| As the supramolecular hosters, Calixarenes have attracted a lot of attention from the word due to their unique cavity ringlike structures that have provided favorable environment for many chemical reactions. Recently, Resorcinarenes play an important role in the research area because of their excellent physical and chemical properties as well as their simple synthesis routes. In addition, Resorcinarenes have significant application in the fields of supramolecular chemistry such as molecular recognition, fluorescent probe, drug encapsulation, self-assembly and nanomaterials, etc. Calixarenes can take control of the preparation of micro-nanomaterial as protective and induced agent by functional modification, which is a very meaningful exploration and will provide new ideas and methods for the control of micro-nanomaterial and is a worthy subject. According to the principle of Colloid and Interface Chemistry, a novel surfactant molecules were synthesized and used in the morphological regulation of ZnO synthesis. In this paper, ball-like and flower-like ZnO materials were achieved successfully by the protection of 2,4,6,8-tetrapropyl-1,3,5,7 (1,3)-tetrabenzenacyclotetraphan-1,3,5,7 (6-hydroxy-5-oxo-21I-chromene-3)-carboxylic acid surfactant (TTCC) and 2,4,6,8-tetrahexyl-1,3,5,7 (1,3)-tetrabenzenacyclooctaphan-14,16,34,36,54,56,74,76-octaol surfactant (TTO), respectively. Then, we did much research on the formation mechanism, physical and chemical properties, photocatalytic properties and photocatalylic principle of ZnO micro-nanomaterials. Effects of preparation conditions on the morphology were mainly discussed and focused on the formation mechanism in the experiments of preparing ball-like ZnO micro-nanomalerial. Then, the pholocatalylic activities were analyzed and the catalytic mechanism was proposed. The usages of Zinc resource and surfactant were discussed in the process of synthesizing flower-like ZnO micro-nanomaterial. The superior degradation of methyl violet solution (MV) might be caused by the defects on ZnO, and then the catalytic mechanism was raised. The morphology and composition of samples were characterized and analyzed by means of SEM, TEM, XRD, TG and FT-IR.The main content is as follows:1. Firstly, TTCC was prepared by a simple and efficient method by using hydroxyphenol as raw material as reported. Then we created target compound TTCC by further hydrolization the product that the TTCC reaction with Methylmalonate to produce. The product purity was characterized by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Spectrometry (FT-IR). Besides, we did much research on the aqueous solution of TTCC. It was found that TTCC surfactant performed good foaming and foaming properties in the testing process. The Critical Micelle Concentration (CMC) of TTCC was measured by Wilhelmy plate and conductivity method, respectively. The results indicated that the TTCC had a low CMC about 0.13 mM, which were in consistent with the results of fluorescence spectra.2. The ball-like ZnO micro-nanomaterial was obtained by a simple reflux method with uniform morphology and size, using Ammonia as complexing agent, zinc nitrate as zinc source and TTCC as protective agent. The diameter of ball-like ZnO is located from 800 nm to 1000 nm, which is built by nanoparticles with 20 nm to 30 nm diameter under template effect of TTCC assembly. The X-ray diffraction pattern (XRD) exhibits that the ball-like ZnO we achieved can be attributed to the hexagonal ZnO wurtzite structure. Next, the effects of different reaction conditions on morphology and size were investigated. It could be seen that the white ball-like ZnO possessed mesoporous structure after calcination. As a result, the TTCC surfactant could not only take control of the morphology of material, but also could participate in the framework. The results were verified by SEM, TEM, TG and FT-IR. The photocatalytic activity of ZnO could be evaluated by Methyl violet in aqueous solution as a model reaction. UV-visible spectrophotometry demonstrated that the ZnO before and after calcination in methyl violet aqueous solution showed good decolorization performance.3. Likewise, we obtaioned the flower-like ZnO with uniform morphology and size by the simple reflux method. In detail, it could be seen that the average diameter of flower-like ZnO is about 1 urn which possessed a petal consist of side edge length and width of 500 nm and 200 nm nanoflake by using TTO as inducer, zinc nitrate as zinc source and ammonia as complexing agent. XRD results showed that the synthesized samples have hexagonal wurtzite structure and were grown along the (002) crystal surface direction, which were verified by HR-TEM images. TG carves displayed that TTO played not only a very good induction effect, but also might form some force adsorption on the surface as the flower like ZnO presented pink in the ZnO synthesis process, which was supported by the results that the contact angle experiments reified. Then, we investigated the influence on morphology and size of flower-like ZnO by the usages of TTO and zinc nitrate. Otherwise, photochemical properties of flower-like ZnO were tested that the ZnO could not only absorb the UV light, but also absorb the visible light by FT-IR and UVDRS. The flower-like ZnO performed excellent catalytic activity to methyl violet dye in the photodegradation experiments,18 min of the decolorization rate reached 96.6 percent under ultraviolet light irradition and 270 min of the decolorization rate reached 67.96 percent under visible irradiation. Photocatalytic degradation of dyes mainly related to oxygen vacancies that provided composite centers for free electrons back to the holes in semiconductor metal oxides. Then the Raman, PL and XPS characterization methods were used to analyze the oxygen vacancies, which stated high oxygen vacancies in the flower-like ZnO. |
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