Metal–Organic Framework-Assisted Synthesis of Compact Fe_2O_3 Nanotubes in Co_3O_4 Host with Enhanced Lithium Storage Properties

Transition metal oxides are promising candidates for the high-capacity anode material in lithium-ion batteries.The electrochemical performance of transition metal oxides can be improved by constructing suitable composite architectures. Herein, we demonstrate a metal–organic framework(MOF)-assisted strategy for the synthesis of a hierarchical hybrid nanostructure composed of Fe_2O_3 nanotubes assembled in Co_3O_4 host. Starting from MOF composite precursors(Fe-based MOF encapsulated in a Cobased host matrix), a complex structure of Co_3O_4 host and engulfed Fe_2O_3 nanotubes was prepared by a simple annealing treatment in air. By virtue of their structural and compositional features, these hierarchical composite particles reveal enhanced lithium storage properties when employed as anodes for lithium-ion batteries.

Advanced metal–organic frameworks for aqueous sodium-ion rechargeable batteries

Inexpensive and abundant sodium resources make energy storage systems using sodium chemistry promising replacements for typical lithium-ion rechargeable batteries(LIBs).Fortuitously,aqueous sodium-ion rechargeable batteries(ASIBs),which operate in aqueous electrolytes,are cheaper,safer,and more ionically conductive than batteries that operate in conventional organic electrolytes;furthermore,they are suitable for grid-scale energy storage applications.As electrode materials for storing Na~+ ions in ASIBs,a variety of multifunctional metal-organic frameworks(MOFs) have demonstrated great potential in terms of having porous 3 D crystal structures,compatibility with aqueous solutions,long cycle lives(≥1000 cycles),and ease of synthesis.The present review describes MOF-derived technologies for the successful application of MOFs to ASIBs and suggests future challenges in this area of research based on the current understanding.

Metal-organic frameworks for highly efficient oxygen electrocatalysis

Metal‐organic frameworks(MOFs)are a series of highly porous crystalline materials,which are built from inorganic metal nodes and organic linkers through coordination bonds.Their unique porous structural features(such as high porosity,high surface areas,and highly ordered nanoporous structures)and designable structures and compositions have facilitated their use in gas capture,separation,catalysis,and energy storage and conversion.Recently,the design and synthesis of pure MOFs and their derivatives have opened new routes to develop highly efficient electrocatalysts toward oxygen reduction reactions(ORR)and oxygen evolution reactions(OER),which are the core electrode reactions in many energy storage and conversion techniques,such as metal‐air batteries and fuel cells.This review first discusses recent progress in the synthesis and the electrocatalytic applications of pure MOF‐based electrocatalysts toward ORR or OER,including pure MOFs,MOFs decorated with active species,and MOFs incorporated with conductive materials.The following section focuses on the advancements of the design and preparation of various MOF‐derived materials-such as inorganic nano‐(or micro‐)structures/porous carbon composites,pure porous carbons,pure inorganic nano‐(or micro‐)structured materials,and single‐atom electrocatalysts-and their applications in oxygen electrocatalysis.Finally,we present a conclusion and an outlook for some general design strategies and future research directions of MOF‐based oxygen electrocatalysts.

Adsorption behavior and mechanism of Hg(Ⅱ)on highly stable Zn-based metal organic frameworks

A novel adsorbent(MTZ-MOFs)was synthesized by a one-step reaction of zinc nitrate hexahydrate and 1-(2-dimethylaminoethyl)-1H-5-mercaptotetrazole to remove mercury from waste water.The results showed that MTZ-MOFs had excellent selectivity and repeatability for Hg(Ⅱ),the optimum pH was 3.0,the maximum adsorption capacity was 872.8 mg/g,and the process was a spontaneous exothermic reaction.The adsorption behavior was chemisorption,which conformed to the pseudo-second-order kinetic and Freundlich isothermal model.Moreover,the adsorption mechanism showed that the adsorption process mainly depended on ion exchange and chelation,and the synergistic action of S and N atoms played a key role.So,MTZ-MOFs were an efficient adsorbent for mercury ion removal.

A Three-dimensional Porous Metal-organic Framework Based on Cyano Unit and 1,4-Bis(1,2,4-triazol-1-yl)butane(btb):{[Cu_8(btb)_2(CN)_8].3H_2O}_n

The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938（3）,b = 1.9422（5）,c = 0.9406（2） nm,β = 121.891（4）°,V = 2.0066（9） nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ（MoKα） = 4.209 mm？1,F（000） = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ（I）.In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.

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.

Novel Metal-organic Framework Compound Pb(C_5H_4NCOO)_2 Showing One-dimensional Channel Defined as Four Leads and Four Nicotinic Acids

A novel metal-organic framework（MOF） compound of Pb（C5H4NCOO）2 was hydrothermally synthesized and structurally determined by X-ray single-crystal diffraction. The data of unit cell： orthorhombic space group Pccn, a=1.0325（2） nm, b=1.3597（3） nm, c=0.8499（2） nm, V=1.1931（4） nm^3, Z=4, Dc=2.513 g/cm^3, R1=0.047 were obtained on the basis of 1365 reflections with Fo〉2σ（Fo）. PbN2O6 polyhedron adopts the distorted cubic configuration which is assigned to the holodirected geometry. These PbN2O6 polyhedra can form the zigzag chain by edge-sharing mode along（001） direction. Pb atom is connected by six nicotinic acid molecules, leading neutral 3D metal-organic framework with a channel defined by four Pb atoms and four nicotinic acid molecules.

Industrial Outlook on Zeolites and Metal Organic Frameworks

水晶的 nanoporous 材料在工业化学服务众多的枢轴的功能。他们为工业应用程序提供关键特征，例如高表面区域，一致的孔，互连的毛孔 / 隧道系统，可存取的毛孔卷，高吸附能力，离子交换能力，提高的催化活动，和形状 / 尺寸选择。作为 nanoporous 材料的一个生长得很好的家庭，沸石具有为化学、石油化学的工业的重要重要性。多孔的材料的一个新兴的班叫了器官的框架(MOF ) 也在各种各样的应用为诺言提供的金属。沸石和 MOF 能在为我们的工业化社会的未来是批评的地里起重要作用。在为原料变化的探索，沸石用作向基础化学药品提供要求的形状 / 尺寸选择的催化剂。在转移进象氢那样的另外的交通燃料的全球努力， MOF 用作精力存储媒介。在对环境污染的战斗，沸石不仅参加有害物质的俘获和消退，而且为许多工业过程提供环境地良性的选择。在这评论，为现在和将来的应用的沸石和 MOF 的合成和利用上的一个工业观点被介绍。

A new strategy for the fabrication of covalent organic framework‐metal‐organic framework hybrids via in‐situ functionalization of ligands for improved hydrogen evolution reaction activity

The development of novel porous materials have attracted significant attention owing to its possible application in several fields.In this study,we designed a novel covalent organic framework‐metal‐organic framework(COF‐MOF)material through an in‐situ ligand self‐assembly method.The in‐situ modified ligands not only act as nucleation sites to form Ti‐MOF,but also as a channel to rapidly transfer photogenerated electrons without introducing additional chemical bonds.The photocatalytic hydrogen production rate achieved over B‐CTF‐Ti‐MOF(1:1)was 1975μmol·g^(–1)·h^(–1) with an apparent quantum efficiency of 4.76%,which is 11.8 times higher than that of the pure CTF‐1.In addition,compared with the sample prepared by separating the ligands(CTF‐1/Ti‐MOF),B‐CTF‐Ti‐MOF shows excellent activity and stability.Finally,a reasonable photocatalytic mechanism was proposed using the results of electrochemical tests and spectral analyses.This study provides a universal method for the construction of highly efficient and stable COF/MOF materials with excellent properties.

Plasma-assisted Co/Zr-metal organic framework catalysis of CO_(2)hydrogenation:influence of Co precursors

In this study,Co/Zr-metal organic framework(MOF)precursors were obtained by a roomtemperature liquid-phase precipitation method and the equivalent-volume impregnation method,respectively,using a Zr-MOF as the support,and Co/Zr-MOF-M and Co/Zr-MOF-N catalysts were prepared after calcination in a hydrogen-argon mixture gases(VAr:V_(H_(2))=9:1)at 350℃for 2 h.The catalytic activities of the prepared samples for CO_(2)methanation under atmosphericpressure cold plasma were studied.The results showed that Co/Zr-MOF-M had a good synergistic effect with cold plasma.At a discharge power of 13.0 W,V_(H_(2)):VCO_(2)=4:1 and a gas flow rate of 30 ml·min^(-1),the CO_(2)conversion was 58.9%and the CH4 selectivity reached 94.7%,which was higher than for Co/Zr-MOF-N under plasma(CO_(2)conversion 24.8%,CH4 selectivity 9.8%).X-ray diffraction,scanning electron microscopy,transmission electron microscopy,N_(2)adsorption and desorption(Brunauer-Emmett-Teller)and x-ray photoelectron spectroscopy analysis results showed that Co/Zr-MOF-M and Co/Zr-MOF-N retained a good Zr-MOF framework structure,and the Co oxide was uniformly dispersed on the surface of the Zr-MOF.Compared with Co/Zr-MOF-N,the Co/Zr-MOF-M catalyst has a larger specific surface area and higher Co^(2+)/Cototaland Co/Zr ratios.Additionally,the Co oxide in Co/ZrMOF-M is distributed on the surface of the Zr-MOF in the form of porous particles,which may be the main reason why the catalytic activity of Co/Zr-MOF-M is higher than that of Co/ZrMOF-N.

H₂and CH₄Sorption on Cu-BTC Metal Organic Frameworks at Pressures up to 15 MPa and Temperatures between 273 and 318 K

Sorption isotherms of methane and hydrogen on Cu3(BTC)2 have been measured in the temperature range from 273 to 318 K and at pressures up to 15 MPa. H2 excess sorption capacities of the Cu3(BTC)2 amounted to 3.9 mg/g at 14 MPa. Promising maximum CH4 excess sorption capacities on the same sample were reached at approximately 5 MPa. They amounted to 101, 100, 92 and 80 mg/g at 273, 278, 293 and 318 K, respectively. The sorbed phase density was essestially the same for all temperatures and amounted to ~600 kg/m3. Structural changes of the Cu3(BTC)2 samples after thermal activation and treatment with high pressure H2 and CH4 were tested. It was found that the initial micropore structure has virtually disappeared as evidenced by a decrease of the Langmuir specific surface area by a factor ~3 and CO2 micropore volume by a factor of ~4 for H2 and ~3 for CH4. This is in line with an increase in the average pore diameter from initially 9.2 to 15.7 for H2 and 12.8 for CH4.

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.

金属有机骨架(MOFs)基复合质子交换膜的研究进展

近年来,金属有机骨架(MOFs)材料由于具有超大的比表面积和丰富的孔道结构,作为一种新型的质子导体在质子交换膜中的应用受到越来越多的关注。随着研究的不断深入,为进一步提升MOFs复合质子交换膜的各项性能,MOFs材料在质子交换膜中的物理形态逐渐由颗粒状向连续相发展,MOFs材料的组分也呈现出由单一组分到双组分的发展态势。本文以质子交换膜中MOFs材料的物理形态为主线,将其划分为MOFs晶体/聚合物质子交换膜、第三相增强MOFs/聚合物复合质子交换膜和MOFs纳米纤维/聚合物复合质子交换膜,全面综述了MOFs材料在质子交换膜中的研究进展,并对MOFs复合质子交换膜的发展方向进行了展望。

Synthesis of spherical tremella-like Sb2O3 structures derived from metal-organic framworks and its lithium storage properties

A novel spherical tremella-like Sb2O3 was prepared by using metal-organic frameworks(MOFs)method under a mild liquid-phase reaction condition,and was further employed as an anode material for lithium-ion batteries(LIBs).The effect of reaction temperature and time on morphologies of Sb2O3 was studied.The results from SEM and TEM demonstrate that the tremella-like Sb2O3 architecture are composed of numerous nanosheets with high specific surface area.When the tremella-like Sb2O3 was used as LIBs anode,the discharge and charge capacities can achieve 724 and 446 mA·h/g in the first cycle,respectively.Moreover,the electrode retains an impressive high capacity of 275 mA·h/g even after 50 cycles at 20 mA/g,indicating that the material is extremely promising for application in LIBs.

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。

MOFs基微流控电化学芯片对多种重金属离子的实时在线检测

将具有丰富微孔的ZIF-8金属有机框架和电化学技术对金属离子的富集作用与微流控器件对溶液流动的可控性相结合,构建了一种新型传感器,实现了高通量、实时和快速检测环境中的多种金属离子污染物.研制的ZIF-8-Nafion/ITO基微流控电化学传感器对Cd^(2+),Pb^(2+)及Hg^(2+)离子在0.1~100μmol/L的浓度范围内具有良好的线性关系,检出限分别为0.055,0.0025及0.0016μmol/L(S/N=3).该微流控芯片对于样品的需求量少,可降低对能源的消耗;同时由聚二甲基硅氧烷拓印的微流控器件还有望实现柔性电极的功能,对便携式电化学柔性器件在生物和环境样品的集成化和自动化检测具有重要意义.

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。

金属有机框架材料(MOFs)的电子束辐射稳定性

本研究在不同气氛(空气、氮气)、分散液(水、甲醇、乙醇)以及不同剂量条件下对4种典型的金属有机框架材料(MOFs)(MIL-101(Cr)、ZIF-8、UiO-66和UiO-66-NH2)进行了电子束辐照处理。通过傅里叶变换红外光谱、X射线衍射谱和扫描电子显微镜等方法对MOFs材料在辐照前后的化学组成、晶体结构和表面形貌进行表征。结果表明,上述4种MOFs材料在高于5000 kGy的剂量辐照后,其相应的红外特征峰、衍射峰和表面形貌特征均未产生显著变化,表现出了良好的辐射稳定性。这为MOFs材料在辐射环境下的进一步应用提供了研究基础。

聚合物基MOFs复合材料抗菌研究进展

金属有机骨架(MOFs)是一类备受瞩目的新兴材料,在抗菌领域有着广泛的应用。将聚合物与MOFs进行复合制备聚合物基MOFs(PolyMOFs)复合材料,不仅可以增强MOFs的稳定性、机械强度等,还可以进一步扩展其应用范围。该文重点综述了PolyMOFs复合材料在抗菌方面的研究进展,概述了功能性MOFs的制备和主要抗菌机制,以及PolyMOFs复合材料的制备方法;总结了具有抗菌功能的PolyMOFs复合材料在医疗健康、食品保鲜、空气净化、水污染防治、纺织品防护领域的应用;最后对具有抗菌功能的PolyMOFs复合材料目前在抗菌领域面临的挑战和未来包括特定功能增强、制备工艺优化和应用领域拓展等方面的发展方向进行了展望。

基于组分设计的MOFs衍生碳基吸波材料的研究进展

金属有机骨架(MOFs)具有孔隙率高、比表面积大等特点,其衍生物重量轻、带宽宽、损耗能力强,具有有序规整以及易设计性的组分结构而被广泛用于电磁波吸收研究。总结了单金属、双金属及金属氧化物MOFs碳基吸波材料作为微波吸收材料的性能、优势及其在电磁波吸收方面的应用等,分析了不同组分和组分设计对电磁波吸收性能的影响。尽管还面临许多的挑战,但MOFs衍生物作为电磁波吸收材料显示出广阔的发展潜力。