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?%).     

A 2-dimensional gradual period photonic heterostructure possessing omnidirectional band gap in visible range made by holography

A 2-dimensional gradual period photonic heterostructure was made with holography by use of non-uniform swelling effect of dichromated gelatin during processing. In this structure, the symmetric point group of triangle lattice was debased to C_2V from C_6V. Theoretical analysis and experimental results show that omnidirectional band gap in visible range can be achieved with this kind of heterostructure made by low refractive index materials.     

Hydrolysis kinetics of silane coupling agents studied by near-infrared spectroscopy plus partial least squares model

Abstract

A method of Fourier transform near-infrared (FT-NIR) spectroscopy combined with partial least squares (PLS) model was successfully applied to investigate the hydrolysis kinetics of four kinds of silane coupling agents (phenyltriethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltriethoxysilane) in an acid-catalyzed EtOH system. The fast scanning speed and high sensitivity of the FT-NIR spectroscopy, and the powerful data processing ability of the PLS, enabled the method to quantitatively and accurately catch the fast changing H₂O concentration during the hydrolysis processes without delay, realizing the study of the fast-paced hydrolysis reactions of the silane coupling agents. The results showed that electrophilic substitution occurred in the hydrolysis reactions, which followed second-order reactions and greatly depend on the catalyst concentration and reaction temperature. The hydrolysis rate constants, activation energy, and Arrhenius Frequency factors were gained. In conclusion, the FT-NIR PLS model is a powerful tool for hydrolysis kinetics researching of the silane coupling agents.