核壳结构金属-有机骨架的研究

核壳结构(core-shell)金属-有机骨架(metal-organic frameworks,MOFs)是多功能MOFs复合材料中最为典型的一类构型,是由MOFs材料和另一种材料(如MOFs、碳材料、无机化合物、有机聚合物等)组装形成的核壳结构,其中MOFs既可作核,亦可作壳。因结合了核层和壳层两种材料,核壳结构MOFs展现出了优于核层或者壳层的独特性能,例如结构稳定、选择性分离、气体吸附等,为MOFs材料实现工业化应用带来了新的潜力。本文综述了近年来核壳结构MOFs材料的研究进展,介绍了各类构型核壳结构MOFs材料(例如MOF@MOF、MOF@carbon、metal oxide@MOF、polymer@MOF等)的合成方法及应用研究,并对其今后的发展进行了展望。     

核壳结构金属-有机骨架及其衍生物在锂离子电池负极材料中的应用

金属-有机骨架(MOFs)材料具有比表面积较大、孔径可调、制备容易、结构与功能多样性等优势,被广泛应用于电化学能源转化与储存领域。其中独特的核壳结构材料由于表面修饰的作用往往更能表现出内核与壳层之间的协同作用。本文介绍了核壳结构MOFs作为锂离子电池负极材料的发展现状,并重点综述其衍生物(多孔碳材料、金属氧化物、金属硫/硒化物以及金属/金属氧化物)的制备方法以及在锂离子电池负极中的应用。MOFs经高温煅烧或改变化学反应条件可制备出结构可调的无机电极材料并表现出更优异的电化学性能。最后总结了核壳结构MOFs材料作为锂电负极材料存在的问题和挑战,并提出可能的解决途径和未来的应用前景。     

高效氧催化反应中的金属有机骨架材料（英文）

氧电催化反应包括氧气还原反应(ORR)和氧气析出反应(OER).作为核心电极反应,这两个反应对诸多能源存储与转换技术(比如燃料电池、金属空气电池以及全水分解制氢等)的能量效率起决定性作用.然而,ORR和OER涉及多个反应步骤、多个电子转移过程以及多相界面传质过程.这些复杂的过程较大程度上限制了ORR和OER的反应速率.从理论和实践两个方面来看,ORR和OER都需要高效电催化剂的参与来促进其反应速率,从而能够最终提高上述能源存储与转换技术的能量转换或利用效率.目前,以Pt,Pd,Ir,Ru为代表的贵金属基电催化剂具有十分突出的电催化性能.但是,过高的成本和过低的储量始终制约着贵金属基电催化剂在催化ORR和OER反应方面,乃至在能源存储与转换技术领域的规模化应用.因而,开发高效非贵金属基氧电催化剂成为近年来能源存储与转换领域的研究重点之一.在众多已经报道的非贵金属基氧电催化剂中,金属有机骨架材料(MOFs)备受瞩目.MOFs是一类由有机配体和金属节点通过配位键自组装而成的晶态多孔材料.它们具备超高比表面积、超高孔隙率以及规则性纳米孔道.相比较其他传统的多孔材料(比如活性炭、分子筛、介孔炭、介孔氧化硅等),MOFs最主要的优势在于它们的结构和功能可以依据需求通过选择合适的有机配体和金属节点进行便利地设计,或通过后处理进行必要的改性和调节.基于独特的多孔特性以及结构与功能的可设计、可调节性,MOFs在气体分离与存储、异相催化、化学传感、药物输送、环境保护以及能源存储与转化等领域都具有潜在的应用价值.因而,近年来,MOFs备受基础研究领域和工业界的青睐.针对MOFs开展的基础研究和应用开发逐渐成为诸多领域的研究焦点.也正由于MOFs具有的上述优异特性,尤其是结构与功能的可设计、可调节性,使得设计制备基于单纯MOFs以及MOFs衍生材料成为开发高效非贵金属基氧电催化剂的新途径.本综述首先论述了基于单纯MOFs的氧电催化剂(包括纯MOFs、活性物种修饰的MOFs以及与导电材料构成的复合MOFs)的合成以及它们在ORR或OER催化反应中应用的研究进展.在第二部分论述中,本综述主要针对MOFs衍生的各类氧电催化剂(包括无机微米-纳米结构/多孔碳复合材料、纯多孔碳材料、纯无机微米-纳米结构材料以及单原子型电催化材料)的研究进展进行了简要介绍和讨论.最后,本综述对MOFs基氧电催化剂目前存在的挑战进行了简要分析;同时,也对这类氧电催化剂的通用设计准则以及未来发展方向进行了展望.尽管存在诸多挑战,MOFs始终被认为是极好的"平台"材料.充分利用它们将有利于开发高效且实用的非贵金属基氧电催化剂.     

MOFs传感器在癌症及其生物标志物检测中的应用

癌症是世界上最致命的疾病之一,因此癌细胞的有效捕获和敏感检测对基础研究以及临床诊断和治疗都具有重要意义.基于金属有机骨架(MOFs)的催化活性和固有的发光性能等特点,MOFs已被成功地开发为传感平台实现对癌症及其标志物的检测.综述了基于MOFs的电化学、荧光、电化学发光、比色传感器在癌细胞及核酸、蛋白质等生物标志物检测...     

中空MOFs材料制备及电催化应用的研究进展

水分裂、金属-空气电池和燃料电池等能源转换技术对解决未来的能源危机和环境问题至关重要.氧还原反应(ORR)、氧析出反应(OER)和氢析出反应(HER)作为其核心反应,存在反应动力学速率较慢的问题,因此,开发研制高效的非贵金属电催化剂具有重要意义.金属有机骨架(MOFs)材料因具有高度可调的组成和多孔晶体结构,在不同的应用领域引起了越来越多的关注.中空MOFs纳米材料具有MOFs材料高度可调的组成和结构优势,又具有中空结构纳米材料的优点(如更快的物质传输、更丰富的孔隙率、灵活多变的活性组分、更多的暴露活性位点及对苛刻条件的更好相容性等),在电催化领域显现出巨大的应用潜力.本文对近几年来基于中空结构MOFs材料的制备及在电催化方面应用的研究进展进行了综合评述,并对该领域面临的挑战和发展前景进行了总结和展望.     

基于金属有机框架的纳米酶及其在生物分析中的应用

纳米酶是一类具有类酶活性的纳米材料,在分析化学和疾病诊疗领域具有良好的发展潜力。金属有机框架（MOFs）材料是由金属节点和有机配体形成的多孔晶体材料,其结构与天然酶有一定的相似性。目前,研究者已经开发了多种基于MOFs的纳米酶,包括具有类过氧化物酶、类氧化酶、类超氧化物歧化酶和类水解酶活性的纳米酶等,并显示出广阔的应用前景。本文根据材料的结构特点,将基于MOFs的纳米酶分为原始MOFs、化学修饰MOFs、MOFs复合材料和MOFs衍生物4类,介绍了这4类纳米酶制备的基本原理与最新研究进展。在此基础上,根据比色传感、荧光传感和电化学传感等分析策略,综述了MOFs基纳米酶在生物分析方面的研究和应用进展,讨论了其在实际应用中所面临的挑战和未来的发展趋势。     

金属有机框架(MOFs)基光催化剂的设计及其在太阳能燃料生产和污染物降解领域的研究进展（英文）

金属有机骨架(MOFs)具有较高的比表面积,丰富的金属/有机物种,较大的孔体积以及结构和成分可调节的特性,因此在太阳能燃料生产和污染物的光降解领域具有广泛的应用.根据其结构特点,研究者们主要从有机配体和孔道结构两方面对MOFs进行调控:(1)对有机配体进行修饰,如将杂原子、羟基、卤素原子、金属离子、生物大分子等引入MOFs结构;(2)将无机纳米粒子引入MOFs孔道内,如将贵金属、金属氧化物、多金属氧酸盐等纳米粒子封装在MOFs的孔道内.这些策略可有效增强MOFs的导电性、稳定性等,并进一步提高MOFs基催化剂的光催化性能.本文首先概述了四种经典MOFs类型,即UiO, ZIF, MIL和PCN系列的结构特点和催化性能.其次,总结了在设计MOFs基光催化材料过程中,根据不同类型MOFs特点着重考虑的五方面因素,即稳定性、能带结构、吸附作用、选择性和电导性.再次,讨论了提高MOFs基光催化剂活性的策略,如助催化剂修饰、构建异质结、配体或金属中心修饰和缺陷工程.最后,总结了MOFs基光催化材料在催化还原CO₂、分解水制氢和降解有机污染物反应中的应用进展及影响其催化性能的...     

金属-有机骨架材料在色谱分离中的应用

金属-有机骨架材料（Metal-organic frameworks,MOFs）,因其具有较好的热稳定性、化学稳定性、可设计性等特点,广泛应用于气体吸附、物质分离、提纯、催化等领域,同时也作为模板制备各种功能材料.MOFs作为色谱分离的材料已得到了较多的研究与应用.按照被分离物质的类别,综述和总结了不同MOFs材料作为色谱固定相的分离效果,重点介绍了MOFs材料的色谱分离机理.MOFs材料的孔径、功能基团和不饱和金属位点在分离中起到重要的作用,最后对MOFs在色谱分离应用中的问题和前景进行了分析和展望.     

金属有机框架抗菌材料的研究进展

细菌耐药问题已经成为了中国乃至全球的重大公共健康威胁,设计合成新型抗菌材料以减少抗生素依赖成为当前化学化工、材料和生物医学领域中的重要研究课题.金属有机框架(Metal-organic frameworks, MOFs)材料是由有机配体和金属离子或团簇通过配位键自组装形成的多孔晶态材料,在气体吸附与分离、传感和催化等领域都扮演着重要角色.为了寻求更好应对细菌威胁的方式方法,国内外研究者们纷纷构建出不同结构的MOFs材料,并将其应用于抗菌领域.本综述从细菌耐药性的产生和MOFs抗菌机理等方面出发,分类概述了不同金属中心和配体MOFs材料、MOFs包覆金属纳米粒子材料和药物缓释MOFs材料等在抗菌、促进伤口愈合等方面的应用,归纳概括了MOFs材料在抗菌领域应用中仍需解决的科学问题,并对该领域的发展趋势进行了展望.     

金属-有机骨架材料的改性方法及其光催化制氢应用

能源问题一直是关乎人类命运的重要问题,光催化制氢被认为是有望解决这一问题的潜在途径之一.金属有机框架(MOFs)由于其多孔、高比表面积、带隙可调等特性,在光催化制氢方面得到了广泛关注.我们综述了近些年来在金属-有机骨架材料光催化制氢领域的各种改性方法 ,包括修饰有机连接配体、修饰金属中心、金属纳米粒子沉积、染料敏化与其他功能材料结合等.概括了改性后的MOFs光催化制氢性能,指出了MOFs基光催化制氢存在的问题和可能的解决思路,并展望了MOFs基光催化制氢剂的绿色未来.     

无酶葡萄糖电化学传感器的研究进展

随着各种新型材料的层出不穷及其在葡萄糖电化学传感器方面应用的发展,无酶葡萄糖电化学传感器的研制成为葡萄糖电化学传感器的另一个研究热点.本文综述了近年来无酶葡萄糖电化学传感器的研究进展,重点介绍了电流型无酶葡萄糖传感器所使用的各种电极材料,总结了最近五年各种新型结构材料在该类传感器研制方面的应用,并对无酶葡萄糖电化学传感器发展方向和趋势进行了展望.     

Electrochemical non-enzymatic glucose sensors

The electrochemical determination of glucose concentration without using enzyme is one of the dreams that many researchers have been trying to make come true. As new materials have been reported and more knowledge on detailed mechanism of glucose oxidation has been unveiled, the non-enzymatic glucose sensor keeps coming closer to practical applications. Recent reports strongly imply that this progress will be accelerated in ‘nanoera’. This article reviews the history of unraveling the mechanism of direct electrochemical oxidation of glucose and making attempts to develop successful electrochemical glucose sensors. The electrochemical oxidation of glucose molecules involves complex processes of adsorption, electron transfer, and subsequent chemical rearrangement, which are combined with the surface reactions on the metal surfaces. The information about the direct oxidation of glucose on solid-state surfaces as well as new electrode materials will lead us to possible breakthroughs in designing the enzymeless glucose sensing devices that realize innovative and powerful detection. An example of those is to introduce nanoporous platinum as an electrode, on which glucose is oxidized electrochemically with remarkable sensitivity and selectivity. Better model of such glucose sensors is sought by summarizing and revisiting the previous reports on the electrochemistry of glucose itself and new electrode materials.     

Copper‐based Metal‐organic Framework for Non‐enzymatic Electrochemical Detection of Glucose

A non‐enzymatic electrochemical glucose sensor based on a Cu‐based metal‐organic framework (Cu‐MOF) modified electrode was developed. The Cu‐MOF was prepared by a simple ionothermal synthesis, and the characterizations of the Cu‐MOF were studied by Fourier transform infrared spectroscopy (FT‐IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), single‐crystal X‐ray powder diffraction (SCXRD), and X‐ray powder diffraction (XRD). Electrochemical behaviors of the Cu‐MOF modified electrode to glucose were measured by differential pulse voltammetry (DPV). The electrochemical results showed that the Cu‐MOF modified electrode exhibited an excellent electro‐catalytic oxidation towards glucose in the range of 0.06 μM to 5 mM with a sensitivity of 89 μA/mM cm² and a detection limit of 10.5 nM. Moreover, the fabricated sensor showed a high selectivity to the oxidation of glucose in coexistence with other interferences. The sensor was satisfactorily applied to the determination of glucose in urine samples. With the significant electrochemical performances, MOFs may provide a suitable platform in the construction of kinds of electrochemical sensors and/or biosensors and hold a great promise for sensing applications.     

Metalloporphyrin-Based Metal–Organic Frameworks on Flexible Carbon Paper for Electrocatalytic Nitrite Oxidation

Deposition of redox-active metal–organic frameworks (MOFs) as thin films on conductive substrates is of great importance to improve their electrochemical performance and durability. In this work, a series of metalloporphyrinic MOF crystals was successfully deposited as thin films on carbon fiber paper (CFP) substrates, which is an alternative to rigid glass substrates. The specific dimensions of the obtained films could be adjusted easily by simple cutting. Metalloporphyrinic MOFs on CFP with different active metal species have been employed for electrochemical conversion of the carcinogenic nitrite into the less toxic nitrate. The MOFs on CFP exhibit remarkable improvement in terms of the electrocatalytic performance and reusability compared with the electrodes prepared from MOF powder. The contribution from metal species of the porphyrin units and reaction mechanisms was elucidated based on the findings from X-ray photoelectron spectroscopy (XPS) and in situ X-ray absorption near edge structure (XANES) measured during the electrochemical reaction. By integrating the redox-active property of metalloporphyrinic MOFs and high conductivity of CFP, MOF thin films on CFP provided a significant improvement of electrocatalytic performance to detoxify the carcinogenic nitrite with good stability.     

Determination of Buprenorphine (BUP) with Molecularly Imprinted Polymer Zn/La3+ Metal Organic Framework on Modified Glassy Carbon Electrode (GCE)

In this study we report the Zn/La³⁺ metal organic frameworks (MOFs) were synthesized with the co-precipitation assisted microwave method. Zn/La³⁺ MOFs were used as a new nanocomposite for the design and construction of a nanosensor based on glassy carbon electrode (GCE). MOFs due to their unique and excellent physicochemical properties can be used in sensors based on glassy carbon electrode (GCE). The synergistic effect of MOFs on glassy carbon electrode increases the power of the limits of detection (LOD). In this study, a new chemical sensor was fabricated by electro polymerization to measure buprenorphine with MOFs based on molecularly imprinted polymer. Zn/La³⁺ MOFs nanostructures were identified with scanning electron microscopy (SEM), Dynamic light scattering (DLS), Transmission electron microscopy (TEM) and the Fourier-transform infrared spectroscopy (FT-IR) spectra. Buprenorphine was used as a template, pyrrole was used as a monomer, potassium ferrocyanide as an electrochemical active tracer in electropolymerization processes and the parameters affecting the sensor response were optimized. At the Zn/La³⁺ MOF/MIP electrode, the calibration curve in the linear region was obtained in the concentration range between 4 to 50 ng/ml and the detection limit was 1.08 ng/ml. In a new strategy, Zn/La³⁺ MOFs nanostructures can be introduced as new materials with high efficiency which used at chemical sensors for detection of the opiates in all over the world.     

A novel non-enzymatic glucose sensor based on Cu nanoparticle modified graphene sheets electrode

A novel, stable and sensitive non-enzymatic glucose sensor was developed by potentiostatically electrodepositing metallic Cu nanoparticles on graphene sheets. The electrochemical performance of the Cu-graphene sheets electrode for detection of glucose was investigated by cyclic voltammetry and chronamperometry. The Cu-graphene sheets electrode displayed a synergistic effect of copper nanoparticles and graphene sheets towards the oxidation of glucose in alkaline solution, showing higher oxidation current and negative shift in peak potential. At detection potential of 500 mV, the Cu-graphene electrode sensor presented a wide linear range up to 4.5 mM glucose with a detection limit of 0.5 μM (signal/noise = 3). In addition, the sensor responds very quickly (<2 s) with addition of glucose. Furthermore, the Cu-graphene sheets electrode exhibits high stability and selectivity to glucose, and the poisoning by chloride ion as well as interference from the oxidation of common interfering species (ascorbic, dopamine, uric acid and carbohydrate) are effectively avoided. The Cu-graphene sheets electrode allows highly selective and sensitive, stable and fast amperometric sensing of glucose, which is promising for the development of non-enzymatic glucose sensor.     

Metal–Organic Frameworks: Opportunities for Catalysis

The role of metal–organic frameworks (MOFs) in the field of catalysis is discussed, and special focus is placed on their assets and limits in light of current challenges in catalysis and green chemistry. Their structural and dynamic features are presented in terms of catalytic functions along with how MOFs can be designed to bridge the gap between zeolites and enzymes. The contributions of MOFs to the field of catalysis are comprehensively reviewed and a list of catalytic candidates is given. The subject is presented from a multidisciplinary point of view covering solid‐state chemistry, materials science, and catalysis.     

金属有机框架材料对Cr(Ⅵ)离子的吸附去除研究进展

重金属离子污染问题一直备受关注.开发利用多孔材料吸附去除水中重金属离子一直是材料、环境等相关学科领域的研究热点之一.金属有机框架材料(metal-organic frameworks,MOFs)是一类新型的多孔材料,具有结构多样、比表面积大、孔径可调、孔表面特征易设计调控等特点,在气体分离、催化、传感等领域表现出极大的...