Regulating charge transfer to achieve specific transfer path can improve electron utilization and complete efficient photoreduction of CO_(2).Here,we fabricated a S-scheme heterojunction of CN/Fe-MOF by an in-situ ass...Regulating charge transfer to achieve specific transfer path can improve electron utilization and complete efficient photoreduction of CO_(2).Here,we fabricated a S-scheme heterojunction of CN/Fe-MOF by an in-situ assembly strategy.The S-scheme charge transfer mechanism was confirmed by band structure,electron spin resonance(ESR)and work function(Φ)analysis.On the one hand,the response of Fe-MOF in the visible region improved the utilization of light energy,thus increasing the ability of CN/Fe-MOF to generate charge carriers.On the other hand,CN,as the active site,not only had strong adsorption capacity for CO_(2),but also retained photogenerated electrons with high reduction capacity because of S-scheme charge transfer mechanism.Hence,in the absence of any sacrificial agent and cocatalyst,the optimized 50CN/Fe-MOF obtained the highest CO yield(19.17μmol g^(–1))under UV-Vis irradiation,which was almost 10 times higher than that of CN.In situ Fourier transform infrared spectra not only revealed that the photoreduction of CO_(2) occurred at the CN,but also demonstrated that the S-scheme charge transfer mechanism enabled 50CN/Fe-MOF to have a stronger ability to generate HCOO–than CN.展开更多
Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a...Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a novel pyrazine-based Fe-MOFs(MIL-101(Fe)-Pz)by substituting the 1,4-dicarboxybenzene acid ligands in typical MIL-101(Fe)with 2,5-pyrazinedicarboxylic acid(PzDC),in which sodium acetate was used as coordinative modulator to control the crystal size(2–3μm).The incorporation of Fe-pyridine N coordination structures originated from PzDC ligands gave MIL-101(Fe)-Pz narrowed band gap(1.45 eV)than MIL-101(Fe)(2.54 eV)resulting in improved visible-light adsorption capacity(λ>420 nm),and also increased the proportion of Fe(Ⅱ)in the Fe-clusters.Thus MIL-101(Fe)-Pz exhibited a synergistic enhanced photo-Fenton-like catalytic performance under visible-light irradiation.The MIL-101(Fe)-Pz/H_(2)O_(2)/Vis system could degrade 99%of sulfamethoxazolewithin 30min,whichwas 10-fold faster than that of the pristine MIL-101(Fe),it also effectively removed other organic micropollutants with high durability and stability.Mechanistic analysis revealed that the PzDC ligands substitution decreased the band gap of MIL-101(Fe),giving MIL-101(Fe)-Pz appropriate band structure(-0.40∼1.05 V vs.NHE)which can cover several light-driven process for the generation of reactive oxygen species,including Fe(Ⅲ)reduction and H_(2)O_(2) activation for accelerating•OH generation,as well as oxygen reduction reaction for generating H_(2)O_(2),O_(2)^(•−) and ^(1)O_(2).This study highlights the role of pyridine-N containing ligands in regulating the band structure of Fe-MOFs,providing valuable guidance for the design of Fe-MOFs photocatalysts.展开更多
文摘Regulating charge transfer to achieve specific transfer path can improve electron utilization and complete efficient photoreduction of CO_(2).Here,we fabricated a S-scheme heterojunction of CN/Fe-MOF by an in-situ assembly strategy.The S-scheme charge transfer mechanism was confirmed by band structure,electron spin resonance(ESR)and work function(Φ)analysis.On the one hand,the response of Fe-MOF in the visible region improved the utilization of light energy,thus increasing the ability of CN/Fe-MOF to generate charge carriers.On the other hand,CN,as the active site,not only had strong adsorption capacity for CO_(2),but also retained photogenerated electrons with high reduction capacity because of S-scheme charge transfer mechanism.Hence,in the absence of any sacrificial agent and cocatalyst,the optimized 50CN/Fe-MOF obtained the highest CO yield(19.17μmol g^(–1))under UV-Vis irradiation,which was almost 10 times higher than that of CN.In situ Fourier transform infrared spectra not only revealed that the photoreduction of CO_(2) occurred at the CN,but also demonstrated that the S-scheme charge transfer mechanism enabled 50CN/Fe-MOF to have a stronger ability to generate HCOO–than CN.
基金supported by the National Natural Science Foundation of China(Nos.52300120 and 52070144)the Fundamental Research Funds for the Central Universities(No.22120240465).
文摘Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a novel pyrazine-based Fe-MOFs(MIL-101(Fe)-Pz)by substituting the 1,4-dicarboxybenzene acid ligands in typical MIL-101(Fe)with 2,5-pyrazinedicarboxylic acid(PzDC),in which sodium acetate was used as coordinative modulator to control the crystal size(2–3μm).The incorporation of Fe-pyridine N coordination structures originated from PzDC ligands gave MIL-101(Fe)-Pz narrowed band gap(1.45 eV)than MIL-101(Fe)(2.54 eV)resulting in improved visible-light adsorption capacity(λ>420 nm),and also increased the proportion of Fe(Ⅱ)in the Fe-clusters.Thus MIL-101(Fe)-Pz exhibited a synergistic enhanced photo-Fenton-like catalytic performance under visible-light irradiation.The MIL-101(Fe)-Pz/H_(2)O_(2)/Vis system could degrade 99%of sulfamethoxazolewithin 30min,whichwas 10-fold faster than that of the pristine MIL-101(Fe),it also effectively removed other organic micropollutants with high durability and stability.Mechanistic analysis revealed that the PzDC ligands substitution decreased the band gap of MIL-101(Fe),giving MIL-101(Fe)-Pz appropriate band structure(-0.40∼1.05 V vs.NHE)which can cover several light-driven process for the generation of reactive oxygen species,including Fe(Ⅲ)reduction and H_(2)O_(2) activation for accelerating•OH generation,as well as oxygen reduction reaction for generating H_(2)O_(2),O_(2)^(•−) and ^(1)O_(2).This study highlights the role of pyridine-N containing ligands in regulating the band structure of Fe-MOFs,providing valuable guidance for the design of Fe-MOFs photocatalysts.
