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,它具有结构可调、孔隙率高、比表面积大等特点,在抗菌领域有着广泛的应用。将MOFs材料与聚合物进行复合制备聚合物基MOFs (PolyMOFs)复合材料,不仅可以增强其稳定性、机械强度等,还可以进一步扩展它的应用范围。本文重点综述了聚合物基MOFs复合材料在抗菌方面的研究进展,包括MOFs材料的制备和主要抗菌机制及聚合物基MOFs复合材料的制备方法,并总结了聚合物基MOFs复合材料在医疗健康、食品保鲜、空气净化、水污染防治、纺织品防护领域的抗菌应用。最后,讨论了聚合物基MOFs复合材料在抗菌领域目前面临的挑战和未来发展的前景。     

Separation of Xenon and Krypton in the Metal–Organic Frameworks M2(m-dobdc) (M=Co,Ni)

The separation of Xe and Kr from air is challenging owing both to the very low atmospheric concentrations of these gases and the need for their distillation at cryogenic temperatures. Alternatively, separation processes based on adsorption could provide a less energy-intensive route to the isolation of these gases. Here, we demonstrate that the metal–organic frameworks M₂(m-dobdc) (M=Co, Ni; m-dobdc⁴⁻=4,6-dioxido-1,3-benzenedicarboxylate) effectively separate Xe and Kr at ambient temperatures based on the different adsorption enthalpies of each gas at the coordinatively-unsaturated M²⁺ sites in each material. In situ Xe- and Kr-dosed powder X-ray diffraction studies further reveal key differences in the binding of Xe and Kr within the materials. In particular, while both gases adsorb near the framework open metal sites at 200 K, much higher Xe occupancies are observed at these sites relative to Kr, corroborating a stronger interaction of the polarizing M²⁺ cations with Xe. Further, while krypton is only found located above the open metal sites, two additional adsorption sites are observed for xenon, correlating with the stronger adsorption of Xe over Kr in these materials. These results suggest the possible utility of employing M₂(m-dobdc) materials in the adsorptive separation of Xe and Kr.     

利用氧化铜室温下水蒸气辅助老化法合成MOF-505

以氧化铜与3,3’,5,5’-联苯四甲酸为原料,室温下分别以水、乙醇和N,N-二甲基甲酰胺(DMF)为溶剂,利用预盐湿磨法对于反应原料的混合物进行预研磨处理,再在不同的蒸汽(水、甲醇、DMF)中熏蒸辅助老化(VAG),制得VAG-MOF-505。结果显示,常温下乙醇预盐湿磨后配合水蒸气熏蒸20h即可得到高结晶度的VAG-MOF-505。利用PXRD、FTIR、TGA、SEM、BET对其进行结构表征与孔结构分析。SEM与PXRD结果显示,VAG-MOF-505具有与溶剂热法合成产品相似的结晶度。VAG-MOF-505的BET比表面积达到1281 m2/g,平均孔径为0.66 nm。该文为VAG法在MOFs的绿色大规模合成方面的应用提供了新的研究思路。     

Degree of crosslinking and mechanical properties of crosslinked poly(vinyl alcohol) beads for use in solid-phase organic synthesis

The limited swellability in polar media of the commonly used polystyrene/divinylbenzene (PS-DVB) support materials for solid-phase organic synthesis has led to the development of novel, highly swellable hydrophilic gels designed for use in aqueous or polar media. Poly(vinyl alcohol) beads crosslinked with epichlorohydrin (PVA-EP) were prepared by a two-step inverse-suspension polymerization method. While it is known that the morphology of the resulting beads can be controlled by the ratio of EP versus PVA as well as by the pre-crosslinking time, the actual degree of crosslinking of the beads and their mechanical properties remain unknown. It is therefore the purpose of this study to evaluate the actual degree of crosslinking of beads prepared with different quantities of crosslinker in the feed by spectroscopic (Raman, nuclear magnetic resonance) and chemical (functional group loading) methods. The mechanical properties of these swollen PVA-EP beads will be evaluated by single-bead unconfined compression in solvents such as water, N,N-dimethylformamide (DMF), and tetrahydrofuran (THF) and compared to model PS-DVB beads commonly used for solid phase synthesis.     

Zr系列MOFs催化乙酸乙酯N-酰胺化反应

以二氯氧锆（ZrOCl₂）和不同的有机配体,如对苯二甲酸、均苯三甲酸、1,2,4-苯三甲酸和1,2,4,5-苯四甲酸为原料,采用溶剂热法合成了一系列Zr基金属-有机框架（Zr-MOFs）材料。利用X射线粉末衍射（XRD）、氮吸附脱附等温线、傅里叶变换红外光谱（FTIR）、热重分析（TGA）和扫描电子显微镜（SEM）对材料进行一系列表征。以乙酸乙酯与苯甲胺反应转化为N-乙酰苄胺为模型反应,研究所得Zr-MOFs材料的催化性能。结果表明,Zr-MOFs材料的催化活性可以通过改变有机配体中羧酸基团的数目和位置来调控,有机配体中羧基数目主要影响Zr-MOFs材料的晶体结构以及Lewis酸性和Br?nsted酸性,从而影响催化活性。相同条件下,具有MOF-808晶体结构的Zr-MOF材料催化活性最高,80℃反应12h,N-乙酰苄胺的产率高达95%。此外,该催化剂具有良好的循环使用稳定性,重复使用5次后,N-乙酰苄胺的产率仍保持90%。     

发光金属有机框架的分子识别研究进展

发光稀土金属有机框架由于具有突出的发光特性,因此在光学材料以及识别领域有着巨大的应用价值。基于发光稀土金属有机框架的化学传感器具有易操作、反应快速、灵敏度高以及选择性好等优点,因此开展此领域的研究很有必要。本文概述了此领域的最新研究进展情况。     

Amberlite XAD-2 impregnated organophosphinic acid extractant for separation of uranium(VI) from rare earth elements

Amberlite XAD-2 resin was impregnated with Cyanex272 {bis (2,4,4-trimethylpentyl) phosphinic acid} and Cyanex302 {bis (2,4,4-trimethylpentyl) monothiophosphinic acid}. Systematic studies of Cyanex302 impregnated XAD-2 were carried out to develop optimum conditions for uranium(VI) sorption and devise its separation from rare earth elements. Amberlite XAD-2 impregnated with Cyanex302 had poor distribution coefficients for lanthanum(III) and neodymium(III) while uranium(VI) was quantitatively sorbed from 1×10–3 M HNO3 and was recovered with 1 M HCl from the solid phase. The method proposed is simple, selective and reproducible for determination of uranium(VI) with a relative standard deviation (RSD) of 0.4 %.     

分子印迹材料的制备与应用

分子印迹技术（molecularly imprinted technique,MIT）来源于免疫学、生物化学,是模拟生物体内抗体与抗原、酶与底物等分子之间的识别过程,是合成对某一种分子具有专一识别性的聚合物的方法。本文对分子印迹材料的合成方法——共价法、非共价法和半共价法等进行了综述,并介绍了分子印迹材料与技术在分析化学与生物领域的应用。     

Experimental based full process simulation of alumina selective laser processed parts densified by cold isostatic pressing and solid state sintering

The compound process of cold isostatic pressing (CIP) of alumina selective laser processed (SLP) parts and solid state sintering (SSS) and its full process simulation were realized in this paper, focusing on studying the overall deformation, relative density distribution, grain growth and sintering stress variation during the process. Especially, correlation was established between the macroscopic deformation and microscopic evolution. Model parameters for alumina are presented, which were optimized in accordance with the experimental results. CIPed part still exhibited density inhomogeneity, of which SSS tended to increase the overall density and homogenize density distribution. The sintering behavior was studied with the employment of dilatometer experiments. Furthermore, compared with conventional heating strategy, fast firing turned out to decrease sintering production time as well as drive the matter diffusion and densification process. The master sintering curve (MSC) moves upward a little under the condition of fast firing.     

金属有机骨架基复合相变储热材料研究进展

固-液相变材料的品种多且潜热大,是潜热储热技术的重要工作介质。因其存在的液相泄漏问题,现阶段常将此类相变材料与多孔载体复合以提升相变材料的应用性能及使用寿命。金属有机骨架（MOFs）是一种新型多孔材料,具有高比表面积、高孔隙率以及孔径和表面性质可调控等优势,将其用作相变材料的载体具有潜在的发展前景。本文对MOF基复合相变材料的研究进行了全面综述,详细介绍了以MOFs为载体、以MOFs衍生多孔碳为载体和以MOFs原位生长于高导热基体所得复合材料为载体而制得的多种复合相变材料。MOFs的微孔结构所产生的强毛细管力对固-液相变材料有很强的固定作用;制备较大孔径的MOFs或者对MOFs进行修饰以调节MOF与相变材料间的相互作用,都有利于提高相变材料的负载率,从而提升复合相变材料的潜热;对MOFs进行高温碳化处理得到MOFs衍生多孔碳能有效解决MOFs孔径过小的问题,并能通过对其进行氮掺杂或磷掺杂来增强载体与相变材料间的氢键作用,从而获得具有高负载率和相变潜热的复合相变材料;为了增强MOF基复合相变材料的导热性能,先将MOFs原位合成在高导热基体上以利用高导热基体提供连续的传热网络,可以有效提升复合相变材料的导热系数。将原位生长在高导热基体上的MOFs进行高温碳化处理可以得到MOFs衍生多孔碳与高导热基体的复合材料,将其作为载体可以进一步增强复合相变材料的导热性能。文中最后指出,今后对于MOF基复合相变储热材料所用MOFs和相变材料的种类、MOFs与相变材料间相互作用对储热性能的影响、MOFs与相变材料复合后的稳定性等方面还需进一步探索,将MOFs的催化、检测等功能与相变材料的储热控温功能相结合制备多功能材料也是未来的发展方向之一。     

基于MOFs材料的低碳烃（C1~C3）分离研究进展

低碳烃（C₁~C₃）混合物的分离和纯化是化工过程中最重要且耗能最大的过程单元之一,开发温和条件下低能耗高选择性吸附分离C₁~C₃分子的固体吸附材料迫在眉睫。金属有机框架材料（MOFs）作为一类相对新颖的多孔有机-无机杂化材料,因其可控的拓扑结构和多样的化学微环境,在低碳烃分离和纯化领域受到广泛关注。本文概述了MOFs作为分离和纯化低碳烃气体吸附剂的特性,重点关注了MOFs材料在C₁（CO₂/CH₄）、C₂、C₃烯/烷烃以及烯/炔烃分离领域的应用进展。首先归纳了MOFs材料在C₁~C₃烃类物质分离过程中的三种常见分离机制,并据此回顾了近年来MOFs材料对常见C₁~C₃烃类分子的吸附及分离性能;分析了MOFs材料在C₁~C₃烃类物质分离过程中的构效关系,总结了MOFs材料的孔道尺寸/形状、骨架柔性和表面功能的调控理念与方法,并提出MOFs材料成本高、水热稳定性差、主客体关系难以精准探测等制约其应用发展的现状。文章指出未来研究重点为开发低成本多样化专一性的新型配体,构造复合型吸附剂,并明确吸附分离过程中分离体系主客体性质,为MOFs材料用于低碳烃分离的定向设计提供了探索方向。     

提高水相法氯化聚乙烯弹性体热稳定性的实验

对水相法氯化聚乙烯(CPE)弹性体的氯化浆料进行了实验室研究,找出了导致CPE弹性体热稳定性较差、热分解温度偏低的原因,通过改造使CPE的热分解温度稳定在170℃以上。