Photocatalytic CO_(2)reduction using H_(2)O as the electron donor offers a sustainable pathway for carbon-neutral fuel synthesis;however,its efficiency is limited by sluggish charge separation and insufficient CO_(2)a...Photocatalytic CO_(2)reduction using H_(2)O as the electron donor offers a sustainable pathway for carbon-neutral fuel synthesis;however,its efficiency is limited by sluggish charge separation and insufficient CO_(2)activation.Herein,we develop a ruthenium-decorated,fluorine-doped TiO_(2)photocatalyst(Ru/F-TiO_(2))that overcomes these limitations through spatially directed charge modulation and cooperative electronic engineering.Fluorine doping introduces oxygen vacancies that narrow the bandgap and form surface Ti-F bonds,suppressing charge recombination.Simultaneously,Ru nanoparticles serve as efficient CO_(2)adsorption and activation centers while introducing additional surface defects that further strengthen CO_(2)binding.The strong coupling between Ru and semiconductor forms a Schottky junction,establishing a strong built-in electric field that promotes directional electron migration toward Ru sites and hole accumulation on F-TiO_(2).Consequently,Ru/F-TiO_(2)exhibits outstanding activity and durability,delivering CO and CH_(4)production rates of 124.8 and 19.8μmol/(g·h),respectively.In situ diffuse reflectance infrared Fourier-transform spectroscopy analysis reveals key proton-coupled,multi-electron intermediates,elucidating the reaction pathway.This study demonstrates that the synergistic integration of non-metal doping and metal cocatalyst engineering provides a powerful strategy to regulate charge dynamics and boost solar-driven CO_(2)conversion.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22302039 and 22372035).
文摘Photocatalytic CO_(2)reduction using H_(2)O as the electron donor offers a sustainable pathway for carbon-neutral fuel synthesis;however,its efficiency is limited by sluggish charge separation and insufficient CO_(2)activation.Herein,we develop a ruthenium-decorated,fluorine-doped TiO_(2)photocatalyst(Ru/F-TiO_(2))that overcomes these limitations through spatially directed charge modulation and cooperative electronic engineering.Fluorine doping introduces oxygen vacancies that narrow the bandgap and form surface Ti-F bonds,suppressing charge recombination.Simultaneously,Ru nanoparticles serve as efficient CO_(2)adsorption and activation centers while introducing additional surface defects that further strengthen CO_(2)binding.The strong coupling between Ru and semiconductor forms a Schottky junction,establishing a strong built-in electric field that promotes directional electron migration toward Ru sites and hole accumulation on F-TiO_(2).Consequently,Ru/F-TiO_(2)exhibits outstanding activity and durability,delivering CO and CH_(4)production rates of 124.8 and 19.8μmol/(g·h),respectively.In situ diffuse reflectance infrared Fourier-transform spectroscopy analysis reveals key proton-coupled,multi-electron intermediates,elucidating the reaction pathway.This study demonstrates that the synergistic integration of non-metal doping and metal cocatalyst engineering provides a powerful strategy to regulate charge dynamics and boost solar-driven CO_(2)conversion.
