Synthesis Of Supported Cobalt Thioporphyrazines And Their Application In Bio-inspired Photocatalytic Process

Catalytic science has been playing an important role in the development of human civilization.Duing to the crisis of enviroment and energy,traditional catalytic process with harsh conditions is no longer suited for the green demands.Therefore,developing a catalyst that can attain excellence catalytic activity under mild conditions is the goal of catalysis scientists worldwide.This distertion designs and synthesizes two novel cobalt thioporphyrazines supported catalyst and applied to the platform molecule HMF oxidation.These experiment results show that cis/trans cobalt thioporphyrazine supported on Al2O3 can convert HMF to FFCA、DFF and FDCA under room temperature and ambient pressure.Especially,the cis-isomer can obtain 73.4%FDCA under alkaline conditions.In order to deeply expolre the reaction mechanism,we use molecular modelling methods to reveal the catalytic process.It is find that the symmetry of CoPz and type of S atom both have an influence on the CoPz’s photocatalytic activity.Meanwhile,the results from quantum chemistry also show that photocatalytic active site of cis-trans CoPz locate in the central metal ion rather than on the ligand.Then we also design and synthesize a kind of CoPz-（SBu）₈ dispersed on g-C₃N₄.The model reaction is also the HMF oxidation.By adjusting the pH of the reaction system,attain 96.1%FDCA in pH=9.18 and 72.2%DFF in pH=4.01 using CoPz-（SBu）₈/g-C₃N₄ as photocatalyst.Meanwhile,the stability test of catalyst display that it’s photocatalytic activity unchanged after five cycles.Furthermore,there is a energy transition process between CoPz-（SBu）₈ and g-C₃N₄ during the process.This design method of catalyst give a new route to prepare catalyst to production of value-added chemicals from biomass.