聚合物载体上合成金属有机骨架材料MOF-5的研究

研究了在尼龙66滤膜载体上MOF-5晶体的合成。考察了合成方法及反应物配比对MOF-5晶体性能的影响,采用SEM、XRD和TGA分析技术对所制备的样品进行了表征。研究结果表明,尼龙66滤膜可以作为MOF-5晶体生长的良好载体,且在反应温度130℃、反应时间4 h的条件下,当硝酸锌/对苯二甲酸的摩尔比在2.0∶1.0～2.5∶1.0时,通过溶剂热法可以在尼龙66滤膜载体上合成结构规整、呈立方体形态、晶体大小（〈50μm）和分布都较小的MOF-5晶体。     

不同方法合成金属有机骨架材料MOF-5的比较研究

针对金属有机骨架材料MOF-5的制备,采用了水热合成法、直接加入法以及在直接法中额外滴加H₂O₂的3种方法分别合成MOF-5晶体。利用X射线衍射仪（XRD）、扫描电子显微镜（SEM）、傅里叶红外光谱仪（FTIR）以及热重分析仪（TG）等仪器对MOF-5晶体进行了表征。研究了不同合成方法对其结构、形貌及热稳定性等性质的影响。结果表明：3种方法所制备的晶体XRD衍射峰与文献中MOF-5晶体的特征峰相符,即均可合成MOF-5晶体。但SEM、FTIR以及TG结果表明：水热法合成的晶体具有粒径较小和结构规则的特点,但热稳定性较差;其余2种方法合成的产物为微米级无规则聚集状晶体,与水热法相比晶体性质有一定差异。此外,滴加H₂O₂有助于晶粒的快速形成以及晶粒分散。     

金属有机骨架材料UiO-66的制备及表征

以氯化锆为金属盐,对苯二甲酸为有机配体,N,N-二甲基甲酰胺为有机溶剂,采用溶剂热法制备Ui O-66。通过考察金属盐、有机溶剂、有机配体、晶化温度、晶化时间的影响,确定出的优化合成条件为:n(金属盐)/n(有机配体)为1.0、n(有机溶剂)/n(有机配体)为25、晶化温度为100℃、晶化时间为25 h。在此条件下,可合成出相对结晶度较高的Ui O-66。     

MIL-53(Fe)金属有机骨架材料对刚果红的高效吸附

通过水热法制备规则外形的MIL-53(Fe)金属有机骨架材料(MOF),并通过傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、扫描电镜(SEM)和透射电镜(TEM)对材料进行表征。以刚果红作为目标物,研究所制得的MOF材料对其的吸附行为。结果表明,MIL-53(Fe)对刚果红的吸附动力学符合准二级动力学,吸附模型符合Langmuir吸附模型。MIL-53(Fe)材料对刚果红的最大吸附量为1 482 mg/g,是可望用于去除染料废水刚果红的高效吸附材料。     

金属有机框架材料M-MOF-74(M=Ni、Co、Fe)的制备及表征

以金属氧化物(Ni O、CoO、Fe O)和2,5-二羟基对苯二甲酸(H4(dhbdc))为原料,采用溶剂热法制备M-MOF-74(M=Ni、Co、Fe)。经X射线衍射(XRD)测定证明产物具有良好晶体结构,通过扫描电镜(SEM)观察产物晶体颗粒大小和外貌,通过比表面积测定仪(BET)测定产物的比表面积,Ni-MOF-74为1114m~2/g,Co-MOF-74为1238m~2/g,Fe-MOF-74为1050m~2/g。     

烧结金属有机骨架材料制备多孔材料及其应用

金属有机骨架材料(MOFs)作为近十年来新兴的配位化合物,具有有序的孔道结构、大比表面积、高的空隙率和,其结构和性质可调性,可应用于气体储存和分离、催化等方面。但是由于MOFs相对较差的稳定性,其大规模工业应用受到限制。目前,研究们试图将其这一缺点利用起来,如将MOFs进行烧结,将裂解后的材料用于气体吸附、电化学催化、锂电池、传感器、燃料电池中的氧气还原反应等等方面。本文对烧结MOFs制备多孔材料及其应用进行了归纳总结。     

金属有机骨架材料研究进展

近年来,金属有机骨架材料作为新型多功能材料的出现,在工业领域和学术界吸引了相当多的关注。它相比于传统的多孔材料,具有拓扑结构丰富,比表面积大的优点,又同时兼具有可设计,可剪裁,功能化容易的特点,在发光,分离,储气,催化,传感器及生物化学等领域有广阔的应用前景。在文章中,主要对金属有机骨架材料研究进展进行综述,此外,还介绍了MOFs材料作为功能材料的前言发展和在设计合成中的应用。     

金属有机骨架材料(MOFs)基催化剂在加氢反应中的研究进展

加氢是精细化学品生产过程中一类重要的反应。在加氢反应中,高活性和高选择性催化剂的设计是关键因素也是面临的巨大挑战。近年来,金属有机骨架材料(MOFs)由于其比表面积大、孔道尺寸可调和活性点位负载方式多样等特点被广泛应用于加氢催化剂的制备中。从MOFs基催化剂在不饱和烃的加氢反应、醛的加氢反应和CO₂加氢反应3个方面的应用出发,综述MOFs基催化剂在加氢反应中的研究现状和存在的问题,并对MOFs基催化剂在加氢领域的发展方向进行展望。     

金属有机骨架材料的制备及其吸附应用

金属有机骨架材料（MOFs）是利用配位键自组装金属离子和有机配体形成的一类新型骨架材料。近年来,MOFs材料研究受到科研人员的广泛关注,其应用范围也越来越广泛。论述了常见的MOFs材料的制备方法,并系统介绍了MOFs材料在有机物吸附方面,尤其是染料吸附、抗生素去除及天然产物提取分离等领域的应用。通过文献调研,论文对MO...     

金属有机骨架材料(MOFs)优化方法综述

金属有机骨架材料(MOFs)是由金属离子(簇)与有机配体通过配位键形成的一类有机-无机杂合多孔晶体材料,由于其巨大的比表面积、密度低、可调的结构等优良性能,在吸附、分离、催化等方面应用广泛,为了不断提高该材料的应用效果,可以对材料进行特殊处理。本文论述了三种方法去优化其性能,第一种是金属掺杂和修饰金属离子,第二种是官能团修饰有机配体,第三种是将金属有机骨架材料与功能性材料复合。     

Green Electro-Synthesized MIL-101(Fe) and Its Aspirin Detoxification Performance Compared to MOF-808

In this research, the performance of metal–organic frameworks (MOFs) of MIL-101(Fe) and MOF-808 as aspirin detoxification agents was evaluated. MIL-101(Fe) was successfully prepared for the first time using the electrochemical method for 30 min under room temperature and pressure. MIL-101(Fe) detoxification capacity was compared to that of MOF-808, which was synthesized by a common solvothermal method at 135 °C for 24 h. The obtained materials were fully confirmed by X-ray diffraction (XRD) with the appearance of MIL-101(Fe) characteristic peaks (at 2θ 8.5°; 9°;16.7°) and MOF-808 (at 2θ 8.3°; 8.7°; 10°; 10.9°), and also confirmed by Fourier transform infrared (FTIR) spectroscopy that shows the coordination between metal and ligand. Based on scanning electron and transmission electron microscopy (SEM and TEM), MIL-101(Fe) has a micro-spindle shape with average particles size of 649.12?±?73.32 nm, while MOF-808 showed irregular shape with average particle sizes of 169.73?±?31.87 nm. Nitrogen sorption isotherm confirmed that both materials could be classified as micro to-meso porous materials by the pore radius of 1.89 nm for each materials with BET surface areas of 131 for MIL-101(Fe), and 847 m²/g for MOF-808, respectively. Based on an in vitro test, in a gastric simulation, MIL-101(Fe) decreased 11.78% of aspirin, while MOF-808 decreased 7.99%. In the intestinal simulation, MIL-101(Fe) and MOF-808 decreased aspirin by 24.06% and 26.74%, respectively. XRD analysis of the MOFs after the detoxification test showed that MIL-101(Fe) has lower stability than MOF-808. FTIR spectra confirmed that aspirin was successfully adsorbed into the MOFs. Transmission electron microscopy showed that aspirin interacted with MIL-101(Fe) on the outer surface and with MOF-808 on the inside of the pores.

Graphical Abstract

     

MOF-808@PAN纳米纤维制备及其降解芥子气模拟剂性能

芥子气（HD）是难降解可致死的最广泛使用的化学战剂,锆基金属有机框架材料（Zr-MOFs）MOF-808对其有很好的降解效果。但现阶段研究MOF-808对HD的降解多以粉末态使用,易团聚难回收,为解决此问题,研究使用静电纺聚丙烯腈（PAN）来固定回收MOF-808,并验证了MOF-808@PAN对芥子气有优异的降解效果。以ZrOCl2、均苯三甲酸为原料,三氟乙酸为调节剂,基于水为溶剂无模板的合成了MOF-808@PAN纳米纤维材料。采用SEM、XRD、FTIR、TG及氮气吸脱附对催化剂结构进行了表征。实验结果表明,MOF-808@PAN纳米纤维具有441.5m2/g的比表面积。在5μL芥子气模拟剂（CEES）下暴露20个小时,CEES的降解效率可达83.7%。为芥子气的降解提供另一解决思路。     

Pd Nanoparticles Embedded Into MOF-808: Synthesis,Structural Characteristics,and Catalyst Properties for the Suzuki–Miyaura Coupling Reaction

Catalysis Letters - A heterogeneous single-site catalyst Pd@MOF-808 was successfully synthesized by water-based, green synthesis procedure. The catalytic experiments exhibited the Pd@MOF-808...     

Hydrogen adsorption on metal-organic framework (MOF-5) synthesized by DMF approach

Metal-organic frameworks (MOFs), especially MOF-5, are believed to be promising new porous materials for hydrogen adsorption. A comparative study of material synthesis, characterization and hydrogen adsorption was performed to examine the effects of different synthesis conditions on crystal structure, pore textural property and hydrogen adsorption performance of MOF-5 materials. Three MOF-5 samples synthesized with dimethyl formamide (DFM) as solvent and slightly different procedures have shown similar phase structure and chemical composition, diverse crystal structures, varying pore textural properties and different hydrogen adsorption performance. It was established from the experimental results that higher order of crystallinity in the MOF-5 materials generates better adsorbents with larger crystal size, higher specific surface area, uniform pore size distribution (PSD), larger hydrogen adsorption capacity and faster hydrogen diffusion rate in MOF-5 adsorbents. The best MOF-5 sample synthesized in this work (MOF-5(γ)) has a Langmuir specific surface area of 1157 m²/g; it can adsorb 0.5 wt.% of hydrogen at 77 K and 800 mmHg; and results in hydrogen diffusivity inside MOF-5 crystal of 2.3 × 10⁻⁹ cm²/s. The density functional theory reasonably predicts the presence of mesopores and macropores in all three MOF-5 samples synthesized in this work.     

808VAE增强型乳液的研制

介绍了一种复合交联制备VAE增强乳液的方法。在乳液聚合过程中,以AP-02为保护胶、以丙烯酸乙酯、醋酸乙烯为软硬单体,同时添加适量的交联单体NMAM和AA等参与共聚;重点讨论了AP-02、NMAM和AA及反应温度对乳液聚合及性能的影响。实验结果表明:以EA、VAC为软硬单体、交联单体NMAM用量为总投料量的0.8%、AA为总投料量的0.5%,保护胶用量为总投料量的1.2%、反应温度为75~80℃,聚合反应平稳,制得的乳液成本低廉,性能优异,与进口VAE增强乳液均能满足产品的使用要求,并且无明显差异。     

A comparison of hydrogen storage in activated carbons and a metal-organic framework (MOF-5)

A hydrogen storage study, on gravimetric and volumetric bases, has been carried out on three adsorbents having similar adsorption capacities: two activated carbons and a metal organic framework (MOF-5). These three samples have similar hydrogen storage on a gravimetric basis. However, expressed on a volumetric basis, both AC have higher hydrogen storage than MOF-5. Wrong conclusions could be avoided, when comparing these two types of adsorbents, if their hydrogen storage data were reported on a volumetric basis, using reliable measurable densities. Tap or packing densities are the most suitable. Crystal density, mostly used for reporting hydrogen storage on MOF, gives unrealistically high volumetric storage values.     

La0．8Ba0．2MnO3纳米晶的制备与表征

用溶胶-凝胶法制备了La0.8Ba0.2MnO3纳米粉体材料,对样品的凝胶进行热差热熏和红外光谱分析,结果表明,凝胶的加热煅烧过程中可以分为脱吸附水、有机物分解、硝酸根分解和钙态矿形成四个阶段。X射线衍射分析表明它是单一的钙态矿结构,扫描电子显微镜分析表明粉体呈球形巍径约80nm。     

Novel (Zr,Ti)B2-(Zr,Ti)C-SiC ceramics via reactive hot pressing

Fully dense (Zr, Ti)B₂-(Zr, Ti)C-SiC ceramics were prepared by reactive hot-pressing using ZrB₂, TiC, and SiC as the initial materials for the first time. Effects of SiC addition on the microstructure evolution and mechanical properties were reported. The in-situ reaction between ZrB₂ and TiC as well as the SiC addition leads to the grain refinement. Besides, elongated (Zr, Ti)B₂ plate-like grains are obtained due to the occurrence of a transient liquid phase, which leads to the crack deflection in the matrix effectively. Mechanical properties are improved significantly due to grain-refinement and solid solution strengthening, and plate-like grains toughening effects. The ZrB₂-10 mol%TiC composite with 10 mol% SiC additional exhibits good comprehensive mechanical properties of the hardness of 20.2 GPa, the flexural strength of 803 MPa, and the fracture toughness of 5.7 MPa m^1/2.     

Screening of ATP hydrolysis by Zr(IV) and Eu(III) complexes

The dephosphorylation of adenosine triphosphate (ATP) by various zirconium (IV) and europium (III) complexes is described. Release of phosphate was followed by an automated, robotics-based colorimetric assay which is compatible with the presence of these high-valent metal ions.