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Green Catalytic Materials: The Study On Synthesis, Structure And The Catalytic Activity In Cyclohexane Oxidation Of Transition Metal Supramolecular Complexes

Posted on:2015-08-11Degree:MasterType:Thesis
Country:ChinaCandidate:L T XuFull Text:PDF
GTID:2181330431490176Subject:Physical chemistry
Abstract/Summary:PDF Full Text Request
Catalytic oxidation of cyclohexane (Cy) has attracted much attention in catalyticchemistry. The main products of Cy oxidation are cyclohexanol and cyclohexanone, whichare important organic materials for the production of adipic acid and caprolactum, and furthersynthesize the nylon-6,6’, nylon-6, polyamide-6, polyurethane foams, pharmaceuticals, paints,dyes and lubricating additives. However, there are some problems in the conventional processof Cy oxidation, such as much by-products, low selectivity and emissions and environmentalpollution. Therefore, it is imperative to seek a high selectivity, high stability andenvironmentally friendly catalyst.In this thesis, Co(IAA)2(phen)(H2O)(1) and Ni(IAA)2(phen)(H2O)(2) complexes weresynthesized using IAA and phen (IAA=indole acetic acid, phen=1,10-phenanthroline) asligands; iron complex [Fe(H2L)2]·(CH3COO)2·(OH)·H2O (3) with H2L(H2L=2,6-bis(5-methyl-1H-pyrazol-3-yl) pyridine) was synthesized; another four complexeswith H2L and H2dipic (H2dipic=2,6-pyridine dicarboxylic acid) ligands were synthesized asCuCl2(H2L)(4),[Ni(HL)2]·4CH3CH2OH (5),[Cu(H2L)(dipic)]·0.5Glycol·2H2O (6) and[Ni(H2L)(dipic)]·0.5Glycol·2H2O (7). The complexes1-2and4-7were synthesized firstly.The structure of these complexes were characterized by single-crystal X-ray diffraction,elemental analysis, IR spectroscopy and UV spectroscopy. In addition, the complexes3-7were also characterized by powder X-ray diffraction. The complexes1-2were characterizedby thermal gravimetric analysis (TG). The main work is that the catalytic properties ofcomplexes1-7were studied in detail.To seek the active catalysts for Cy oxidation, all complexes were applied forhomogeneous oxidation with H2O2as oxidant and the effects of various factors such asamount of acid and H2O2, temperatures, as well as the kind of solvent were evaluated. Inaddition, the influence of intermediate species cyclohexylhydroperoxide on the turnovernumber of C6H10O and C6H11OH were studied. Also, the most effective acid additives werediscussed.
Keywords/Search Tags:Transition Metal Supramolecular Complexes, 2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine, Cyclohexane Oxidation, Homogeneous Catalysis, Catalytic mechanism
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