Metal–organic framework of amine‐MIL‐53(Al) as active and reusable liquid‐phase reaction inductor for multicomponent condensation of Ugi‐type reactions

Metal–organic framework of NH₂‐MIL‐53(Al), with coordinative unsaturated aluminium sites, has been shown to be active in the Groebke–Blackburn–Bienaymé multicomponent coupling reaction based on Ugi‐type amine and aldehyde condensation over isocyanide and then a cyclization process. Interestingly this reaction occurred under solvent‐free conditions with high yield, in which the NH₂‐MIL‐53(Al) could be recovered and reused for five reaction cycles, giving a total turnover number of 455.     

Self-Assembly Approach Towards MoS2-Embedded Hierarchical Porous Carbons for Enhanced Electrocatalytic Hydrogen Evolution

Transition metal-based nanoparticle-embedded carbon materials have received increasing attention for constructing next-generation electrochemical catalysts for energy storage and conversion. However, designing hybrid carbon materials with controllable hierarchical micro/mesoporous structures, excellent dispersion of metal nanoparticles, and multiple heteroatom-doping remains challenging. Here, a novel pyridinium-containing ionic hypercrosslinked micellar frameworks (IHMFs) prepared from the core–shell unimicelle of s-poly(tert-butyl acrylate)-b-poly(4-bromomethyl) styrene (s-PtBA-b-PBMS) and linear poly(4-vinylpyridine) were used as self-sacrificial templates for confined growth of molybdenum disulfide (MoS₂) inside cationic IHMFs through electrostatic interaction. After pyrolysis, MoS₂-anchored nitrogen-doped porous carbons possessing tunable hierarchical micro/mesoporous structures and favorable distributions of MoS₂ nanoparticles exhibited excellent electrocatalytic activity for hydrogen evolution reaction as well as small Tafel slope of 66.7 mV dec⁻¹, low onset potential, and excellent cycling stability under acidic condition. Crucially, hierarchical micro/mesoporous structure and high surface area could boost their catalytic hydrogen evolution performance. This approach provides a novel route for preparation of micro/mesoporous hybrid carbon materials with confined transition metal nanoparticles for electrochemical energy conversion.     

Self‐assembly of metal–organic framework thin films containing metalloporphyrin and their photocatalytic activity under visible light

With [5,10,15,20‐tetra(4‐carboxyphenyl)porphyrin]Mn(III) and sterically controlled 2,2¢‐dimethyl‐4,4¢‐pyridine as the main raw materials, metal–organic framework thin films containing metalloporphyrin (MnPor‐MOF) with catalytically active sites were built up on functionalized quartz glass surfaces using a layer‐by‐layer self‐assembly method. Retaining active catalytic sites and having a porous reticular structure, the MnPor‐MOF films possessed remarkable photocatalytic activity for oxidative degradation of methylene blue in the presence of hydrogen peroxide under visible‐light irradiation. Most meaningfully, the MnPor‐MOF films were highly stable and simply and conveniently reusable, and are thus a potentially new organic material for photocatalytic wastewater treatment. Copyright © 2015 John Wiley & Sons, Ltd.     

Novel CD-MOF NIR-II fluorophores for gastric ulcer imaging

Gastric ulcers are one of the most common stomach diseases that often accompanied by inflammation, congestion, edema, scar tissue formation, and pyloric obstruction. Fiberoptic endoscopy and X-ray analysis of the upper GI tract have become the diagnostic procedure of choice for patients. However, conventional diagnosis technology is either invasive or radioactive. Herein, a novel CD-MOF NIR-II fluorophore (GPs-CH1055) was developed. The relative fluorophore intensity was largely consistent at various media and pH buffers, and it can swell into gel particles in solvents and be completely expelled from the gastrointestinal tract without being assimilated. GPs-CH1055 has been further evaluated in vivo, and exhibited strong retention effect on the gastric ulcer sites, bright NIR-II signals with high spatial and temporal resolution. Therefore, GPs-CH1055 shows great promise for realizing real-time gastric ulcer imaging and diagnosis.     

Covalent Organic Frameworks(COFs) for Sequestration of99TcO4–

Covalent organic frameworks(COFs), as a class of crystalline porous materials with periodic lattices and porous structures, have received extensive attention in the fields of gas storage and separation, energy storage, catalysis and optoelectronics and so on. However, COFs are still in their infancy in the field of nuclear waste treatment, especially for sequestration of long-live problematic radionuclides, such as ⁹⁹Tc. Battle of decontamination of pertechnetate(TcO₄^–), a main existence of ⁹⁹Tc under aerobic environments, is far from finished. In this review, recent progresses of COFs and some relative materials in the sequestration of pertechnetate, and perspective on surmounting the unmet issues are elucidated.     

Successive stepwise evolution of host layer‐stacking framework upon the intercalation of mobile vapor guests within side‐chain layers

For the ordered phases of hairy‐rod semiconductive poly(2,5‐bis(3‐tetradecylthiophene‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT) sandwiched in between crystalline platelets of hexamethylbenzene, the successive stepwise evolution of layer‐stacking framework upon guest intercalation has been studied in this research. The direct consequence of the guest intercalation into side‐chain layers is evaluated to cause the lateral shift of thiophene backbones along π–π stacking, resulting in stepwise shift of ultraviolet absorption wavelength. The thermal motions of vapor guests within disordering side‐chain layers subsequently cause progressive expansion of host stacking framework. With the increase in side‐chain length, thicker layers of disordering side chains in liquid crystals (LCs) accommodate additional vapor guests and larger amplitudes of thermal motions of guests, hence promoting the level of reversible d‐spacing change. The mixing between mobile vapor guests and aliphatic side chains is clarified as the mechanism of guest intercalation, which rationalizes successive guest intercalation during heating and the contribution of disordering side‐chain layers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1448–1456     

High-throughput syntheses of iron phosphite open frameworks in ionic liquids

Three open-framework iron phosphites: Fe^п₅(NH₄)₂(HPO₃)₆ (1), Fe^п₂Fe^♯(NH₄)(HPO₃)₄ (2) and Fe^♯₂(HPO₃)₃ (3) have been synthesized under ionothermal conditions. How the different synthesis parameters, such as the gel concentrations, synthetic times, reaction temperatures and solvents affect the products have been monitored by using high-throughput approaches. Within each type of experiment, relevant products have been investigated. The optimal reaction conditions are obtained from a series of experiments by high-throughput approaches. All the structures are determined by single-crystal X-ray diffraction analysis and further characterized by PXRD, TGA and FTIR analyses. Magnetic study reveals that those three compounds show interesting magnetic behavior at low temperature.     

A Superacid-catalyzed Synthesis of Fluorescent Covalent Triazine Based Framework Containing Perylene Tetraanhydride Bisimide for Sensing to O-nitrophenol with Ultrahigh Sensitivity

Abstract

A mesoporous covalent triazine framework, PCPDI, was synthesized via an aromatic nitrile trimerization reaction of N,N′-di(4-cyanphenyl)- 3,4,9,10-tetracarboxydiimide (CPDI) by CF₃SO₃H catalyzed at 40?°C and this method avoids the use of noble metal catalyzers or high temperature reaction. PCPDI exhibits high thermal stability and strong fluorescence. The PCPDI shows ultrahigh sensitivity to tracing o-nitrophenol in chloroform with K_SV constant of 1.74?×?10⁵ L mol^?1 and detection limit (LOD) of 1.72?×?10^?11?mol L^?1.     

CuNPs@Cu（Ⅱ）-AMTD金属有机凝胶复合材料的合成及其催化性能

在Cu（Ⅱ）-AMTD金属有机凝胶基质中原位生长铜纳米粒子,得到了CuNPs@Cu（Ⅱ）-AMTD纳米复合材料,并分别进行了IR,SPR,SEM,TEM,EDX,XPS等测试分析其形貌组成。所得材料对4-硝基酚还原为4-氨基酚以及其他硝基苯的还原反应显示了优良的催化性能。同时也讨论了催化反应的机理。