Herein,the catalysts of ultrathin g-C_(3)N_(4)surface-modified hollow spherical Bi2MoO6(g-C_(3)N_(4)/Bi2MoO6,abbreviated as CN/BMO)were fabricated by the co-solvothermal method.The variable valence Mo^(5+)/Mo^(6+)ioni...Herein,the catalysts of ultrathin g-C_(3)N_(4)surface-modified hollow spherical Bi2MoO6(g-C_(3)N_(4)/Bi2MoO6,abbreviated as CN/BMO)were fabricated by the co-solvothermal method.The variable valence Mo^(5+)/Mo^(6+)ionic bridge in CN/BMO catalysts can boost the rapid transfer of photogenerated electrons from Bi2MoO6to g-C_(3)N_(4).And the synergy effect of g-C_(3)N_(4)and Bi2MoO6components remarkably enhance CO_(2)adsorption capability.CN/BMO-2 catalyst has the best performances for visible light-driven CO_(2)reduction compared with single Bi2MoO6and g-C_(3)N_(4),i.e.,its amount and selectivity of CO product are 139.50μmol g-1and 96.88%for 9 h,respectively.Based on the results of characterizations and density functional theory calculation,the photocatalytic mechanism for CO_(2)reduction is proposed.The high-efficient separation efficiency of photogenerated electron-hole pairs,induced by variable valence Mo^(5+)/Mo^(6+)ionic bridge,can boost the rate-limiting steps(COOH*-to-CO*and CO*desorption)of selective visible light-driven CO_(2)conversion into CO.It inspires the establishment of efficient photocatalysts for CO_(2)conversion.展开更多
Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions...Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.展开更多
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
The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical in...The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical industry.Here,we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method.By changing the reduction temperature,catalysts with different oxidation state could be precisely constructed.Moreover,the important correlation between the ratio of Pd^(0)/Pd^(2+)and catalytic activity is revealed during the selective hydrogenation of HMF.The Pd/g—C_(3)N_(4)—300 catalyst with a Pd^(0)/Pd^(2+)ratio of 3/2 showed the highest catalytic activity,which could get 96.9%5-hydroxymethylfurfural conversion and 90.3%2,5-dihydroxymethylfuran selectivity.Further density functional theory calculation revealed that the synergistic effect between Pd0and Pd2+in Pd/g—C_(3)N_(4)—300 system could boost the adsorption of the substrate and the dissociation of hydrogen.In this work,we highlight the important correlation between metal oxidation state and catalytic activity,which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.展开更多
基金supported by the National Natural Science Foundation of China(21972166)the Beijing Natural Science Foundation(2202045)the National Key Research and Development Program of China(2019YFC1907600)。
文摘Herein,the catalysts of ultrathin g-C_(3)N_(4)surface-modified hollow spherical Bi2MoO6(g-C_(3)N_(4)/Bi2MoO6,abbreviated as CN/BMO)were fabricated by the co-solvothermal method.The variable valence Mo^(5+)/Mo^(6+)ionic bridge in CN/BMO catalysts can boost the rapid transfer of photogenerated electrons from Bi2MoO6to g-C_(3)N_(4).And the synergy effect of g-C_(3)N_(4)and Bi2MoO6components remarkably enhance CO_(2)adsorption capability.CN/BMO-2 catalyst has the best performances for visible light-driven CO_(2)reduction compared with single Bi2MoO6and g-C_(3)N_(4),i.e.,its amount and selectivity of CO product are 139.50μmol g-1and 96.88%for 9 h,respectively.Based on the results of characterizations and density functional theory calculation,the photocatalytic mechanism for CO_(2)reduction is proposed.The high-efficient separation efficiency of photogenerated electron-hole pairs,induced by variable valence Mo^(5+)/Mo^(6+)ionic bridge,can boost the rate-limiting steps(COOH*-to-CO*and CO*desorption)of selective visible light-driven CO_(2)conversion into CO.It inspires the establishment of efficient photocatalysts for CO_(2)conversion.
文摘Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.
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.
基金supported by the National Key Research and Development Program of China(2021YFA1500500)。
文摘The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical industry.Here,we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method.By changing the reduction temperature,catalysts with different oxidation state could be precisely constructed.Moreover,the important correlation between the ratio of Pd^(0)/Pd^(2+)and catalytic activity is revealed during the selective hydrogenation of HMF.The Pd/g—C_(3)N_(4)—300 catalyst with a Pd^(0)/Pd^(2+)ratio of 3/2 showed the highest catalytic activity,which could get 96.9%5-hydroxymethylfurfural conversion and 90.3%2,5-dihydroxymethylfuran selectivity.Further density functional theory calculation revealed that the synergistic effect between Pd0and Pd2+in Pd/g—C_(3)N_(4)—300 system could boost the adsorption of the substrate and the dissociation of hydrogen.In this work,we highlight the important correlation between metal oxidation state and catalytic activity,which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.
