The Preparation, Characterization And Catalytic Activity Of Interface Catalysts For Degradation Of Typical Organic Pollution

The design and fabrication of interface catalysts based on the model compounds as the active centers of metalloenzyme is the highlight in the industrial chemistry. In the dissertation, a new synthetic route has been proposed based on solid-phase organic synthesis to prepare the resin-supported interface catalysts having the MMO active centers, and their structural characteristics and catalytic performances and selectivity have also been investigated. The catalytic mechanisms have been proposed based on the catalytic results.Six interface catalysts were successfully prepared with four polystyrene resins. All the interface catalysts were characterized by elemental analysis, infrared spectra (IR), nuclear magnetic resonance spectra (NMR) and electron spin resonance (ESR). The results indicated that the structures of interface catalysts were coincident with that of the designed ones. The six resin-based interface catalysts exhibited monooxygenase-like activity, which depended on substrates and structures of interface catalysts. Many factors, such as resin, oxidant, anion and acetate, showed effect on the catalytic performance of interface catalysts having MMO active centers. Catalysts supported by macroporous aminomethyl resin (30-60 mesh) could efficiently catalyze oxidation of ethylbenzene. The optimal anion and oxidant were ClO4- and tert-butyl hydroperoxide (TBHP). Under these conditions described above, the best turnover number (TN) of catalytic reaction was up to 64.7. The oxidant showed clear impact on the reaction. The selectivity of the reaction could be changed using different oxidant. The formation of by-products could be inhibited once adding acetate in the reaction systems. The coupling reaction of 2,6-di-tert-pehenol was catalyzed under the TBHP oxidant and the crystal structure was determined by X-ray diffractometerThe sugar-based carbonaceous materials were prepared by glucose,β-cyclodextrin and starch precursors, and their structures have been characterized by IR, elemental analysis, TG-DSC, PXRD and so on. The sugar-based carbonaceous materials have been sulfated by conc. H2SO4. The BET surfaces of sugar-based carbonaceous materials vary greatly from more than 370 m2 g-1 to about 4 m2 g-1, and the thermostablity decreases from 550 to below 200oC before and after sulfonation. The adsorption of metal ions on the materials has been investigated and shows that the materials all have the good adsorption capability to metal ions and the strongest adsorption of Fe(III) ion is the carbonaceous material from starch. The absorption process obeys the Freundlich isotherms and is affected on the metal removal by the carbonaceous material dosage, initial concentration, shaking time, pH value and solution temperature. The sulfated materials can catalyze the esterification reaction including MMF synthesis. The sulfonated catalyst shows good catalytic activities in the formation of alkyl acetate with the best yield of 87% in 5 h.The carbonaceous material from starch can catalyze the degradation of 2-chlorophenol after it absorbs the Fe(III) ion. The removal ratio of 2-chlorophenol was 99.6% and the COD deceased 37.4%. A absorption-degradation reactor has been proposed and the degradation of 2-chlorophenol was stimulated under the flow rate of 15ml/min,microwave power of 200W and 80oC. The removal of Fe(III) ion was 97.2% and COD decreased 28.3% after recycling 18h, and the catalytic mechanism are proposed..The metal-intermingled photo-catalysts have been prepared based on the gluconate metals. the degradation of methyl orange was catalyzed by the catalysts under O2 and H2O2, and the best results were 61.3% and 98.9%。The most catalytic capabilities were ZnO-C and Fe2O3-C. The removal of phenol was 96.3%和98.6% after 6h by the ZnO-C,and COD values decreased 72.1% and 82.2%。The catalytic capability was kept intact after 4 cycles.The high value metal oxidation-based pathway and radical pathway mechanisms are proposed, and a good agreement was reached by comparison with experiment data. This study provides not only a clue to know the knowledge of fundamental enzymology, but also a novel and efficient route for the preparation of heterogeneous interface catalysts having MMO centers. It is the first time to bring forward the carbonaceous materials with the simultaneous absorption and catalytic performance.