A Thorium Metal-Organic Framework with Outstanding Thermal and Chemical Stability

A new thorium metal-organic framework (MOF), Th(OBA)₂, where OBA is 4,4′-oxybis(benzoic) acid, has been synthesized hydrothermally in the presence of a range of nitrogen-donor coordination modulators. This Th-MOF, described herein as GWMOF-13, has been characterized by single-crystal and powder X-ray diffraction, as well as through a range of techniques including gas sorption, thermogravimetric analysis (TGA), solid-state UV/Vis and luminescence spectroscopy. Single-crystal X-ray diffraction analysis of GWMOF-13 reveals an interesting, high symmetry (cubic Ia d) structure, which yields a novel srs-a topology. Most notably, TGA analysis of GWMOF-13 reveals framework stability to 525 °C, matching the thermal stability benchmarks of the UiO-66 series MOFs and zeolitic imidazolate frameworks (ZIFs), and setting a new standard for thermal stability in f-block based MOFs.     

High-Porosity Metal-Organic Framework Glasses

We report a synthetic strategy to link titanium-oxo (Ti-oxo) clusters into metal-organic framework (MOF) glasses with high porosity though the carboxylate linkage. A new series of MOF glasses was synthesized by evaporation of solution containing Ti-oxo clusters Ti₁₆O₁₆(OEt)₃₂, linkers, and m-cresol. The formation of carboxylate linkages between the Ti-oxo clusters and the carboxylate linkers was confirmed by Fourier-transform infrared (FT-IR) spectroscopy. The structural integrity of the Ti-oxo clusters within the glasses was evidenced by both X-ray absorption near edge structure (XANES) and ¹⁷O magic-angle spinning (MAS) NMR. After ligand exchange and activation, the fumarate-linked MOF glass, termed Ti-Fum, showed a N₂ Brunauer–Emmett–Teller (BET) surface areas of 923 m² g⁻¹, nearly three times as high as the phenolate-linked MOF glass with the highest BET surface area prior to this report.     

一个基于偶氮六酸的稀土金属-有机框架

采用1,2,3-三羧基-(1′,2′,3′-三羧基偶氮苯)-苯(H₆TTAB)连接线性四核铕配位单元, 组装形成具有 {4¹⁴·6²⁰·8¹¹}{4³}₂{4⁵·6}拓扑结构的稀土金属-有机框架Eu-TTAB. Eu-TTAB具有高的热和溶剂稳定性, 在紫外光激发下具有发光性质, 且其发光性能可以被铽离子调控并被银离子大幅度提升.     

A Paramagnetic Compass Based on Lanthanide Metal-Organic Framework

Macroscopic compass-like magnetic alignment at low magnetic fields is natural for ferromagnetic materials but is seldomly observed in paramagnetic materials. Herein, we report a “paramagnetic compass” that magnetically aligns under ∼mT fields based on the single-crystalline framework constructed by lanthanide ions and organic ligands (Ln-MOF). The magnetic alignment is attributed to the Ln-MOF's strong macroscopic anisotropy, where the highly-ordered structure allows the Ln-ions’ molecular anisotropy to be summed according to the crystal symmetry. In tetragonal Ln-MOFs, the alignment is either parallel or perpendicular to the field depending on the easiest axis of the molecular anisotropy. Reversible switching between the two alignments is realized upon the removal and re-adsorption of solvent molecules filled in the framework. When the crystal symmetry is lowered in monoclinic Ln-MOFs, the alignments become even inclined (47°-66°) to the field. These fascinating properties of Ln-MOFs would encourage further explorations of framework materials containing paramagnetic centers.     

Separating Xylene Isomers with a Calcium Metal-Organic Framework

The purification of p-xylene (pX) from its xylene isomers represents a challenging but important industrial process. Herein, we report the efficient separation of pX from its ortho- and meta- isomers by a microporous calcium-based metal–organic framework material (HIAM-203) with a flexible skeleton. At 30 °C, all three isomers are accommodated but the adsorption kinetics of o-xylene (oX) and m-xylene (mX) are substantially slower than that of pX, and at an elevated temperature of 120 °C, oX and mX are fully excluded while pX can be adsorbed. Multicomponent column breakthrough measurements and vapor-phase/liquid-phase adsorption experiments have demonstrated the capability of HIAM-203 for efficient separation of xylene isomers. Ab initio calculations have provided useful information for understanding the adsorption mechanism.     

A Novel Aluminum-Based Metal-Organic Framework with Uniform Micropores for Trace BTEX Adsorption

Metal-organic frameworks (MOFs) are potential porous adsorbents for benzene, toluene, ethylbenzene and xylene (BTEX). A novel MOF, using low toxic aluminum (Al) as the metal, named as ZJU-620(Al), with uniform micropore size of 8.37±0.73 Å and specific surface area of 1347 m² g⁻¹, was synthesized. It is constructed by one-dimensional rod-shaped AlO₆ clusters, formate ligands and 4,4′,4′′-(2,4,6-trimethylbenzene-1,3,5-triyl) tribenzoic ligands. ZJU-620(Al) exhibits excellent chemical-thermal stability and adsorption for trace BTEX, e.g., benzene adsorption of 3.80 mmol g⁻¹ at P/P₀=0.01 and 298 K, which is the largest one reported. Using Grand Canonical Monte Carlo simulations and Single-crystal X-ray diffraction analyses, it was observed that the excellent adsorption could be attributed to the high affinity of BTEX molecules in ZJU-620(Al) micropores because the kinetic diameters of BTEX are close up to the pore size of ZJU-620(Al).     

一个具有eea拓扑和高甲烷存储量的金属有机骨架材料

合成了含有2个羧基和1个N配位点的双官能团有机配体5-（quinolin-6-yl）isophthalic acid （H₂L）,并成功制得一个新的三维的多孔金属-有机骨架{[CuL]·x（Solvent）}_n （1）。金属-有机骨架1具有eea拓扑的网络结构,点（Schläfli）符号为{4².6}₂{4⁴.6².8⁶.10³}。值得一提的是,除去溶剂分子的1还表现出较大的CH₄吸附焓,在298 K和高压下对CH₄有高的吸附量。     

功能金属-有机骨架材料的应用

金属有机骨架（Metal-Organic Framework,MOFs）材料由于其特殊的结构引起了科学家的广泛关注,它作为多孔材料与无机或有机的多孔材料相比具有特殊的优势,是目前新功能材料研究领域的一个热点。本文总结了金属有机骨架多孔材料在分离纯化、催化、微反应器、负离子交换、复合功能材料等方面的应用进展,并对这种新型多功能材料在设计、合成与应用方面的广阔前景作了展望。     

Controlled Thermal Release of L-Menthol with Cellulose-Acetate-Fiber-Shelled Metal-Organic Framework

Fragrances have been widely used in many customer products to improve the sensory quality and cover flavor defects. The key to the successful application of fragrance is to realize controlled fragrance release, which relies on the use of an appropriate carrier for fragrance. An ideal fragrance carrier helps to achieve the stable storage and controlled release of fragrance. In this work, a novel composite fragrance carrier with MIL-101 (Cr) as the fragrance host and cellulose acetate fiber (CAF) as the protective shell was developed. The encapsulation effect of MIL-101 (Cr) and the protective function of the CAF shell significantly improved the storage stability of L-menthol (LM). Only 5 wt % of LM was lost after 40 days of storage at room temperature. Encapsulated LM could also be effectively released upon heating due to the thermal responsiveness of CAF. In addition, the composite carrier was highly stable with neglectable Cr leaching under different conditions. The results of this work showed that the developed composite carrier could be a promising carrier for the thermally triggered release of fragrance.     

一个具有eea拓扑和高甲烷存储量的金属有机骨架材料

合成了含有2个羧基和1个N配位点的双官能团有机配体5-（quinolin-6-yl）isophthalic acid （H₂L）,并成功制得一个新的三维的多孔金属-有机骨架{[CuL]·x（Solvent）}_n （1）。金属-有机骨架 1具有eea拓扑的网络结构,点（Schläfli）符号为{4².6}₂{4⁴.6².8⁶.10³}。值得一提的是,除去溶剂分子的1还表现出较大的CH₄吸附焓,在298 K和高压下对CH₄有高的吸附量。     

Exploiting multi-function Metal-Organic Framework nanocomposite Ag@Zn-TSA as highly efficient immobilization matrixes for sensitive electrochemical biosensing

A novel multi-function Metal-Organic Framework composite Ag@Zn-TSA (zinc thiosalicylate, Zn(C₇H₄O₂S), Zn-TSA) was synthesized as highly efficient immobilization matrixes of myoglobin (Mb)/glucose oxidase (GOx) for electrochemical biosensing. The electrochemical biosensors based on Ag@Zn-TSA composite and ionic liquid (IL) modified carbon paste electrode (CPE) were fabricated successfully. Furthermore, the properties of the sensors were discussed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and amperometric current-time curve, respectively. The results showed the proposed biosensors had wide linear response to hydrogen peroxide (H₂O₂) in the range of 0.3–20,000 μM, to nitrite (NO₂⁻) for 1.3 μM–1660 μM and 2262 μM–1,33,000 μM, to glucose for 2.0–1022 μM, with a low detection limit of 0.08 μM for H₂O₂, 0.5 μM for NO₂⁻, 0.8 μM for glucose. The values of the apparent heterogeneous electron transfer rate constant (k_s) for Mb and GOx were estimated as 2.05 s⁻¹ and 2.45 s⁻¹, respectively. Thus, Ag@Zn-TSA was a kind of ideal material as highly efficient immobilization matrixes for sensitive electrochemical biosensing. In addition, this work indicated that MOF nanocomposite had a great potential for constructing wide range of sensing interface.     

1,3,5-均苯三羧酸根金属-有机多重框架结构配合物

综述了近年来1,3,5-均苯三羧酸(H3BTC)与金属配位形成金属配合物的研究进展。对1,3,5-均苯三羧酸根(BTC)作为桥基时的配位特点及其桥联多核配合物的合成方法和结构特点进行了简要介绍,并对今后BTC类超分子网络配合物应用与结构研究的发展方向进行了展望。     

一例对二硫化碳具有荧光传感性能的Mg-金属有机框架化合物

通过溶剂热合成了一例Mg-MOF化合物[Mg₄(1,4-NDC)₄(DMA)₂(CH₃OH)₂(H₂O)₂]·DMA·CH₃OH(1,1,4-H₂NDC=1,4-萘二酸,DMA=N,N'-二甲基乙酰胺),并对其结构表征及荧光性能进行了研究。 单晶X射线研究结果表明,化合物结晶于P2₁/c空间群,其晶体学数据为a=2.06090(12) nm, b=2.21014(13) nm, c=1.50385(10) nm, β=111.399(3)°, V=6.3776(7) nm³, Z=4, D_c=1.403 g/cm³, F(000)=2824, R=0.0596, wR=0.1225(I>2σ(I))。 化合物1中,二核的镁作为次级构筑单元通过桥连配体1,4-NDC连接形成沿c轴方向拓展的一维链。 一维链间进一步通过配体连接形成3D框架的化合物。 荧光性能研究表明,化合物1对CS₂具有灵敏的荧光传感性能,在0.4%的体积分数条件下可引起CS₂荧光的完全淬灭。 此外,化合物1的热稳定性也通过热重分析进行了研究,发现其可稳定到140 ℃左右。     

金属有机骨架材料的复合成型

金属有机骨架材料(MOFs)是由有机配体与金属离子(簇)配位而成的有序杂化多孔框架晶体材料,具有比表面积高、密度低、孔结构可调、配体可设计及易修饰等特性,已广泛应用于分离、催化、传感和药物递送等研究领域。MOFs本身以粉体形式存在,在实际应用中不易于加工处理和回收再利用,甚至会导致粉体污染。因此对MOFs粉末进行复合成型,制备成复合颗粒或者膜材料,有利于推进其工业应用。本文按照MOFs制备和成型的先后顺序,对MOFs复合微珠、薄膜和混合基质膜成型体的制备方法进行综述,对推进MOFs成型体的大规模制备以及开发新的MOFs成型方法提供技术参考。     

草酰胺功能化的荧光阴离子骨架及其对亚甲基蓝的选择性吸附

由于对人类和环境的严重威胁,染料的吸附已经引起研究工作者的广泛关注。 本论文中利用四齿配体5,5'-[oxalylbis(azanediyl)]diisophthalic acid(H₄L)成功地合成出了草酰胺功能化的阴离子骨架材料{[(CH₃)₂NH₂]₂(CdL)}·x(Solvent)(1)。 单晶X射线衍射分析表明化合物1具有二重穿插的三维骨架,(3,3,4)-连接的新拓扑网络结构和{8³}₂{8⁶}的点(施莱夫利)符号。 更有趣的是,它不仅对亚甲基蓝呈现出选择性的吸附行为,而且在可见光区具有荧光发光性质。     

A Two-Dimensional Semiconductive Metal-Organic Framework for Highly Efficient Microwave Absorption

Advanced microwave absorbing materials(MAMs)are urgently required to eliminate and attenuate microwaves to address the ubiq-uitous microwave radiations and inte...     

A Universal Synthesis Strategy for Tunable Metal-Organic Framework Nanohybrids**

Metal-organic frameworks (MOFs) with encapsulated nanoparticles (NPs) enjoy a vastly expanded application potential in catalysis, filtration, and sensing. The selection of particular modified core-NPs has yielded partial successes in overcoming lattice mismatch. However, restrictions on the choice of NPs not only limit the diversity, but also affect the properties of the hybrid materials. Here, we show a versatile synthesis strategy using a representative set of seven MOF-shells and six NP-cores that are fine-tuned to incorporate from single to hundreds of cores in mono-, bi-, tri- and quaternary composites. This method does not require the presence of any specific surface structures or functionalities on the pre-formed cores. Our key point is to regulate the diffusion rate of alkaline vapors that deprotonate organic linkers and trigger the controlled MOF-growth and encapsulation of NPs. This strategy is expected to pave the way for the exploration of more sophisticated MOF-nanohybrids.     

Fluorescence Ratiometric Antibiotic Detection with a Single Lanthanide Metal-Organic Framework

Antibiotic residues are currently an increasing threat for human health and the ecosystem, and specific and rapid real-time sensing of antibiotics is a big challenge. To realize specific sensing by rapid fluorescent sensors, a lanthanide metal-organic framework (MOF) containing dual emissive centers has been developed with high sensing selectivity and sensitivity. Owing to the self-calibration ability, the dual-center Tb-MOF exhibits higher selectivity towards furazolidone (FZD) and nitrofural (NZF) among the reported MOF sensors. Additionally, the corresponding ratiometric detection mode also realized specific sensing of other tested antibiotics. Besides, the single-Tb³⁺-based dual-emission MOF in this work is expected to support the development of fluorescent sensors with high sensitivity and selectivity for environmental safety purposes.