Photocatalytic Activity Of Copper Porphyrin Based One Dimensional Nanostructures For Carbon Dioxide Reduction

In recent years,increasing anthropogenic CO₂ emissions have caused severe energy and environmental issues.In response to these problems,much research has concentrated on exploring effective ways to achieve the artificial conversion of CO₂.Inspired by the natural photosynthesis,this paper imitates the porphyrin molecules in the natural chlorophyll,constructs the porphyrin and semiconductor composite structure,and realizes the efficient photocatalytic carbon dioxide system.1.In this work,we reported a facile hydrothermal method method to fabricate Cd S/Cu TCPP one-dimensional and core-shell structure to construct the artificial photosynthesis system.Cu TCPP can not only be used as photosensitizer,but also increased the light capture ability of the material.More importantly,the Cd S/Cu TCPP heterojunction can be used as a charge transfer channel,which further improved electron transfer.Cd S/Cu TCPP composite structure showed excellent photocatalytic activity for the reduction of CO₂ to CO.The Cd S/Cu TCPP photocatalyst achieved the highest CO generation rate of 16.1μmol h^-1(322μmol h^-1 g^-1)for CO₂ reduction.In addition,the sample showed high stability and excellent reusability in CO₂ reduction reaction.This work provides a progress for the application of porphyrins in artificial photosynthesis.2.Cu₂O/Au/Cu TCPP one-dimensional nanoarrays were synthesized by in situ growth method.The Cu₂O/Au/Cu TCPP composite structure can effectively absorb visible light and increase the active area,which is conducive to the adsorption of CO₂.The Cu₂O and Cu TCPP photocatalyst formed a close contact interface with Au.The analytical characterization results verified the role of Au as an electron mediator,which improved the rapid extraction of photoinduced electrons and enhanced the reduction ability of CO₂.The Cu₂O/Au/Cu TCPP nanowires exhibited superior catalytic performance with high faradic efficiency（82%for CO）.In addition,the photostability of the Cu₂O/Au/Cu TCPP was also greatly improved in the electrolyte solution,81.3%faradic efficiency was maintained even after 14 hours continuous light illumination without any protective coating layer.An in situ Raman spectroscopic study further confirms the existence of COOH*species and the engineering intermediates adsorption.This work provides a fundamental insight to the ternary heterojunction in artificial photosynthesis system.