Preparation Of Porphyrinic Functional Materials And Their Application On The Carbon-chloride Bond Activation

Organochlorine pollutants（OCPs）,due to the high toxicity,bio-accumulation and long-term residue,have been hugely damaged our common life.The electroreductive catalysis technology is pollution-free and easily operated and has been adopted as an ideal choice to treat organochlorine pollutants.Electron-rich metallo-phthalocyanines,Co（Ⅱ）(α-α’OC₅H₁₁)8-Pc and Mn（Ⅲ）Cl(α-α’OC₅H₁₁)8-Pc,were rationally prepared and applied as catalyst for carbon-chloride bond cleavages of p,p’-dichlorodiphenyltrichloroethane（DDT）,hexachlorocyclohexanes（HCHs）through electrochemical catalysis in non-aqueous media.The electronic structure was characterized by spectroscopy（UV-vis and magnetic circular dichroism（MCD）spectra）,electrochemistry,in-situ spectroelectrochemistry and TD-DFT theoretical calculations.In addition,the detailed comparision between the electronic structure and catalytic efficiency is also clearly illustrated.In the chapter Ⅱ,the Co（Ⅱ）Pc electrochemically catalyzed carbon-chloride bond cleavage reactions were carried out by controlled potential electrolysis,and the reaction kinetics were also investigated by time-dependent GC-MS analysis.According to the results we have obtained from the current research,we have achieved the first example of full dechlorination of DDT including C（SP3）-Cl and C（SP2）-Cl bond cleavage.More interestingly,the novel C-C bond cleavage and C-O bond formation were also confirmed at the same time,and the reaction mechanism was also investigated by various techniques.In the chapter Ⅲ,the Mn（Ⅲ）Cl-Pc was used to study the enantioselective carbon-chloride bond cleavage of hexchlorocyclohexanes（α-HCH,β-HCH and γ-HCH）through electrochemical catalysis.We hereby confirmed that the electrochemical reactivity of hexchlorocyclohexanes were enhanced arising from the increase of the number of e-type carbon-chloride bond of hexchlorocyclohexanes.In chapter IV,the Co（Ⅱ）porphyrin docurated magnetic catalyst Fe₃O₄@SiO₂@Cobalt（Ⅱ）porphyrins was repared and the structure was characterizedby XRD,SEM,SQUID.Morover,the electrochemistry and electrochemically catalyzed carbon chloride bond cleavages of environmentally toxic DDT,α-HCH and γ-HCH were also included.This synthesized heterogeneous catalyst,Fe₃O₄@SiO₂@Co（Ⅱ）porphyrins,was the fisrt example of highly efficiect and recyclable carbon-chloride bond cleavage of toxic organochlorides that may have great potential applications.