The solar-driven reduction of CO_(2) into valuable products is a promising method to alleviate global environmental problems and energy crises.However,the low surface charge density limits the photocatalytic conversio...The solar-driven reduction of CO_(2) into valuable products is a promising method to alleviate global environmental problems and energy crises.However,the low surface charge density limits the photocatalytic conversion performance of CO_(2).Herein,a polymeric carbon nitride(PCN)photocatalyst with Zn single atoms(Zn1/CN)was designed and synthesized for CO_(2) photoreduction.The results of the CO_(2) photoreduction studies show that the CO and CH_(4) yields of Zn1/CN increased fivefold,reaching 76.9 and 22.9μmol/(g·h),respectively,in contrast to the unmodified PCN.Ar+plasma-etched X-ray photoelectron spectroscopy and synchrotron radiation-based X-ray absorption fine structure results reveal that Zn single atom is mainly present in the interlayer space of PCN in the Zn–N_(4) configuration.Photoelectrochemical characterizations indicate that the interlayer Zn–N_(4) configuration can amplify light absorption and establish an interlayer charge transfer channel.Light-assisted Kelvin probe force microscopy confirms that more photogenerated electrons are delivered to the catalyst surface through interlayer Zn–N_(4) configuration,which increases its surface charge density.Further,in-situ infrared spectroscopy combined with density functional theory calculation reveals that promoted surface charge density accelerates key intermediates(*COOH)conversion,thus achieving efficient CO_(2) conversion.This work elucidates the role of internal single atoms in catalytic surface reactions,which provides important implications for the design of single-atom catalysts.展开更多
Aluminosilicate clay mineral(ACM)is a kind of typical raw materials that used widely in manufacturing industry owing to the abundant reserve and low-cost exploring.In past two decades,in-depth understanding on unique ...Aluminosilicate clay mineral(ACM)is a kind of typical raw materials that used widely in manufacturing industry owing to the abundant reserve and low-cost exploring.In past two decades,in-depth understanding on unique layered structure and abundant surface proper-ties endows ACM in the emerging research and application fields.In field of solar-chemical energy conversion,ACM has been widely used to support various semiconductor photocata-lysts,forming the composites and achieving efficient conversion of reactants under sunlight irradiation.To date,classic ACM such as kaolinite and montmorillonite,loaded with semi-conductor photocatalysts has been widely applied in photocatalysis.This review summaries the recent works on ACM-based composites in photocatalysis.Focusing on the properties of surface and layered structure,we elucidate the different features in the composition with various functional photocatalysts on two typical kinds of ACM,i.e.,type 1∶1 and type 2∶1.Not only large surface area and active surface hydroxyl group assist the substrate adsorption,but also the layered structure provides more space to enlarge the application of ACM-based photocatalysts.Besides,we overview the modifications on ACM from both external surface and the inter-layer space that make the formation of composites more efficiently and boost the photo-chemical process.This review could inspire more upcoming design and synthesis for ACM-based photocatalysts,leading this kind of economic and eco-friendly materials for more practical application in the future.展开更多
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences,China(Nos.XDA23010300 and XDA23010000)the National Natural Science Foundation of China(Nos.51878644 and 41573138)the CAS Youth Interdisciplinary Team.
文摘The solar-driven reduction of CO_(2) into valuable products is a promising method to alleviate global environmental problems and energy crises.However,the low surface charge density limits the photocatalytic conversion performance of CO_(2).Herein,a polymeric carbon nitride(PCN)photocatalyst with Zn single atoms(Zn1/CN)was designed and synthesized for CO_(2) photoreduction.The results of the CO_(2) photoreduction studies show that the CO and CH_(4) yields of Zn1/CN increased fivefold,reaching 76.9 and 22.9μmol/(g·h),respectively,in contrast to the unmodified PCN.Ar+plasma-etched X-ray photoelectron spectroscopy and synchrotron radiation-based X-ray absorption fine structure results reveal that Zn single atom is mainly present in the interlayer space of PCN in the Zn–N_(4) configuration.Photoelectrochemical characterizations indicate that the interlayer Zn–N_(4) configuration can amplify light absorption and establish an interlayer charge transfer channel.Light-assisted Kelvin probe force microscopy confirms that more photogenerated electrons are delivered to the catalyst surface through interlayer Zn–N_(4) configuration,which increases its surface charge density.Further,in-situ infrared spectroscopy combined with density functional theory calculation reveals that promoted surface charge density accelerates key intermediates(*COOH)conversion,thus achieving efficient CO_(2) conversion.This work elucidates the role of internal single atoms in catalytic surface reactions,which provides important implications for the design of single-atom catalysts.
基金This work was supported by the National Natural Science Foundation of China(21976054)the National Key Research and Development Program of China(2017YFA0207002)Beijing Outstanding Young Scientist Program.
文摘Aluminosilicate clay mineral(ACM)is a kind of typical raw materials that used widely in manufacturing industry owing to the abundant reserve and low-cost exploring.In past two decades,in-depth understanding on unique layered structure and abundant surface proper-ties endows ACM in the emerging research and application fields.In field of solar-chemical energy conversion,ACM has been widely used to support various semiconductor photocata-lysts,forming the composites and achieving efficient conversion of reactants under sunlight irradiation.To date,classic ACM such as kaolinite and montmorillonite,loaded with semi-conductor photocatalysts has been widely applied in photocatalysis.This review summaries the recent works on ACM-based composites in photocatalysis.Focusing on the properties of surface and layered structure,we elucidate the different features in the composition with various functional photocatalysts on two typical kinds of ACM,i.e.,type 1∶1 and type 2∶1.Not only large surface area and active surface hydroxyl group assist the substrate adsorption,but also the layered structure provides more space to enlarge the application of ACM-based photocatalysts.Besides,we overview the modifications on ACM from both external surface and the inter-layer space that make the formation of composites more efficiently and boost the photo-chemical process.This review could inspire more upcoming design and synthesis for ACM-based photocatalysts,leading this kind of economic and eco-friendly materials for more practical application in the future.
