A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the ph...A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO_(2) catalyst,which was much higher than that of pristine TiO_(2)(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO_(2) promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO_(2) also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.展开更多
CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed gra...CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed graphite-CeO_(2) interfaces to enhance solar-driven photothermal catalytic DRM.Compared with carbon nanotubes-modified CeO_(2)(CeO_(2)-CNT),graphite-modified CeO_(2)(CeO_(2)-GRA)constructed graphite-CeO_(2) interfaces with distortion in CeO_(2),leading to the formation abundant oxygen vacancies.These graphite-CeO_(2) interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers.The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3℃,boosting light-to-thermal conversion.The synergy between photogenerated carriers and localized heat enabled Ni/CeO_(2)-GRA to achieve a CO production rate of 9985.6 mmol/(g·h)(vs 7192.4 mmol/(g·h)for Ni/CeO_(2))and a light-to-fuel efficiency of 21.8%(vs 13.8%for Ni/CeO_(2)).This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.展开更多
基金supported by the National Key R&D Program of China(2021YFF0500703)Natural Science Foundation of Shanghai(22JC1404200)+3 种基金Program of Shanghai Academic/Technology Research Leader(20XD1404000)Natural Science Foundation of China(U22B20136,22293023)Science and Technology Major Project of Inner Mongolia(2021ZD0042)the Youth Innovation Promotion Association of CAS。
文摘A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO_(2) catalyst,which was much higher than that of pristine TiO_(2)(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO_(2) promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO_(2) also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.
文摘CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed graphite-CeO_(2) interfaces to enhance solar-driven photothermal catalytic DRM.Compared with carbon nanotubes-modified CeO_(2)(CeO_(2)-CNT),graphite-modified CeO_(2)(CeO_(2)-GRA)constructed graphite-CeO_(2) interfaces with distortion in CeO_(2),leading to the formation abundant oxygen vacancies.These graphite-CeO_(2) interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers.The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3℃,boosting light-to-thermal conversion.The synergy between photogenerated carriers and localized heat enabled Ni/CeO_(2)-GRA to achieve a CO production rate of 9985.6 mmol/(g·h)(vs 7192.4 mmol/(g·h)for Ni/CeO_(2))and a light-to-fuel efficiency of 21.8%(vs 13.8%for Ni/CeO_(2)).This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.
