A Porphyrin-Based Covalent Organic Framework for Metal-Free Photocatalytic Aerobic Oxidative Coupling of Amines

Imines are important intermediates in drug synthesis. Photocatalytic aerobic oxidative coupling of amines has been considered as a clean and promising way to produce imines and has attracted great attention. Herein, we designed and synthesized a novel two-dimensional porphyrin-based covalent organic framework (Por-BC-COF) which adopts an AA stacking mode with excellent crystallinity, high Brunauer–Emmett–Teller surface areas (1200 m² g⁻¹), wide light absorption range (200–1300 nm) and good stability in a variety of organic solvents. Por-BC-COF can be used as a metal-free heterogeneous photocatalyst for the photocatalytic oxidation of amines to imines under visible light and red light with a high yield (97 %). This work presents a novel and efficient COF photocatalyst in the application of light-driven organic synthesis.     

Physical,hydrochemical and isotopic characteristics of springs in Beijing,China, compared to historical properties

A physical, hydrochemical and isotopic evaluation of springs in Beijing was conducted in 2009 to reveal apparent changes in the properties of those springs. The results showed that most of the 2nd class springs and more than 50 % of the 1st class springs recorded in the early 1980s were depleted, while the discharges of existing springs have also decreased sharply. In addition, the majority of springs were of the HCO₃–Ca–Mg type and good water quality, with the quality indices changing slightly compared to those recorded 30 years ago. The abundances of ²H, ¹⁸O, and ³H in the springs indicated that most of the springs were of meteoric origin with a relatively close connection to modern atmospheric precipitation. As a result, the springs have a relatively strong renewability within a shallow circulation.     

A new method for preparing TiO2 catalyst honeycombs without sintering

Composite catalyst honeycombs without sintering were prepared via kneading, mulling, extrusion molding, and solidifying at room temperature with the magnesite oxychloride gels modified by nano-rice husk ash (RHA) as a solidifying agent. The effects of nano-RHA and composite water-resistant agents on the water resistance of magnesite materials were studied. The solidification of the modified magnesite gels on TiO₂ catalyst honeycombs was analyzed. The experiments show that the proportional addition of nano-RHA markedly increases the water resistance of magnesite materials without reducing the bending strength, and the softening coefficient increases from 0.29 to 0.78. With further addiition of the complex water-resistant agents, the softening coefficient increases from 0.78 to 0.97. The optimal mass ratio of MgO in the solidifying agent to TiO₂ is 4:1, and the bending strength of unsintered catalyst honeycombs is 11.46 MPa. The desulfurization rate and denitration rate of this composite catalyst honeycomb on simulation smoke was 97 and 65 %, respectively, in 3 h.     

Nanosized Carbon Macrocycles Based on a Planar Chiral Pseudo Meta-[2.2]Paracyclophane

Structural designs combining cycloparaphenylenes (CPPs) backbone with planar chiral [2.2]paracyclophane ([2.2]PCP) lead to optical-active chiral macrocycles with intriguing properties. X-ray crystal analysis revealed aesthetic necklace-shaped structures and size-dependent packages with long-range channels. The macrocycles exhibit unique photophysical properties with high fluorescence quantum yield of up to 82 %, and the fluorescent color varies with ring size. In addition, size-dependent chiroptical properties with moderately large CPL dissymmetry factor of 10⁻³ and CPL brightness in the range of 30–40 M⁻¹ cm⁻¹ were observed.     

Crucial factors affecting the physicochemical properties of sol–gel produced Fe3O4@SiO2–NH2 core–shell nanomaterials

Multifunctional nanomaterials with task-specific physicochemical properties, especially core?Cshell nanostructures with Fe₃O₄ core and NH₂-functional shells (Fe₃O₄@SiO₂?CNH₂), have been extensively investigated as high-performance adsorbents, catalysts and catalyst supports; and in most cases the controllable sol?Cgel technique is the choice for fabrication of this kind of widely applied materials. Herein, we demonstrated that mono-dispersed and spherical Fe₃O₄@SiO₂?CNH₂ nanomaterials with magnetic response core, NH₂-functional shell structure can be facilely prepared by co-condensation of TEOS with APTMS using a versatile sol?Cgel process. It was shown that the proper usage of APTMS and appropriate pre-hydrolysis time of TEOS were crucial and key steps for formation of highly uniform and desirable amino loading Fe₃O₄@SiO₂?CNH₂ materials. The TEOS pre-hydrolysis and the critical time (around 90?min) before the addition of APTMS prove to be vital for uniform structure evolution, while the appropriate concentration of APTMS (~2.28?mmol?L^?1 in our system) leads to well-dispersed materials with relatively high loading of amino functionality. The as-prepared Fe₃O₄@SiO₂?CNH₂ magnetic nanoparticles prepared under optimum conditions possessing superparamagnetic behavior, uniform core?Cshell structure (~200?nm in diameter), relatively large BET surface area (~138?m²/g) and high incorporation of amino-functionality (~2.90?wt?%).