Constructing a suitable heterojunction photocatalytic system from two photocatalytic materials is an efficient approach for designing extremely efficient photocatalysts for a broader range of environmental,medical,and...Constructing a suitable heterojunction photocatalytic system from two photocatalytic materials is an efficient approach for designing extremely efficient photocatalysts for a broader range of environmental,medical,and energy applications.Recently,the construction of a step-scheme heterostructure system(hereafter called the S-scheme)has received widespread attention in the photocatalytic field due to its ability to achieve efficient photogenerated carrier separation and obtain strong photo-redox ability.Herein,a novel S-scheme heterojunction system consisting of 2D O-doped g-C_(3)N_(4)(OCN)nanosheets and 3D N-doped Nb_(2)O_(5)/C(N-NBO/C)nanoflowers is constructed via ultrasonication and vigorous agitation technique followed by heat treatment for the photocatalytic degradation of Rhodamine B(RhB).Detailed characterization and decomposition behaviour of RhB showed that the fabricated material shows excellent photocatalytic efficiency and stability towards RhB photodegradation under visible-light illumination.The enhanced performance could be attributed to the following factors:fast charge transfer,highly-efficient charge separation,extended lifetime of photoinduced charge carriers,and the high redox capability of the photoinduced charges in the S-scheme system.Various trapping experiment conditions and electron paramagnetic resonance provide clear evidence of the S-scheme photogenerated charge transfer path,meanwhile,the RhB mineralization degradation pathway was also investigated using LC-MS.This study presents an approach to constructing Nb_(2)O_(5)-based S-scheme heterojunctions for photocatalytic applications.展开更多
Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production.However,developing effective and stable non‐noble‐metal electrocatalysts which work well at high current densities demand...Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production.However,developing effective and stable non‐noble‐metal electrocatalysts which work well at high current densities demanded by industry still remain great challenge.Herein,taking advantage of the highly tunable metal‐organic framework(MOF)templates,nitrogen doped binary transition metal phosphides electrocatalysts(N‐CoP_(x)/Ni_(2)P)with three‐dimensional(3D)conductive network structure were successfully synthesized.The 3D open porous channels could expose more catalytically active sites;nitrogen doping and the synergistic effect between CoP and Ni_(2)P can increase the electron density of Co atoms at active sites,further optimizing the Gibbs free energy of hydrogen(ΔGH*)and water(ΔG_(H_(2)O*)).As a result,the obtained N‐CoP_(x)/Ni_(2)P catalyst exhibits extraordinary electrocatalytic activity in a wide pH range.Especially,it requires an extremely low overpotential of 152 mV to deliver a high current density of 650 mA cm^(–2) in alkaline media.This work may shed some light on the rational design of cheap electrocatalysts and electrode materials that work well at high current densities.展开更多
Photocatalytic water splitting has increasingly attracted attention as one of the most useful methods of converting solar energy into chemical fuel.However,the undesirable reverse reaction significantly limits the enh...Photocatalytic water splitting has increasingly attracted attention as one of the most useful methods of converting solar energy into chemical fuel.However,the undesirable reverse reaction significantly limits the enhancement of efficiency.Herein,we fabricated an Au nanorods/TiO2 nanodumbbells structure photocatalyst(Au NRs/TiO2 NDs)via a facile synthetic strategy,which has spatially separated oxidation and reduction reaction zones.Owing to the unique structure,the charge separation of these photocatalysts can be significantly improved and the reverse reaction can be efficiently inhibited.The photogenerated electrons were injected from the TiO2 to the Au NRs,and a positively charged TiO2 region and negatively charged Au region were formed under UV irradiation.An enhanced hydrogen production performance was obtained compared with that seen in normal Au-TiO2 heterostructure.Under optimized conditions,the H2-production rate can reach up to 60,264μmol/g/h,about six times higher than previously reported Au/TiO2 photocatalysts.Besides this,our work also demonstrates the key factors of precise synthesis of the Au NRs/TiO2 NDs structure,which provides a new perspective and experience for the design of similar catalysts.展开更多
Carbon nitride(C_(3)N_(4))is promising for photocatalytic hydrogen production,but photogenerated electrons and holes in C_(3)N_(4)usually tend to exist as excitons due to intrinsic Coulomb interactions making its phot...Carbon nitride(C_(3)N_(4))is promising for photocatalytic hydrogen production,but photogenerated electrons and holes in C_(3)N_(4)usually tend to exist as excitons due to intrinsic Coulomb interactions making its photocatalytic activity unsatisfactory.Herein,a well‐designed intramolecular C_(3)N_(4)‐based donor‐acceptor(D‐A)photocatalytic system was constructed to promote exciton dissociation.Due to its good chemical compatibility with melamine and appropriate sublimation property,2‐amino‐4,6‐dichloropyrimidine unit was chosen as the monomer to react with melamine to construct intramolecular D‐A system(CNCl_(x)).The hydrogen evolution rate of CNCl_(0.15)is 15.3 times higher than that of bulk C_(3)N_(4)under visible light irradiation,with apparent quantum efficiency of 13.6%at 420 nm.The enhanced activity is attributed to introduced electron‐withdrawing−Cl group as terminal group in the resulted CNCl_(x) samples,which can build internal electric field to promote the exciton dissociation into free electron and hole.In addition,lower work function value of CNCl_(x) samples indicates that internal electric field can help free electrons and holes transfer to the surface of CNCl_(x) samples for photocatalytic reaction.展开更多
文摘Constructing a suitable heterojunction photocatalytic system from two photocatalytic materials is an efficient approach for designing extremely efficient photocatalysts for a broader range of environmental,medical,and energy applications.Recently,the construction of a step-scheme heterostructure system(hereafter called the S-scheme)has received widespread attention in the photocatalytic field due to its ability to achieve efficient photogenerated carrier separation and obtain strong photo-redox ability.Herein,a novel S-scheme heterojunction system consisting of 2D O-doped g-C_(3)N_(4)(OCN)nanosheets and 3D N-doped Nb_(2)O_(5)/C(N-NBO/C)nanoflowers is constructed via ultrasonication and vigorous agitation technique followed by heat treatment for the photocatalytic degradation of Rhodamine B(RhB).Detailed characterization and decomposition behaviour of RhB showed that the fabricated material shows excellent photocatalytic efficiency and stability towards RhB photodegradation under visible-light illumination.The enhanced performance could be attributed to the following factors:fast charge transfer,highly-efficient charge separation,extended lifetime of photoinduced charge carriers,and the high redox capability of the photoinduced charges in the S-scheme system.Various trapping experiment conditions and electron paramagnetic resonance provide clear evidence of the S-scheme photogenerated charge transfer path,meanwhile,the RhB mineralization degradation pathway was also investigated using LC-MS.This study presents an approach to constructing Nb_(2)O_(5)-based S-scheme heterojunctions for photocatalytic applications.
文摘Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production.However,developing effective and stable non‐noble‐metal electrocatalysts which work well at high current densities demanded by industry still remain great challenge.Herein,taking advantage of the highly tunable metal‐organic framework(MOF)templates,nitrogen doped binary transition metal phosphides electrocatalysts(N‐CoP_(x)/Ni_(2)P)with three‐dimensional(3D)conductive network structure were successfully synthesized.The 3D open porous channels could expose more catalytically active sites;nitrogen doping and the synergistic effect between CoP and Ni_(2)P can increase the electron density of Co atoms at active sites,further optimizing the Gibbs free energy of hydrogen(ΔGH*)and water(ΔG_(H_(2)O*)).As a result,the obtained N‐CoP_(x)/Ni_(2)P catalyst exhibits extraordinary electrocatalytic activity in a wide pH range.Especially,it requires an extremely low overpotential of 152 mV to deliver a high current density of 650 mA cm^(–2) in alkaline media.This work may shed some light on the rational design of cheap electrocatalysts and electrode materials that work well at high current densities.
基金supported by the National Natural Science Foundation of China(21703046)the National Key R&D of China(2016YFF0203803,2016YFA0200902)~~
文摘Photocatalytic water splitting has increasingly attracted attention as one of the most useful methods of converting solar energy into chemical fuel.However,the undesirable reverse reaction significantly limits the enhancement of efficiency.Herein,we fabricated an Au nanorods/TiO2 nanodumbbells structure photocatalyst(Au NRs/TiO2 NDs)via a facile synthetic strategy,which has spatially separated oxidation and reduction reaction zones.Owing to the unique structure,the charge separation of these photocatalysts can be significantly improved and the reverse reaction can be efficiently inhibited.The photogenerated electrons were injected from the TiO2 to the Au NRs,and a positively charged TiO2 region and negatively charged Au region were formed under UV irradiation.An enhanced hydrogen production performance was obtained compared with that seen in normal Au-TiO2 heterostructure.Under optimized conditions,the H2-production rate can reach up to 60,264μmol/g/h,about six times higher than previously reported Au/TiO2 photocatalysts.Besides this,our work also demonstrates the key factors of precise synthesis of the Au NRs/TiO2 NDs structure,which provides a new perspective and experience for the design of similar catalysts.
文摘Carbon nitride(C_(3)N_(4))is promising for photocatalytic hydrogen production,but photogenerated electrons and holes in C_(3)N_(4)usually tend to exist as excitons due to intrinsic Coulomb interactions making its photocatalytic activity unsatisfactory.Herein,a well‐designed intramolecular C_(3)N_(4)‐based donor‐acceptor(D‐A)photocatalytic system was constructed to promote exciton dissociation.Due to its good chemical compatibility with melamine and appropriate sublimation property,2‐amino‐4,6‐dichloropyrimidine unit was chosen as the monomer to react with melamine to construct intramolecular D‐A system(CNCl_(x)).The hydrogen evolution rate of CNCl_(0.15)is 15.3 times higher than that of bulk C_(3)N_(4)under visible light irradiation,with apparent quantum efficiency of 13.6%at 420 nm.The enhanced activity is attributed to introduced electron‐withdrawing−Cl group as terminal group in the resulted CNCl_(x) samples,which can build internal electric field to promote the exciton dissociation into free electron and hole.In addition,lower work function value of CNCl_(x) samples indicates that internal electric field can help free electrons and holes transfer to the surface of CNCl_(x) samples for photocatalytic reaction.
