Synthesis And Application Of Multi-arm Tribipyridinyl Coordination Polymers In Energy Storage And Conversion

The highly directional bonding of metal ligands overcomes the difficulty of the unpredictable coordination geometry of the transition metal center.In the field of metal supramolecular chemistry,N-heteroaromatic ligand[2,2':6',2'']-tridipyridine(tpy)is a kind of ubiquitous tridentate chelating ligand.Due to its monomer tpy-M-tpy connectivity and its ability to cooperate with a variety of transition metals,it is easy to design rigid supramolecular structures by using the coordination properties of tripyridine and metals.This opens the door to a range of new polymer structures.In this paper,tripyridine units were introduced into monomers through a series of designs,and two kinds of topological materials were prepared by appropriate methods,and their related properties were studied.The main research is as follows:1.A kind of tris(tripyridine)coordination polymer thin film with large area,ultra-thin thickness and uniform surface was prepared by liquid-liquid interface polymerization using1,3,5-tri(4-(2,2':6',2''-terpyridine)phenyl)benzene and Fe²⁺ion resources as raw materials.The two-dimensional coordination polymer film has the characteristics of flexibility,good redox activity and narrow band gap.Using PVA/Li Cl as the electrolyte,the synthesized TPPB-Fe film has the following excellent properties,including ultra-high area capacitance(1.25 m F cm^-2),volume energy density(5.8 m Wh cm^-3),good AC line filtering performance(71.3°at 120 Hz)and low resistance capacitance constant(0.06 ms).2.1,1',3,3'-tetrabromo-6,6'-azulene,which is used as the raw material,produces 1,1',3'-tetrabromo-6,6'-azulene,which is then cross-coupled with 4'-(4-boronic phenyl)-2,2':6',2'-triazulene,and then successfully prepared the bridled tetraphenyl triazulene monomer(TBAz).Due to the high complexing constant between tripyridine and transition Metal atoms,the monomer and Metal salt solution were polymerized by solvothermal method,and the coordination polymer containing Metal-N₆ was successfully prepared.The material has physical properties such as high specific surface area and narrow band gap.As an electrocatalyst for electrocatalytic reduction of CO₂,TBAz-Co shows excellent electrocatalytic activity.At-0.5V vs RHE,the Fe _CO is 94%,and after 10 h of continuous testing,the Fe _CO is still more than90%,and the current density has no obvious decrease,which is better than that of TBAz-Fe,TBAz-Ni and other reported catalysts.