of 11.1 Wh kg⁻¹ at 600.1 Wh kg⁻¹ coupled with excellent cycling stability (86.4 %) at 1.2 V. These results demonstrate a new simple grinding method to prepare polyoxometalate-based metal–organic frameworks (POMOFs) for high-performance materials.     

Metal–Covalent Organic Frameworks (MCOFs): A Bridge Between Metal–Organic Frameworks and Covalent Organic Frameworks

Many sophisticated chemical and physical properties of porous materials strongly rely on the presence of the metal ions within the structures. Whereas homogeneous distribution of metals is conveniently realized in metal–organic frameworks (MOFs), the limited stability potentially restricts their practical implementation. From that perspective, the development of metal–covalent organic frameworks (MCOFs) may address these shortcomings by incorporating active metal species atop highly stable COF backbones. This Minireview highlights examples of MCOFs that tackle important issues from their design, synthesis, characterization to cutting-edge applications.     

一种阴离子型三维金属有机框架材料Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)(BDC=对苯二甲酸根,Bipy=联吡啶)的制备及其对甲基紫的吸附性能

以2-氨基对苯二甲酸、4,4'-联吡啶配体和硝酸铜为原料,在溶剂热的条件下,合成了一种的阴离子型三维金属有机框架(MOF)材料Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)(BDC=对苯二甲酸根,Bipy=联吡啶)。通过IR、XRD、SEM、TG、N_2吸附法测比表面积等技术手段表征材料的结构和性能。研究了Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)材料对甲基紫的吸附性能,探讨了甲基紫溶液的初始p H值和初始浓度以及不同吸附温度对吸附量的影响。结果表明,等温吸附模型符合Langmuir等温吸附模型,动力学符合拟二级动力学。热力学参数ΔG0、ΔΗ0和ΔS0,表明Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)对甲基紫的吸附是自发和放热的,在溶液p H=9,温度为20℃条件下,Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)对甲基紫的吸附量为60.09 mg/g,说明Cu(BDC)(4,4'-Bipy)_(0.5)材料可以通过氨基改性,提高其对染料的吸附能力。     

Rational Design of MOF/COF Hybrid Materials for Photocatalytic H2 Evolution in the Presence of Sacrificial Electron Donors

Crystalline and porous covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H₂ evolution due to their long‐range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two‐dimensional (2D) COF with stable MOF. By covalently anchoring NH₂‐UiO‐66 onto the surface of TpPa‐1‐COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H₂ evolution under visible light irradiation. Especially, NH₂‐UiO‐66/TpPa‐1‐COF (4:6) exhibits the maximum photocatalytic H₂ evolution rate of 23.41 mmol g^?1 h^?1 (with the TOF of 402.36 h^?1), which is approximately 20 times higher than that of the parent TpPa‐1‐COF and the best performance photocatalyst for H₂ evolution among various MOF‐ and COF‐based photocatalysts.     

An Ultrastable Crystalline Acylhydrazone-Linked Covalent Organic Framework for Efficient Removal of Organic Micropollutants from Water

As an important member of crystalline porous polymers, acylhydrazone-linked covalent organic frameworks (COFs) have gained much attention in recent years. However, the low structural stability imparts a limit on their practical applications. To tackle this problem, we report a simple strategy to increase the chemical stability of acylhydrazone-linked COFs by incorporating azobenzene groups in the conjugated framework. Through reinforcing the π-π stacking interactions between the adjacent layers with increased π-surface, it is surprising to find that the resulting materials exhibit extreme stability in harsh environments, such as in strong acid, strong base, aqueous educing agent and boiling water, even exposed to air for one year. As a proof-of-concept, such frameworks have been used to remove various organic micropollutants such as antibiotics, plastic components, endocrine disruptors, and carcinogens from water with high capacity, fast speed and excellent reusability over a wide pH range at environmentally relevant concentrations. The results provide a new avenue to significantly enhance the stability of COFs for practical applications.