Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like cov...Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like covalent organic framework(COF)to form a step-scheme(S-scheme)photocata-lyst for H_(2)O_(2)production.The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF.The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and in-situ X-ray photoelectron and femtosecond transient absorption spectroscopies.Photolumi-nescence,time-resolved photoluminescence,photocurrent response,electrochemical impedance spectroscopy,and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability,resulting in enhanced photocatalytic performance.Remarkably,a 10%-ZnSe QD/COF has excellent photocatalytic H_(2)O_(2)-production activity,and the optimal S-scheme composite with ethanol as the hole scavenger yields a H_(2)O_(2)-production rate of 1895 mol g^(-1)h^(-1).This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H_(2)O_(2)production.展开更多
In recent years,ternary heterostructures(HSs)composed of three semiconductors have attracted significant attention because of the effective separation and transfer of photogenerated electrons and holes in these materi...In recent years,ternary heterostructures(HSs)composed of three semiconductors have attracted significant attention because of the effective separation and transfer of photogenerated electrons and holes in these materials.In this work,new ternary Cd S/Zn S/Zn O(CZZ)HSs with one-dimensional(1D)nanofiber morphology have been successfully fabricated for the first time by a series of processes:electrospinning Zn O nanofibers,sulfurizing Zn O in situ to form Zn S/Zn O binary HSs,and depositing Cd S quantum dots in situ on the Zn S/Zn O HSs.Benefiting from the efficient separation and transfer of photoinduced charge carriers,the optimized CZZ ternary HSs exhibit a hydrogen evolution rate of 51.45 mmol h^-1 g^-1(quantum efficiency:26.88%at 420 nm)without any co-catalyst,which is 93.54 and 2.28 times higher than those exhibited by pristine Zn O and Zn S/Zn O binary HSs,respectively,under the same conditions.Furthermore,the rate of hydrogen evolution over the 1D CZZ nanofibers is significantly higher than that over 2D CZZ nanosheets(27.25 mmol h^-1 g^-1,in the presence of a Pt co-catalyst)prepared by the same sulfurization and deposition procedures.This can be ascribed to the significantly smaller geometric sizes of 1D nanofibers compared to those of 2D nanosheets,resulting in effectively suppressed recombination of photogenerated charge carriers and promotion of photocatalytic H2 evolution performance.展开更多
文摘Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like covalent organic framework(COF)to form a step-scheme(S-scheme)photocata-lyst for H_(2)O_(2)production.The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF.The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and in-situ X-ray photoelectron and femtosecond transient absorption spectroscopies.Photolumi-nescence,time-resolved photoluminescence,photocurrent response,electrochemical impedance spectroscopy,and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability,resulting in enhanced photocatalytic performance.Remarkably,a 10%-ZnSe QD/COF has excellent photocatalytic H_(2)O_(2)-production activity,and the optimal S-scheme composite with ethanol as the hole scavenger yields a H_(2)O_(2)-production rate of 1895 mol g^(-1)h^(-1).This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H_(2)O_(2)production.
文摘In recent years,ternary heterostructures(HSs)composed of three semiconductors have attracted significant attention because of the effective separation and transfer of photogenerated electrons and holes in these materials.In this work,new ternary Cd S/Zn S/Zn O(CZZ)HSs with one-dimensional(1D)nanofiber morphology have been successfully fabricated for the first time by a series of processes:electrospinning Zn O nanofibers,sulfurizing Zn O in situ to form Zn S/Zn O binary HSs,and depositing Cd S quantum dots in situ on the Zn S/Zn O HSs.Benefiting from the efficient separation and transfer of photoinduced charge carriers,the optimized CZZ ternary HSs exhibit a hydrogen evolution rate of 51.45 mmol h^-1 g^-1(quantum efficiency:26.88%at 420 nm)without any co-catalyst,which is 93.54 and 2.28 times higher than those exhibited by pristine Zn O and Zn S/Zn O binary HSs,respectively,under the same conditions.Furthermore,the rate of hydrogen evolution over the 1D CZZ nanofibers is significantly higher than that over 2D CZZ nanosheets(27.25 mmol h^-1 g^-1,in the presence of a Pt co-catalyst)prepared by the same sulfurization and deposition procedures.This can be ascribed to the significantly smaller geometric sizes of 1D nanofibers compared to those of 2D nanosheets,resulting in effectively suppressed recombination of photogenerated charge carriers and promotion of photocatalytic H2 evolution performance.
