Photophysics of metal-organic frameworks:A brief overview

Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their diverse structures and excellent tunability.However,the performance of MOF-based optoelectronic applications currently falls short of the industry benchmark.To enhance the performance of MOF materials,it is imperative to undertake comprehensive investigations aimed at gaining a deeper understanding of photophysics and sequentially optimizing properties related to photocarrier transport,recombination,interaction,and transfer.By utilizing femtosecond laser pulses to excite MOFs,time-resolved optical spectroscopy offers a means to observe and characterize these ultrafast microscopic processes.This approach adds the time coordinate as a novel dimension for comprehending the interaction between light and MOFs.Accordingly,this review provides a comprehensive overview of the recent advancements in the photophysics of MOFs and additionally outlines potential avenues for exploring the time domain in the investigation of MOFs.

Research progress on the substrate for metal-organic framework(MOF) membrane growth for separation

During the last decade, metal-organic frameworks(MOFs) have been applied in various fields due to their unique chemical and functional advantages. One of the widespread research hotspots is MOF-based membranes for separations, specifically continuous defect-free MOF membranes, which are usually grown on porous substrates. The substrate not only serves as the MOF layer support but also has a great influence on the membrane fabrication process and the final separation performance of the resultant membrane. In this review, we mainly introduce the progress focused on the substrates for MOF membranes fabrication. The substrate modifications and seeding methods aimed at synthesizing highquality MOF membranes are also summarized systematically.

A Review on Metal-Organic Framework-Derived Porous Carbon-Based Novel Microwave Absorption Materials

The development of microwave absorption materials(MAMs) is a considerable important topic because our living space is crowed with electromagnetic wave which threatens human’s health.And MAMs are also used in radar stealth for protecting the weapons from being detected.Many nanomaterials were studied as MAMs,but not all of them have the satisfactory performance.Recently,metal-organic frameworks(MOFs) have attracted tremendous attention owing to their tunable chemical structures,diverse properties,large specific surface area and uniform pore distribution.MOF can transform to porous carbon(PC) which is decorated with metal species at appropriate pyrolysis temperature.However,the loss mechanism of pure MOF-derived PC is often relatively simple.In order to further improve the MA performance,the MOFs coupled with other loss materials are a widely studied method.In this review,we summarize the theories of MA,the progress of different MOF-derived PC-based MAMs,tunable chemical structures incorporated with dielectric loss or magnetic loss materials.The different MA performance and mechanisms are discussed in detail.Finally,the shortcomings,challenges and perspectives of MOF-derived PC-based MAMs are also presented.We hope this review could provide a new insight to design and fabricate MOF-derived PC-based MAMs with better fundamental understanding and practical application.

Metal-Organic Framework Materials for Electrochemical Supercapacitors

Exploring new materials with high stability and capacity is full of challenges in sustainable energy conversion and storage systems.Metal-organic frameworks(MOFs),as a new type of porous material,show the advantages of large specific surface area,high porosity,low density,and adjustable pore size,exhibiting a broad application prospect in the field of electrocatalytic reactions,batteries,particularly in the field of supercapacitors.This comprehensive review outlines the recent progress in synthetic methods and electrochemical performances of MOF materials,as well as their applications in supercapacitors.Additionally,the superiorities of MOFs-related materials are highlighted,while major challenges or opportunities for future research on them for electrochemical supercapacitors have been discussed and displayed,along with extensive experimental experiences.

State of the Art and Prospects in Metal-Organic Framework-Derived Microwave Absorption Materials

Microwave has been widely used in many fields,including communication,medical treatment and military industry;however,the corresponding generated radiations have been novel hazardous sources of pollution threating human’s daily life.Therefore,designing high-performance microwave absorption materials(MAMs)has become an indispensable requirement.Recently,metal-organic frameworks(MOFs)have been considered as one of the most ideal precursor candidates of MAMs because of their tunable structure,high porosity and large specific surface area.Usually,MOF-derived MAMs exhibit excellent electrical conductivity,good magnetism and sufficient defects and interfaces,providing obvious merits in both impedance matching and microwave loss.In this review,the recent research progresses on MOF-derived MAMs were profoundly reviewed,including the categories of MOFs and MOF composites precursors,design principles,preparation methods and the relationship between mechanisms of microwave absorption and microstructures of MAMs.Finally,the current challenges and prospects for future opportunities of MOF-derived MAMs are also discussed.

Metal-Organic Framework-Based Sulfur-Loaded Materials

Lithium-sulfur batteries(LSBs)are considered promising new energy storage systems given their outstanding theoretical energy densities.Nevertheless,issues such as low electrical conductivity and severe volume expansion,along with the formation of polysulfides during cycling,restrict their practical applications.To overcome these issues,it is necessary to find suitable and effective sulfur host materials.Metal-organic frameworks(MOFs),which are porous crystalline materials in the bourgeoning developmental stages,have demonstrated enormous potential in LSBs owing to their high porosity and tunable porous structure.Herein,we provide a comprehensive overview of MOF-based sulfur-loaded materials and discuss the charge/discharge mechanisms,strategies of enhancing battery performance,sulfur loading methods,and applications in LSBs.An outlook on future directions,prospects,and possible obstacles for the development of these materials is also provided.

MOFs膜在离子分离中的应用研究进展

金属有机框架(MOFs)材料在膜技术领域受到的关注日益增长,其规则且高度可调的亚纳米尺寸孔道结构、高孔隙率以及官能化修饰的灵活性,使MOFs膜在精细化离子筛分方面表现出良好的应用潜力。近年来,离子在MOFs多晶膜、MOFs混合基质膜和MOFs通道膜体系内的选择性传输行为相继被报道,基于MOFs材料的结构-性能关系,通过可控设计以优化膜的选择性和稳定性取得了诸多进展。系统地梳理了上述MOFs膜的制备、离子选择性分离机理和优化思路,对比分析了其各自的特点和实际应用面临的挑战,基于此,提出MOFs膜在离子分离领域的潜在发展方向。

金属有机骨架(MOFs)衍生材料及其在催化领域的研究进展

金属有机骨架(MOFs)材料是一类具有大比表面积和可调孔结构的新型多孔材料,近年来在催化制备精细化学品领域受到广泛关注。在实际催化过程中,MOFs较差的稳定性制约了其在许多反应中的应用。以MOFs为前驱体制备的MOFs衍生材料能够保留MOFs材料结构上的优势,同时解决其稳定性差的问题,极大拓展MOFs材料在催化反应中的应用。综述MOFs衍生材料在催化领域特别是在加氢和氧化制备精细化学品中的研究进展,并对MOF衍生材料面临的问题及其在催化领域的应用前景进行了展望。

Novel in-capsule synthesis of metal-organic framework for innovative carbon dioxide capture system

Metal-Organic Frameworks(MOFs)have been developed as solid sorbents for CO_(2) capture applications and their properties can be controlled by tuning the chemical blocks of their crystalline units.A number of MOFs(e.g.,HKUST-1)have been developed but the question remains how to deploy them for gas-solid contact.Unfortunately,the direct use of MOFs as nanocrystals would lead to serious problems and risks.Here,for the first time,we report a novel MOF-based hybrid sorbent that is produced via an innovative in-situ microencapsulated synthesis.Using a custom-made double capillary microfluidic assembly,double emulsions of the MOF precursor solutions and UV-curable silicone shell fluid are produced.Subsequently,HKUST-1 MOF is successfully synthesized within the droplets enclosed in the gas permeable microcapsules.The developed MOF-bearing microcapsules uniquely allow the deployment of functional nanocrystals without the challenge of handling ultrafine particles,and further,can selectively reject undesired compounds to protect encapsulated MOFs.

锌基MOFs材料在肿瘤治疗领域的应用进展

金属-有机框架(MOFs)是由含氧或氮的有机配体与过渡金属通过自组装连接而形成的具有周期性网状结构的晶体材料。该类材料因具有尺寸结构可调、高孔隙率、比表面积大、低晶体密度等一系列优点,而受到多个学科研究人员的重视。其中,锌(Zn)基MOFs材料因其优越的生物相容性和易功能化修饰等特点,受到了广泛的关注。文章主要从药物递送和协同抗癌等方面总结了Zn基MOFs材料的生物应用.

Recent Progress in Synthesis, Mechanism and Applications of Zinc-Based Metal-Organic Frameworks for Fluorescent Sensing

As more and more pollutants threaten human health, it is necessary and essential to develop sensitive, accurate and rapid methods and sensory materials to detect harmful substance. Metal-organic frameworks (MOFs) are inorganic-organic hybrids assembled from inorganic metal ions or clusters and suitable organic ligands. Zinc-based MOFs (Zn-MOFs) have emerged as one of the most promising sensory material of MOFs for practical applications, and attracted significant attention due to structural diversity and incomparable stability properties. However, there are few reviews on systemic summary of synthesis design, mechanism and application of Zn-MOFs. In this review, we summarize the synthesis design methods, structure types and luminescence mechanism of Zn-MOFs sensor recognition in the past ten years and their applications in metal cations, anions, organic compounds and other analytes. Finally, we present a short conclusion, and look forward to the future development direction of Zn-MOFs.

Equilibrium,Kinetics and Thermodynamics of the Adsorption of Methylene Blue onto a Metal-Organic Frameworks Material,Copper Coordination Polymer with Dithiooxamide

The equilibrium, kinetics and thermodynamics of the adsorption of methylene blue( MB) from aqueous solution onto copper coordination polymer with dithiooxamide( H2dtoaCu),one of the metal-organic frameworks( MOFs),were investigated in a batch adsorption system as a function of initial pH, adsorbent concentration, contact time, initial dye concentration, and temperature. The Langmuir, Freundlich, and DubininRadushkevich( D-R) isotherm models were used for modeling the adsorption equilibrium. It was found that Langmuir model yielded a much better fit than the Freundlich model under different temperatures. The maximum monolayer adsorption capacities of MB were 192. 98,229. 86,and 297. 38 mg /g at 298,308,and 318 K,respectively. The calculated mean adsorption energy( 8. 26-11. 04 kJ /mol) using D-R model indicated that the adsorption process might take place by chemical adsorption mechanism.Otherwise,the kinetic studies revealed that the adsorption process could be well explained by pseudo-second-order rate kinetics and intraparticle diffusion was not the rate-limiting step.Thermodynamic studies indicated that this system was feasible,spontaneous,and endothermic process. Based on these studies,H2dtoaCu can be considered as a potential adsorbent for the removal of MB from aqueous solution.

Research Progress of MOFs Materials in Separation Technology

Metal-organic frameworks(MOFs)are a class of porous crystalline materials,consisting of metal ions or clusters coordinated to organic ligands.It has the advantages of ultra-high specific surface area,diverse structure,good thermal stability,adjustable pore size and properties,and shows important application value in the field of separation.In this paper,the research progress of metal-organic framework materials in gas separation and chromatographic separation is reviewed,and the existing problems and development direction of metal-organic framework materials in adsorption and separation are discussed.

MOFs电极材料的制备及其电化学性能

设计了直接利用金属有机骨架化合物(MOFs)材料制备超级电容器电极的实验,并研究了影响其电化学性能的关键因素。先通过一步搅拌加热法制备MOFs材料,并添加碳材料改善MOFs材料的导电性能,进而提升电化学性能;再以X-射线衍射仪、扫描电子显微镜对产物的结构与形貌进行表征,并用循环伏安法、恒流充放电法进行相应的电化学分析。实验结果表明:所制备的MOFs材料为片状结构,加入不同的碳材料后MOFs电极性能得到了明显的提升,其中加入石墨烯的提升效果最为显著;不同浓度的前驱体、石墨烯的用量以及不同的反应条件均会影响MOFs材料的电化学性能。该结果为直接利用MOFs作为电极材料应用于超级电容器中提供参考。

MOFs衍生碳基复合吸波材料的设计及性能调控策略

开发轻质高效的电磁波吸收材料对抗电磁干扰、信息安全、国防安全等方面具有重要的战略意义。近年来,金属—有机框架(MOFs)衍生的多孔碳基复合材料在轻质吸波材料领域受到广泛关注。得益于MOFs高度可调的孔结构以及可精准设计的组分和微观结构等优势,热解原位生成的金属基吸波基元不仅在多孔碳基质中形成了多界面和多样化的吸波组分,同时还产生了协同交联的导电网络,极大地丰富和强化了电磁波损耗机制,从而显著增强电磁波的吸收效能。其中,多种组分的合理设计和微观结构的可控构建是调控电磁参数的关键。立足于组分和孔结构调控策略,综述了近年来研究者们如何基于金属种类和空间分布、多元MOFs异质结构以及碳基质多孔结构对MOFs衍生碳基复合吸波材料进行理性设计及性能优化和提升。最后,对此类复合吸波材料的挑战和未来发展方向进行了阐述。

A review on anode materials for lithium/sodium-ion batteries

Since lithium-ion batteries(LIBs) have been substantially researched in recent years, they now possess exceptional energy and power densities, making them the most suited energy storage technology for use in developed and developing industries like stationary storage and electric cars, etc. Concerns about the cost and availability of lithium have prompted research into alternatives, such as sodium-ion batteries(SIBs), which use sodium instead of lithium as the charge carrier. This is especially relevant for stationary applications, where the size and weight of battery are less important. The working efficiency and capacity of these batteries are mainly dependent on the anode, cathode, and electrolyte. The anode,which is one of these components, is by far the most important part of the rechargeable battery.Because of its characteristics and its structure, the anode has a tremendous impact on the overall performance of the battery as a whole. Keeping the above in view, in this review we critically reviewed the different types of anodes and their performances studied to date in LIBs and SIBs. The review article is divided into three main sections, namely:(i) intercalation reaction-based anode materials;(ii) alloying reaction-based anode materials;and(iii) conversion reaction-based anode materials, which are further classified into a number of subsections based on the type of material used. In each main section, we have discussed the merits and challenges faced by their particular system. Afterward, a brief summary of the review has been discussed. Finally, the road ahead for better application of Li/Na-ion batteries is discussed, which seems to mainly depend on exploring the innovative materials as anode and on the inoperando characterization of the existing materials for making them more capable in terms of application in rechargeable batteries.

Ni-MOFs@GO复合材料对亚甲基蓝吸附性能研究

采用水热合成法制备镍基金属有机骨架材料(Ni-MOFs),然后以其为载体,采用溶液共混法制备Ni-MOFs@GO复合材料。采用傅里叶红外光谱仪和扫描电镜对其结构和形貌进行了表征。以亚甲基蓝(MB)为目标污染物,考察了Ni-MOFs与GO配比[m(Ni-MOFs)∶m(GO)]、MB初始浓度和Ni-MOFs@GO用量对MB吸附的影响,并对其吸附动力学和吸附等温线类型进行了探讨。结果表明,当m(Ni-MOFs)∶m(GO)为5∶1,MB初始浓度为25mg/L,Ni-MOFs@GO用量为0.6g/L时,对MB的吸附容量为243.898mg/g。吸附过程符合准二级动力学模型(R^(2)>0.999);在25℃条件下,Ni-MOFs@GO对MB平衡吸附量为235.373mg/g。吸附等温线拟合表明,Freundlich(R^(2)_(F)>0.779)模型能较好地描述MB的吸附行为。

The effects of amino groups and open metal sites of MOFs on polymer-based electrolytes for all-solid-state lithium metal batteries

Metal-organic frameworks(MOFs) are becoming more and more popular as the fillers in polymer electrolytes in recent years. In this study, a series of MOFs(NH_(2)-MIL-101(Fe), MIL-101(Fe), activated NH_(2)-MIL-101(Fe) and activated MIL-101(Fe)) were synthesized and added to PEO-based solid composite electrolytes(SCEs). Furthermore, the role of the —NH_(2) groups and open metal sites(OMSs) were both examined. Different ratios of MOFs vs polymers were also studied by the electrochemical characterizations. At last, we successfully designed a novel solid composite electrolyte containing activated NH_(2)-MIL-101(Fe),PEO, Li TFSI and PVDF for the high-performance all-solid-state lithium-metal batteries. This work might provide new insight to understand the interactions between polymers and functional groups or OMSs of MOFs better.

MOFs基碳材料对水体中抗生素的吸附去除

近年来,金属有机框架(metal-organic frameworks,MOFs)所衍生的多孔碳材料得益于其优异的孔隙结构和丰富的表面官能团,对水体中的抗生素表现出优异的吸附能力。并且,MOFs基碳材料制备合成方法简单且多样。为提高该类材料的吸附性能,现今研究人员主要研究集中在MOFs前体选择、制备条件优化、微观形貌调控及表面官能团修饰等方面。文中以MOFs基碳材料含有的元素种类及含量为依据,详细列举和分析了通过不同方法制备的MOFs基碳材料,通过模型拟合深入分析其对水体中抗生素吸附过程和机理,讨论影响吸附过程的不同因素,并对制备高性能MOFs基碳材料提出了见解。

三维纳米花NiCo-MOF非对称超级电容器储能特性

针对储能器件对高比容量、长寿命、高安全性、绿色环保电极材料的应用需求,利用一步溶剂热法制备三维纳米花镍钴双金属有机框架(NiCo-MOF)电极材料,并与活性炭(AC)一起组装了工作电压窗口可达1.45 V的高性能非对称超级电容器。通过调控优化金属前驱体摩尔比和水热时间制备得到NiCo-MOF电极材料。该NiCo-MOF电极材料在电流密度为1.0 A·g^(-1)下,比容量高达1839.23 F·g^(-1),这主要归因于由薄纳米片组成的纳米花NiCo-MOF提供了较大的比表面积和较多的电化学活性位点,极大地促进了电解质的浸入和氧化还原反应的发生。以NiCo-MOF为正极、AC为负极制备的非对称超级电容器在1.0 A·g^(-1)下,其比容量达到105.27 F·g^(-1),经过1000次循环后,比容量保持率为89.85%。结果表明,三维纳米花NiCoMOF电极材料在超级电容器等储能领域具有较好的应用前景。