Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to real...Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to realize carbon-free hydrogen production remains a challenge.Heterojunction photocatalysts with well-defined dimensionality and perfectly matched interfaces are promising for achieving highly efficient solar-to-hydrogen conversion.Herein,we report the fabrication of a novel type of protonated graphitic carbon nitride(PCN)/Ti3C2 MXene heterojunctions with strong interfacial interactions.As expected,the two-dimensional(2D)PCN/2D Ti3C2 MXene interface heterojunction achieves a highly improved hydrogen evolution rate(2181μmol∙g‒1)in comparison with bulk g-C3N4(393μmol∙g‒1)and protonated g-C3N4(816μmol∙g‒1).The charge-regulated surfaces of PCN and the accelerated charge transport at the face-to-face 2D/2D Schottky heterojunction interface are the major contributors to the excellent hydrogen evolution performance of the composite photocatalyst.展开更多
The development of an efficient artificial H_(2)O_(2)photosynthesis system is a challenging work using H_(2)O and O_(2)as starting materials.Herein,3D In2.77S_(4)nanoflower precursor was in-situ deposited on K^(+)-dop...The development of an efficient artificial H_(2)O_(2)photosynthesis system is a challenging work using H_(2)O and O_(2)as starting materials.Herein,3D In2.77S_(4)nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In2.77S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2)production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In2.77S_(4),respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In2.77S_(4)according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2)production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2)around the active centers,the energy barriers of O_(2)protonation and H_(2)O_(2)desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2)photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.展开更多
The photocatalytic activity of catalysts depends on the energy-harvesting ability and the separation or transport of photogenerated carriers.The light absorption capacity of graphitic carbon nitride(g-C_(3)N_(4))-base...The photocatalytic activity of catalysts depends on the energy-harvesting ability and the separation or transport of photogenerated carriers.The light absorption capacity of graphitic carbon nitride(g-C_(3)N_(4))-based composites can be enhanced by adjusting the surface plasmon resonance(SPR)of noble metal nanoparticles(e.g.,Cu,Au,and Pd)in the entire visible region.Adjustments can be carried out by varying the nanocomponents of the materials.The SPR of noble metals can enhance the local electromagnetic field and improve interband transition,and resonant energy transfer occurs from plasmonic dipoles to electron-hole pairs via near-field electromagnetic interactions.Thus,noble metals have emerged as relevant nanocomponents for g-C_(3)N_(4) used in CO_(2) photoreduction and water splitting.Herein,recent key advances in noble metals(either in single atom,cluster,or nanoparticle forms)and composite photocatalysts based on inorganic or organic nanocomponent-incorporated g-C_(3)N_(4) nanosheets are systematically discussed,including the applications of these photocatalysts,which exhibit improved photoinduced charge mobility in CO_(2) photoconversion and H2 production.Issues related to the different types of multi-nanocomponent heterostructures(involving Schottky junctions,Z-/S-scheme heterostructures,noble metals,and additional semiconductor nanocomponents)and the adjustment of dimensionality of heterostructures(by incorporating noble metal nanoplates on g-C_(3)N_(4) forming 2D/2D heterostructures)are explored.The current prospects and possible challenges of g-C_(3)N_(4) composite photocatalysts incorporated with noble metals(e.g.,Au,Pt,Pd,and Cu),particularly in water splitting,CO_(2) reduction,pollution degradation,and chemical conversion applications,are summarized.展开更多
文摘Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to realize carbon-free hydrogen production remains a challenge.Heterojunction photocatalysts with well-defined dimensionality and perfectly matched interfaces are promising for achieving highly efficient solar-to-hydrogen conversion.Herein,we report the fabrication of a novel type of protonated graphitic carbon nitride(PCN)/Ti3C2 MXene heterojunctions with strong interfacial interactions.As expected,the two-dimensional(2D)PCN/2D Ti3C2 MXene interface heterojunction achieves a highly improved hydrogen evolution rate(2181μmol∙g‒1)in comparison with bulk g-C3N4(393μmol∙g‒1)and protonated g-C3N4(816μmol∙g‒1).The charge-regulated surfaces of PCN and the accelerated charge transport at the face-to-face 2D/2D Schottky heterojunction interface are the major contributors to the excellent hydrogen evolution performance of the composite photocatalyst.
文摘The development of an efficient artificial H_(2)O_(2)photosynthesis system is a challenging work using H_(2)O and O_(2)as starting materials.Herein,3D In2.77S_(4)nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In2.77S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2)production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In2.77S_(4),respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In2.77S_(4)according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2)production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2)around the active centers,the energy barriers of O_(2)protonation and H_(2)O_(2)desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2)photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.
基金supported in part by the projects from the National Natural Science Foundation of China(No.51972145)Jinan Science&Technology Bureau,China(No.2021GXRC109)Science and Technology Program of the University of Jinan,China(No.XKY2118).
文摘The photocatalytic activity of catalysts depends on the energy-harvesting ability and the separation or transport of photogenerated carriers.The light absorption capacity of graphitic carbon nitride(g-C_(3)N_(4))-based composites can be enhanced by adjusting the surface plasmon resonance(SPR)of noble metal nanoparticles(e.g.,Cu,Au,and Pd)in the entire visible region.Adjustments can be carried out by varying the nanocomponents of the materials.The SPR of noble metals can enhance the local electromagnetic field and improve interband transition,and resonant energy transfer occurs from plasmonic dipoles to electron-hole pairs via near-field electromagnetic interactions.Thus,noble metals have emerged as relevant nanocomponents for g-C_(3)N_(4) used in CO_(2) photoreduction and water splitting.Herein,recent key advances in noble metals(either in single atom,cluster,or nanoparticle forms)and composite photocatalysts based on inorganic or organic nanocomponent-incorporated g-C_(3)N_(4) nanosheets are systematically discussed,including the applications of these photocatalysts,which exhibit improved photoinduced charge mobility in CO_(2) photoconversion and H2 production.Issues related to the different types of multi-nanocomponent heterostructures(involving Schottky junctions,Z-/S-scheme heterostructures,noble metals,and additional semiconductor nanocomponents)and the adjustment of dimensionality of heterostructures(by incorporating noble metal nanoplates on g-C_(3)N_(4) forming 2D/2D heterostructures)are explored.The current prospects and possible challenges of g-C_(3)N_(4) composite photocatalysts incorporated with noble metals(e.g.,Au,Pt,Pd,and Cu),particularly in water splitting,CO_(2) reduction,pollution degradation,and chemical conversion applications,are summarized.
