Graphene Paper with Sharp‐edged Nanorods of Fe−CuMOF as an Excellent Electrode for the Simultaneous Detection of Catechol and Resorcinol

A flexible composite paper Fe?Cu‐based metal‐organic framework (MOF)/reduced graphene oxide (rGO) (Fe?CuMOF/rGO) electrode was prepared by using a simple electrochemical method for the simultaneous detection of catechol (CC) and resorcinol (RC). Free‐standing, flexible and double‐sided Fe?CuMOF/rGO composite paper was obtained by applying the electrochemical deposition process on the rGO paper electrode in the solution containing Fe?CuMOF composite. The morphological analysis of Fe?CuMOF/rGO composite paper showed that sea urchin‐like structures formed on the rGO electrode surface consist of numerous sharp‐edged nanorods of Fe?CuMOF. Flexible Fe?CuMOF/rGO paper electrode exhibited high sensitivity, wide linear range and low detection limit for the simultaneous determination of CC and RC. The linear ranges of concentration for CC and RC were 0.1–800 and 0.1–720 μM, respectively, and the corresponding limits of detection (S/N=3) were 0.016 and 0.020 μM. The outstanding performance of this flexible electrode could be attributed to the sharp‐edged urchin‐like Fe?CuMOF structures which provide an increment of the surface area and the electrochemical activity of the composite paper electrode. Stability tests showed that Fe?CuMOF/rGO composite paper electrode has excellent flexibility, high durability, and good reproducibility. Furthermore, this electrode exhibited high sensitivity and selectivity for the determination of CC and RC in real sample analysis.     

Mixed matrix membrane comprising polyimide with crystalline porous imide‐linked covalent organic framework for N2/O2 separation

An imide‐linked covalent organic framework (COF) was successfully synthesized by directly heating a mixture of melamine and biphenyltetracarboxylic dianhydride (BPDA) in a tubular oven at 335°C. The crystalline and nanostructure of this COF was characterized by X‐ray diffraction (XRD) and Brunauer‐Emmett‐Teller (BET). A mixed matrix membrane (MMM) was prepared by blending the COF into the commercial P84 polyimide in solution. It is found that the COF particles not only act as gas channels for N₂ and O₂ permeation but also provided an inverse permselective property with higher permeability of N₂. The effect of COF nanostructure and its loading amount on N₂ and O₂ permeability and selectivity has been investigated.     

Nanoscaled porphyrinic metal–organic framework for photodynamic/photothermal therapy of tumor

Nanoagents achieving photodynamic therapy (PDT) and photothermal therapy (PTT) combination treatment with improved therapeutic effect are highly desirable. However, the incorporation of both PDT and PTT into a single nanoagent often requires multistep fabrication process. Herein, we report that photoactive porphyrin ligands have been successfully introduced into Zn‐TCPP structure to construct the nanoagents that possesses photodynamic performance and photothermal performance simultaneously. Such a nanoagent enables the generation of single oxygen and heat under laser irradiation. Additionally, it exhibits satisfactory biocompatibility and high light toxicity against cancer cells. The current work provides a feasible approach to introduce both PDT and PTT into a single nanoplatform.     

荧光性多孔芳香骨架材料的简便制备 及在硝基爆炸物检测中的应用

报道了一种简便的制备高荧光性多孔有机聚合物材料的方法, 即以1,3,6,8-四溴芘(TBrPy)与硼酸类单体为构筑基元, 通过Suzuki偶联反应制备多孔芳香骨架材料LNUs. 利用傅里叶变换红外光谱、 热重分析、 氮气吸附、 固体紫外光谱和荧光光谱等分析方法对其结构与性能进行了系统表征. 分析结果表明, 该类多孔芳香骨架材料具有良好的热化学稳定性和较大的比表面积, 所得材料优异的荧光性能使其非常适合用于硝基爆炸物的选择性检测. 多孔芳香骨架材料LNUs在苯、 溴苯、 苯胺、 甲苯、 氯苯和苯酚等分子存在下, 荧光强度基本不变, 而在加入硝基苯、 对硝基苯酚和对硝基氯苯后, 荧光几乎完全猝灭, 说明该类材料对硝基苯、 对硝基苯酚和对硝基氯苯显示出专一的检测性能. 根据这一特性, 利用LNUs材料制备了一种新型便携式纸传感器, 其可以简便快速实时检测硝基爆炸物, 并在痕量检测方面展现出良好的应用前景.     

UiO-67-Sal-CuCl2在空气中催化芳香醇的选择性氧化

利用水热法一步合成了金属有机骨架(MOFs)材料UiO-67-Sal, 并将3种铜盐固定在其表面, 研究了3种铜MOFs材料催化芳香醇选择性氧化的性能. 结果表明, UiO-67-Sal-CuCl₂催化剂对芳香醇选择性氧化反应具有良好的催化活性, 且在重复使用4次后, 依然保持较好的催化效果.     

微通道连续合成UiO-66系列改性MOF材料

采用内交叉指型微反应器连续合成UiO-66材料. 连续微通道法强化了物料之间的混合, 极大提高了生产效率, 晶体产物呈六面体形, 粒径在100 nm以下. 考察了温度、 总进料流量和停留时间等条件对合成过程及产物的影响. 结果表明, 升高温度有助于晶粒的生长; 随着总进料流量增大, 晶体粒径减小; 晶体的形成需要一定的停留时间, 超过该停留时间, 晶体粒径不再增大. 通过优化实验条件, 可以实现系列纳米级UiO-66-X材料(X=NH₂, NO₂, Br)的连续合成.     

一种高比表面积共价有机框架材料的合成及药物缓释性能

合成了一种具有较高比表面积(S_BET=1804 m ²/g)的新型二维共价有机框架(COF)材料(JUC-516), 并将其应用于模拟人体体液(SBF)中模拟动物体内的药物缓释, 取得了较理想的效果. 通过Materials Studio模拟、 粉末X射线衍射(PXRD)、 N₂吸附-脱附分析、 扫描电子显微镜(SEM)及傅里叶变换红外光谱(FTIR)等方法表征了所得COF材料的结构, 证实JUC-516是一种基于AA堆积hcb拓扑、 具有高结晶度和球状形貌的共价有机框架材料.     

3D Porous Heterometallic Coordination Polymer for the Detection of Nitroaromatic Explosives and Inhibiting Human Cancer Cells Growth

A new heterometallic coordination polymer, namely [Cd₂Sr(bdc)₃(H₂O)₂]_n ( 1 ) (H₂bdc = terephthalic acid), was synthesized via the solvothermal reaction of Cd(NO₃)₂, Sr(NO₃)₂, and H₂bdc. The X‐ray structural analysis reveals that compound 1 is a 3D framework based on 1D rod‐shaped heterometallic metal‐carboxylate chains as building subunits. Viewing along the crystallographic c axis, there exist large 1D rhombic channels with effective dimensions of ca. 10.0 × 18.6 Ų. Moreover, compound 1 emits intense luminescence at room temperature. The investigations of luminescence indicated that compound 1 can be served as a luminescence probe for the detection of nitroaromatic explosives. Furthermore, the anticancer activity of 1 was evaluated against three human cancer cells MCF‐7, MDA‐MB‐231, and MDA‐MB‐435S via the MTT assay.     

A novel nano‐cotton‐like bismuth oxyfluoride (NC‐BiOF) and a novel nanosheet heterogeneous compound BiOF@ZIF‐8 as catalyst for the selective and green oxidation of benzylic alcohols

We describe here for the first time a new morphology of BiOF nanoparticles with a cotton‐like structure, made using a hydrothermal synthesis method. We also prepared heterogeneous nanosheets of BiOF@ZIF‐8 by a one‐pot synthesis under hydrothermal conditions. We demonstrate that in this method the morphology of BiOF and one‐pot synthesis conditions are the main factors for the preparation of the nanosheet BiOF@ZIF‐8. Fourier transform infrared (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy‐dispersive X‐ray (EDX), thermogravimetry‐differential thermal analysis (TG‐DTA), and BET surface area were used to characterize the samples prepared. XRD, SEM, and adsorption–desorption analysis showed that the structure of ZIF‐8 and BiOF form intact only in one‐pot synthesis of BiOF (with nano‐cotton‐like morphology) with Zn(NO₃)₃, while spectral techniques show the successful encapsulation of the sheet BiOF on ZIF‐8. Nanosheet BiOF@ZIF‐8 was found to be a highly efficient heterogeneous catalyst for the selective oxidation of alcohols. BiOF@ZIF‐8 could be reused several times although it got less active with recycling.     

Air‐Free Synthesis of a Ferrous Metal‐Organic Framework Featuring HKUST‐1 Structure and its Mössbauer Spectrum

Single crystals of the Fe^II metal‐organic framework (MOF) with 1,3,5‐benzenetricarboxylate (BTC) as a linker were solvothermally obtained under air‐free conditions. X‐ray diffraction analysis of the crystals demonstrated a structure for Fe^II‐MOF analogous to that of [Cu₃(BTC)₂] (HKUST‐1). Unlike HKUST‐1, however, the Fe^II‐MOF did not retain permanent porosity after exchange of guest molecules. The Mössbauer spectrum of the Fe^II‐MOF was recorded at 80 K in zero field yielding an apparent quadrupole splitting of ΔE_Q = 2.43 mm · s^–1, and an isomer shift of δ = 1.20 mm · s^–1, consistent with high‐spin central iron(II) atoms. Air exposure of the Fe^II‐MOF was found to result in oxidation of the metal atoms to afford Fe^III. These results demonstrate that Fe^II‐based MOFs can be prepared in similar fashion to the [Cu₃(BTC)₂], but that they lack permanent porosity when degassed.