Synthesis And Properties Of Co (?)?Rh (?) And Ir (?) Corroles

Increasing global population accompanied with increase in energy demand resulting in climate change and other factors,has necessitated the pressing for green energy.Electrocatalytic technology has been identified to continuously convert molecules in the atmosphere such as water and carbon dioxide into high-value products through electrochemical conversion,which provides a way for the development of green energy.These energy conversion technologies play a key role because they increase the rate,efficiency and selectivity of the chemical conversions involved,and developing advanced efficient electrocatalysts is a huge challenge.In the continuous exploration in the past,transition metal complexes have high-efficiency electrocatalytic capabilities,have the advantages of rich resources and high cost performance,can replace the traditional precious metal platinum,and have wide application prospects as catalysts for electrocatalytic technology.The core problem of electrocatalytic technology is effective and efficient electrocatalyst.Corrole is a type of porphyrin derivative directly connected by a pyrrole-pyrrole bond.Unlike porphyrin macrocyclic compounds,the three-anion core of corrole can stabilize metal ions in a higher oxidation state.Corroles have potential applications in the fields of sensors,medicinal chemistry and catalysis.The coordination of the macro ring with transition metals is used in electrocatalytic technology,which provides the feasibility for solving the energy crisis.This article aims to design metal corroles of cobalt,rhodium and iridium as molecular catalysts for electrocatalytic technology through surface modification and electronic structure control.The main research contents are as follows:?1?Design seven kinds of A₂B cobalt corrole containing methylthio group.In terms of electron control,the substituents with different electron-withdrawing ability were selected to modify the corrole macrocycle.After completing the basic characterization using UV-Visible spectroscopy,nuclear magnetic resonance spectroscopy and MALDI-TOF mass spectrometry,the electronic structures of our compounds were further explored using electrochemical workstation.CV and DPV were run to further understand the electronic behavior of the seven synthesized corrole compounds.Prior to their electrocatalytic application,the cobalt corrole complexes were immobilized to create SAMs on the surface of Au electrode as a result of a Au-S bond.?2?The same design contains two methylthio groups of corrole,two A₂B type rhodium corroles,and three A₃ type rhodium corroles.Substituents with different electron-withdrawing groups were used to modify the macrocyclic rings.In terms of application,SAMs of A₂B rhodium corroles were developed and applied as electrocatalysts for HER.The test results show that the electrocatalytic performance of rhodium corrole is better than cobalt corrole.On the other hand,A₃ type rhodium corrole nanocomposites were also developed and electrochemically tested to explore its HER performance.?3?By introducing aryl groups with different electron-withdrawing capabilities at the meso and axial positions,and by changing the form of the electron cloud density around the corrole ring,three types of A₂B iridium corroles and three types of A₃iridium corroles were designed.They were characterized via NMR,UV-Vis,CV,DPV and fluorescence and electrochemically tested.It was found that iridium corroles have potential and can serve as excellent ORR electrocatalyst.This potential indicates this type of corrole is an excellent functional material.