Theoretical Study Of CO₂ Reduction Reaction Catalyzed By An Additional Electronic System

In recent years,with the continuous consumption of global energy,it has led to the excessive emission of CO₂,one of the greenhouse gases,which has caused the social environment to face increasingly serious problems.As an attractive C1 building block,CO₂ has the advantages of being cheap,non-toxic and abundant.Therefore,it is of great theoretical and practical significance to design an efficient catalytic CO₂ conversion method to reduce the harm of CO₂ to the environment.At present,traditional catalytic CO₂ mainly includes electrocatalysis,transition metal catalysis,photocatalysis and so on.Fortunately,in recent years,the research on theoretical computational design of CO₂conversion not only avoids the consumption of a large amount of experimental consumables,but also helps to gain insight into the mechanism of CO₂ conversion reaction.This paper was focuced on the theoretically designed of two novel catalysts that are helpful for CO₂ conversion reaction.Moreover,we have get insight into their reaction mechanism.The details are as follows:?1?For the first time,research on the CO₂ conversion reaction triggered by electride is proposed.Density functional theory?DFT?calculations show that Li-doped N3?translation is not accurate,no translation is re quired?forms N3Li with electride characteristics,and produces free N3Li??²-O₂C?by adsorbing CO₂,which can trigger another A reaction of CO₂ and RH?R=H,CH₃ and C₂H₅?to generate organic acid is divided into four steps:?1?the formation of N3Li??²-O₂C?through the combination of N3Li with CO₂;?2?the hydrogen abstraction from RH?R=H,CH₃ and C₂H₅?by N3Li??²-O₂C?to form the radical R·and N3Li??²-O₂C?H;?3?the combination of CO₂with the radical R·to form RCOO·;and?4?intermolecular hydrogen transfer from the intermediate N3Li??²-O₂C?H to RCOO·.In the whole reaction process,the CO₂ moiety in the complex N3Li??²-O₂C?maintains certain radical character at the carbon atom of CO₂ and plays a self-catalyzing role.?2?The new copper-catalyzed CO₂ transformation utilizes the negative ions H^-/OH^-of the hydrogen bond in the complex CuH/CuOH with the ligand6,6''-bis?2,4,6-trimethylanilido?terpyridine(H₂^TpyNMes),unlike the conventional coordination of CO₂ to Cu.We find that the inactive CO₂ can react with negative ions H^-/OH^-through a nucleophilic reaction to obtain respective product HCOOH/H₂CO₃.The calculated total free energy barriers are 8.38 and 24.31 kcal/mol for negative ions H^-and OH^-,respectively.