Discovering highly selective catalysts is key to achieve effective CO_(2) photoreduction to hydrocarbon fuels.In this work,we construct an ultrathin dimension-matched S-scheme Bi_(3)NbO_(7)/g-C_(3)N_(4) heterostructur...Discovering highly selective catalysts is key to achieve effective CO_(2) photoreduction to hydrocarbon fuels.In this work,we construct an ultrathin dimension-matched S-scheme Bi_(3)NbO_(7)/g-C_(3)N_(4) heterostructure,which permits the highly selective photocatalytic reduction of CO_(2) to CH_(4),as shown by 13C isotopic measurements.Density functional theory calculations combined with solid-state characterization confirm the electron transfer from g-C_(3)N_(4) nanosheets to Bi_(3)NbO_(7),establishing an internal electric field.The internal electric field drives photogenerated electrons from Bi_(3)NbO_(7) to g-C_(3)N_(4),as revealed by in-situ X-ray photoelectron spectroscopy,demonstrating the presence of an S-scheme charge transfer path in Bi_(3)NbO_(7)/g-C_(3)N_(4) heterostructures allowing efficient and selective CO2 photoreduction.As a result,the optimized sample achieved a CH_(4) evolution rate of 37.59μmol·g^(-1)·h^(-1),a ca.15-fold enhancement compared to ultrathin g-C_(3)N_(4) nanosheets,and also retained stability after 10 reaction cycles and 40 h of simulated solar irradiation with no sacrificial reagents.The optimized Bi3 Nb O7/g-C_(3)N_(4) composites achieve almost 90%selectivity for CH_(4) production over CO.展开更多
The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is high...The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.展开更多
文摘Discovering highly selective catalysts is key to achieve effective CO_(2) photoreduction to hydrocarbon fuels.In this work,we construct an ultrathin dimension-matched S-scheme Bi_(3)NbO_(7)/g-C_(3)N_(4) heterostructure,which permits the highly selective photocatalytic reduction of CO_(2) to CH_(4),as shown by 13C isotopic measurements.Density functional theory calculations combined with solid-state characterization confirm the electron transfer from g-C_(3)N_(4) nanosheets to Bi_(3)NbO_(7),establishing an internal electric field.The internal electric field drives photogenerated electrons from Bi_(3)NbO_(7) to g-C_(3)N_(4),as revealed by in-situ X-ray photoelectron spectroscopy,demonstrating the presence of an S-scheme charge transfer path in Bi_(3)NbO_(7)/g-C_(3)N_(4) heterostructures allowing efficient and selective CO2 photoreduction.As a result,the optimized sample achieved a CH_(4) evolution rate of 37.59μmol·g^(-1)·h^(-1),a ca.15-fold enhancement compared to ultrathin g-C_(3)N_(4) nanosheets,and also retained stability after 10 reaction cycles and 40 h of simulated solar irradiation with no sacrificial reagents.The optimized Bi3 Nb O7/g-C_(3)N_(4) composites achieve almost 90%selectivity for CH_(4) production over CO.
文摘The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.
