Design,Synthesis And Electrical Properties Of Sulfhydryl Conductive Coordination Polymers

Coordination polymers are diverse in composition,structure,and function,which has been widely studied and applied in many fields such as catalysis,gas storage separation,nonlinear optics,luminescence.However,the electrical research on coordination polymers is relatively scarce,and the poor electrical conductivity severely limits the applications of coordination polymers in energy storage,catalysis,sensing,and electronic devices.In this paper,we designed and synthesized a novel coordination polymer with high conductivity:CuIBTT based on trimercaptobenzene with high symmetry.The structure and basic properties of CuIBTT were analyzed through various characterization analyses,and the application of CuIBTT in the field of electrochemistry was explored.The main research results of this paper are as follows:1.A single crystal of conductive coordination polymer CuIBTT with a three-dimensional structure was synthesized by in situ growth method.The crystal structure of CuIBTT was recorded and analyzed by X-ray single crystal diffractometer and Olex2 software.Its molecular formula is Cu₆（C₆H₃S₃）₂I,which is represented by the armchair type Cu-S-I coordination nanotubes connected with benzene rings.The CuIBTT single-crystal four-electrode devices were prepared by UV lithography,and its conductivity was measured to be as high as 9625 S cm^-1 at room temperature.It was found by testing the temperature-variable resistance that the material exhibited a metallic behavior in which the conductivity decreased with the increase of temperature.2.CuIBTT nanocrystals were uniformly grown on carbon cloth by in situ growth method,and their morphology and structure were characterized.Furthermore,the catalytic performance of CuIBTT@CC for electrochemically catalyzing C-N coupling reaction to synthesize urea was explored through electrochemical testing and electrolysis product analysis.The results show that CuIBTT@CC has good stability and excellent electrocatalytic activity,with a urea formation rate of 100.94μg h^-1cm^-2 at a low overpotential（-0.4 V）and a 55.56%faradaic efficiency at-0.3 V overpotential,which is the highest value reported so far.At the same time,combined with the structural analysis of CuIBTT and synchrotron radiation in situ infrared,the electrocatalytic mechanism of CuIBTT@CC was initially explored.