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
Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by...Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO_(2).Structural characterizations revealed that a distinct TiO_(x) coating on the Ni nanoparticles(NPs)was evident for Ni/TiO_(2)-700 catalyst due to strong metal-support interaction.It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased,thereby enhancing the exposure of Ni active sites.The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4,which led to the much elevated catalytic activity for Ni/TiO_(2)-950 in which rutile dominated.Therefore,the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio.Ni/TiO_(2)-950,characterized by a predominant rutile phase,exhibited the highest DRM reactivity,with remarkable H_(2) and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h),respectively.These rates were approximately 257 and 130 times higher,respectively,compared to those obtained on Ni/TiO_(2)-700 with anatase.This study suggests that the optimization of crystal structure of TiO_(2) support can effectively enhance the performance of photothermal DRM reaction.展开更多
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
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.
基金The project was supported by Natural Science Foundation of China(22072177)Natural Science Foundation of Shanghai(21ZR1471700)Shanghai Youth Science and Technology Talents Sailing Program(21YF1453600)。
基金The project was supported by the National Key R&D Program of China(2021YFF0500702)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Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO_(2).Structural characterizations revealed that a distinct TiO_(x) coating on the Ni nanoparticles(NPs)was evident for Ni/TiO_(2)-700 catalyst due to strong metal-support interaction.It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased,thereby enhancing the exposure of Ni active sites.The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4,which led to the much elevated catalytic activity for Ni/TiO_(2)-950 in which rutile dominated.Therefore,the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio.Ni/TiO_(2)-950,characterized by a predominant rutile phase,exhibited the highest DRM reactivity,with remarkable H_(2) and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h),respectively.These rates were approximately 257 and 130 times higher,respectively,compared to those obtained on Ni/TiO_(2)-700 with anatase.This study suggests that the optimization of crystal structure of TiO_(2) support can effectively enhance the performance of photothermal DRM reaction.
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.
