The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limit...The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limited by sluggish water oxidation kinetics,poor photogenerated charge separation,and insufficient O_(2)adsorption and activation capabilities.Herein,uniformly dispersed single-atom catalysts(SACs)with a Co-N_(4)coordination structure have been synthesized by thermally transforming cobalt phthalocyanine(CoPc)assemblies pre-anchored on phosphate functionalized reduced graphene oxide(Co@rGO-P),and then used to construct heterojunctions with perylenetetracarboxylic acid(PTA)nanosheets for photocatalytic H_(2)O_(2)production by an in-situ growth method.The optimized Co@rGO-P/PTA achieved an H_(2)O_(2)production rate of 1.4 mmol g^(-1)h^(-1)in pure water,with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials.Femtosecond transient absorption spectra,in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N_(4),and to the promoted O_(2)adsorption and activation at Co-N_(4)active sites.This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H_(2)O_(2)production.展开更多
文摘The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limited by sluggish water oxidation kinetics,poor photogenerated charge separation,and insufficient O_(2)adsorption and activation capabilities.Herein,uniformly dispersed single-atom catalysts(SACs)with a Co-N_(4)coordination structure have been synthesized by thermally transforming cobalt phthalocyanine(CoPc)assemblies pre-anchored on phosphate functionalized reduced graphene oxide(Co@rGO-P),and then used to construct heterojunctions with perylenetetracarboxylic acid(PTA)nanosheets for photocatalytic H_(2)O_(2)production by an in-situ growth method.The optimized Co@rGO-P/PTA achieved an H_(2)O_(2)production rate of 1.4 mmol g^(-1)h^(-1)in pure water,with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials.Femtosecond transient absorption spectra,in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N_(4),and to the promoted O_(2)adsorption and activation at Co-N_(4)active sites.This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H_(2)O_(2)production.
