Preparation And Photo-/Electro-catalytic Performance Of Composite Derived From Poly Ionic Liquids (PILs) Coated ZIF-67/Fe-TCPP

Poly ionic liquids?PILs?,or polymerized ionic liquids,are polyelectrolytes that comprise a polymeric backbone and an ionic liquid?IL?species inmonomer repeating units.Recent years,PILs have attracted enormous research interest due to its novel structure and properties,as well as potential application in many fields,such as adsorption,CO₂ capture,electrolyte for fuel cells and supercapacitors.The synthetic strategy and property manipulation of PILs are becoming more and moe practical with a surge of research work.However,since the lack of catalytic active sites,the application of PILs in catalysis field is limited.Given that,this paper is based on the design of the new coordination complex@PILs material and further studies the synthetic strategy and catalytic performance of the coordination complex@PILs derived composites.Firstly,in order to explore the structure-activity relationship and catalytic reaction mechanism of coordination complex@PILs material derived composites,we prepared ordered-carbon coated Co nanoparticle?Co@ONPC?and disordered-carbon coated Co nanoparticle?Co@DO-NPC?by using 1-Vinyl-3-ethylimidazolium tetrafluoroborate??VEIm?BF₄?and ZIF-67 microcrystal as precursor.Electrochemical measurements uncover the better ORR performance of Co@O-NPC than Co@DO-NPC.A combination of molecular dynamic calculations and experimental results reveals that the ordered porous structure can effectively improve the diffusivity of O₂ and H₂O molecules and thereby enhance the performance of ORR.Furthermore,molecular scale DFT calculation results identified the catalytic active sites of Co@O-NPC and confirmed the synergistic effect between Co metal and N-doped porous carbon.In view of the good photocatalytic reduction of CO₂ performance of the porphyrin iron coordination complex,we consider whether the porphyrin iron coordination complex@PILs material possess enhanced catalytic performance as PILs have good adsorption ability for CO₂.Thereby,we prepared1-Vinyl-3-ethylimidazolium tetrafluoroborate??VEIm?BF₄?confined tetra?4-carboxyphenyl?porphyrin iron?III??Fe-TCPP?complex-Fe-TCPP@PILs by using a facile method.Photocatalytic reduction of CO₂ results showed that the catalytic activity of Fe-TCPP@PILs catalyst increased significantly compared with pure Fe-TCPP catalyst.The initial judgement for the reason is the strong CO₂adsorption ability of polyionic liquids is conducive to the chemisorption CO₂ on active sites of catalysts.Since this project is still in progress,the catalytic reaction mechanism needs to be further verified with the combination of experiment and therotical calculation.