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.

Recent Progress on Engineering Highly Efficient Porous Semiconductor Photocatalysts Derived from Metal–Organic Frameworks

Porous structures o er highly accessible surfaces and rich pores, which facilitate the exposure of numerous active sites for photocatalytic reactions, leading to excellent performances. Recently, metal–organic frameworks(MOFs) have been considered ideal precursors for well-designed semiconductors with porous structures and/or heterostructures, which have shown enhanced photocatalytic activities. In this review, we summarize the recent development of porous structures, such as metal oxides and metal sulfides, and their heterostructures, derived from MOF-based materials as catalysts for various light-driven energy-/environment-related reactions, including water splitting, CO_2 reduction, organic redox reaction, and pollution degradation. A summary and outlook section is also included.

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。

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。

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。

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。

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。

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.

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.

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.

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.

Carbon-based derivatives from metal-organic frameworks as cathode hosts for Li–S batteries

Lithium-sulfur batteries(Li–S batteries) are promising candidates for the next generation high-energy rechargeable Li batteries due to their high theoretical specific capacity(1672 m Ahg-1) and energy density(2500 Wh kg-1). The commercialization of Li–S batteries is impeded by several key challenges at cathode side, e.g. the insulating nature of sulfur and discharged products(Li2S 2 and Li2S), the solubility of long-chain polysulfides and volume variation of sulfur cathode upon cycling. Recently, the carbonbased derivatives from metal-organic frameworks(MOFs) has emerged talent in their utilization as cathode hosts for Li–S batteries. They are not only highly conductive and porous to enable the acceleration of Li +/e-transfer and accommodation of volumetric expansion of sulfur cathode during cycling, but also enriched by controllable chemical active sites to enable the adsorption of polysulfides and promotion of their conversion reaction kinetics. In this review, based on the types of MOFs(e.g. ZIF-8, ZIF-67, Prussian blue, Al-MOF, MOF-5, Cu-MOF, Ni-MOF), the synthetic methods, formation process and morphology, structural superiority of MOFs-derived carbon frameworks along with their electrochemical performance as cathode host in Li–S batteries are summarized and discussed.

CNT@Ni-MOFs的制备及其在超级电容器中的应用

金属有机骨架(MOFs)材料因其具有较高的比表面积和结构功能多样性而在超级电容器中具有广阔的应用前景。通过溶剂热法制备电化学性能优异的碳纳米管@镍基金属有机骨架(CNT@Ni-MOFs)复合材料。使用X射线衍射、扫描电子显微镜及X射线光电子能谱对其成分和结构进行表征,研究结果表明:CNT@Ni-MOFs结构是由柔性CNT连接着棒状结构的Ni-MOFs形成的导电网络结构,其棒状结构的Ni-MOFs直径约0.5μm,长度为4~5μm。研究了反应时间对CNT@Ni-MOFs结构和电化学性能的影响,结果表明:当反应时间为12 h时,Ni-MOFs生长完整且均匀,Ni-MOFs颗粒数量适中且均匀负载于CNT上,同时还减少了团聚发生。CNT@Ni-MOFs复合电极具有比单独Ni-MOFs更好的比电容性能,其中CNT@Ni-MOFs12在电流密度1 A/g下的比电容达到719.8 F/g,而Ni-MOFs的比电容仅为87.1 F/g,且CNT的比电容也仅仅为43.5 F/g。此外,扫描速率为200 mV/s下,CNT@Ni-MOFs12电极材料经1 000次的线性伏安循环测试后其比电容保持率为96.8%。

Fe-MOFs衍生碳基吸波材料研究进展

随着社会的快速发展和电子设备的普及,电磁辐射污染问题变得尤为突出,也带来了潜在的危害。因此,开发高效的电磁波吸收材料以解决电磁辐射污染问题迫在眉睫。铁基金属有机框架(Fe-MOFs)具有高度不饱和的铁金属中心离子和多样的结构类型。通过将Fe-MOFs作为前驱体进行碳化,可以制备出铁/铁氧化物/铁碳化物均匀分布的衍生碳基化合物。这些Fe-MOFs衍生碳基化合物表现出较高的介电损耗和磁损耗能力,可有效克服当前吸波材料存在的吸收频带窄、阻抗匹配性差等问题,成为近年来备受关注的一种新型吸波材料。首先简要介绍了电磁波吸收机制,然后综述了近年来关于单金属、双金属、三金属Fe-MOFs以及由Fe-MOFs与其他材料(包括碳材料、导电聚合物、MXene和生物质)复合制备的衍生碳基吸波材料的研究进展,最后对MOFs衍生碳基吸波材料的未来发展方向进行了展望。

PDMS/Cu-MOFs超疏水织物的制备及性能

以三水合硝酸铜和和1,3,5-苯羧酸为前驱体,在棉织物表面原位生长铜基金属有机框架(Cu-MOFs),赋予棉织物表面一定的粗糙结构,同时借助聚二甲基硅氧烷(PDMS)的疏水整理,制备了具有优异的油水分离能力的超疏水织物。利用扫描电子显微镜(SEM)、傅里叶变换红外光谱(FTIR)和X射线衍射仪(XRD)等对超疏水棉织物表面形貌、结构及组成进行表征,并进行相关性能测试。结果显示:超疏水棉织物不仅具有出色的抗紫外性能,同时也具有良好的自清洁和油水分离性能。在油水分离测试中,对不同种类的油的分离效率均能达到95%以上。

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.

载阿霉素光响应纳米锆基MOFs构建及细胞毒性研究

为了克服乳腺癌治疗药物阿霉素存在毒副作用大、作用时间短等限制,本研究采用含偶氮苯侧链结构的联苯羧酸与Zr4+构建了一种新型光响应纳米金属有机框架(U67-AZO-COOH)作为药物载体,成功地将阿霉素负载其中。通过粉末X射线衍射、扫描电镜、傅里叶变换红外光谱、全自动比表面及孔隙度分析等技术手段对其结构进行了详细表征,得到在紫外光照射下阿霉素的载药率可由18.57%降至7.31%。体外释放实验和细胞毒性实验结果表明,该纳米药物复合物具有高载药量、良好的生物相容性,其在微酸环境下的释放率57.02%高于生理条件39.26%,表现出显著的缓释效果,能够减少对正常细胞的损害,存活率从39.88%提高到81.73%。这为新型光响应纳米金属有机框架在药物传递领域的广泛应用提供了新的可能性。

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.

高模量碳纤维表面双金属MOFs结构的构筑

经高温热处理制备得到的碳纤维具有高惰性表面结构,导致其与基体之间的润湿性较差。为了改善碳纤维与基体间的界面性能,本研究通过采用阴极电沉积法在高模量碳纤维表面原位生长金属有机框架(MOFs)材料,在纤维表面同时引入两种不同金属元素,研究双金属MOFs的引入机制、形貌及其对性能的影响。结果表明:双金属MOFs材料呈一定取向的绣球状形貌,经退火后演变成疏松多孔结构,该结构可显著提高高模量碳纤维表面粗糙度及界面黏结性;双金属MOFs的成核与生长取决于金属还原性,还原性越强、MOF生长速率更快,且沉积量更高;双金属MOFs结构的引入使得纤维电阻率下降至0.05×10^(−5)Ω∙cm,导电性能提升,独特的三维多孔结构也赋予高模量碳纤维高温环境下优异的热稳定性。

MOFs耦合木材复合材料在环境修复方面应用研究进展

在中国积极倡导“绿水青山就是金山银山”的绿色发展理念下,开发高效、低成本、零污染的先进可循环污染物去除技术,对于实现“绿水青山”目标至关重要。然而,当前主流的污染物去除技术,如活性炭吸附、高级氧化、膜分离等,虽具备成本优势,却常伴随去除效率低、能耗高及二次污染等问题。在此背景下,以纳米材料为核心的环境纳米技术(涵盖吸附、催化、膜分离等领域)凭借其高效性和功能多样性,在环境修复领域引发了广泛关注。金属有机骨架材料(MOFs)作为一类由金属离子与有机配体构筑的、具有1~3维结构的多功能晶态材料,因其有序的孔道结构、丰富的化学组成及高比表面积,在环境修复领域展现出良好的应用前景。然而,MOFs的粉末形态及其固有的易碎性、不宜加工性及低相容性,限制了其在回收、成型等方面的应用,从而阻碍了其在实际场景中的广泛推广。生物质材料,特别是木材,因其种类丰富、成本低廉及天然的高孔隙率等特性,在环境修复领域备受青睐。木材的多维孔道结构、丰富的羟基/羧基官能团以及良好的加工性能,使其成为固定粉末状MOFs的理想载体。近年来,国内外学者利用木材的这些本征特性,将MOFs作为新型载体,引入功能化纳米粒子或非均相催化剂等活性组分,构建了一系列新型复合结构体系,这些体系在木材、纤维素、凝胶等生物质及其衍生物基复合材料的制备和生物质催化转化中展现出巨大潜力。本文系统阐述了MOFs与木材的耦合策略,包括混合浸泡法、真空浸渍法、溶剂热法及原位生长法等,并深入解析了MOFs负载于木材表面形成MOFs/木材复合材料的机理,如物理吸附、润湿作用、毛细现象及构造成核位点等。同时,梳理并总结了当前MOFs材料在生物质及其衍生化学品领域的研究进展,重点讨论了MOFs/木材复合材料在气相污染物吸附、重金属离子去除、有害颗粒物过滤及高级氧化等环境修复领域的应用现状,并阐明了MOFs微观结构设计与复合材料宏观性能之间的内在联系。最后,展望了MOFs/木材复合材料未来发展所面临的机遇与挑战,为构建面向环境实际应用的MOFs基复合材料提供了新视角,有望进一步推动其在环境修复领域的广泛应用。