Metal-organic frameworks(MOFs)are attracting increasing interests as photocatalysts for solar-driven hydrogen production from water.This paper reports on a comparative study of using either acetic acid(AA)or trifluoro...Metal-organic frameworks(MOFs)are attracting increasing interests as photocatalysts for solar-driven hydrogen production from water.This paper reports on a comparative study of using either acetic acid(AA)or trifluoroacetic acid(TFA)as the representative UiO-66 organic modulators for synthesizing visible light responsive UiO-66(Zr)-X(X:NH_(2) or NO_(2))photocatalysts for water splitting.The results show that photocatalytic hydrogen generation from a water/methanol mixture can be improved by varying the nature and amount of the modulator employed to prepare the different UiO-66(Zr)-X(X:NH_(2) or NO_(2))solid derivatives.UiO-66(Zr)-NH_(2) was the most active photocatalyst,followed by UiO-66(Zr)-NO_(2),both prepared with 12 equivalents of AA with respect to the organic ligand.This UiO-66(Zr)-NH_(2) solid was more active than the parent MOF in photocatalytic overall water splitting(OWS)(H_(2) and O_(2) production of 450 and 160μmol·g^(-1),respectively,in 5 h;apparent quantum yield(AQY)at 400 nm of 0.06%)in the absence of methanol and compares favourably with analogous reports.Information on the photocatalytic activity of the most active solids of both series was obtained by means of a series of techniques,including ultraviolet-visible(UV-vis)diffuse reflectance,X-ray photoelectron spectroscopy(XPS),laser flash photolysis(LFP),electron spin resonance(ESR),photoluminescence and photoelectrochemical measurements together with density functional theory(DFT)calculations.The results showed that organic acid modulators can be used to enhance the photocatalytic activity of missing linker UiO-66 defective materials in solar-powered water splitting.展开更多
基金support of PRE2019-089877 funded by MCIN/AEI/10.13039/501100011033 and by ESF Investing in your future.V.D-C.is grateful to the European Union’s Horizon 2020 Research and Innovation Program project MOF2H2(GA No.101084131)for the financial supportthe Centre informatique national de l'enseignement supérieur(CINES)Supercomputing facilities and the local ICGM clusters.I.V.thanks the support of grant PID2020-115010RB-I00 funded by MCIN/AEI/10.13039/501100011033support of grant PID2021-123856OBI00 funded by MCIN/AEI/10.13039/501100011033 and by ERDF A way of making Europe.
文摘Metal-organic frameworks(MOFs)are attracting increasing interests as photocatalysts for solar-driven hydrogen production from water.This paper reports on a comparative study of using either acetic acid(AA)or trifluoroacetic acid(TFA)as the representative UiO-66 organic modulators for synthesizing visible light responsive UiO-66(Zr)-X(X:NH_(2) or NO_(2))photocatalysts for water splitting.The results show that photocatalytic hydrogen generation from a water/methanol mixture can be improved by varying the nature and amount of the modulator employed to prepare the different UiO-66(Zr)-X(X:NH_(2) or NO_(2))solid derivatives.UiO-66(Zr)-NH_(2) was the most active photocatalyst,followed by UiO-66(Zr)-NO_(2),both prepared with 12 equivalents of AA with respect to the organic ligand.This UiO-66(Zr)-NH_(2) solid was more active than the parent MOF in photocatalytic overall water splitting(OWS)(H_(2) and O_(2) production of 450 and 160μmol·g^(-1),respectively,in 5 h;apparent quantum yield(AQY)at 400 nm of 0.06%)in the absence of methanol and compares favourably with analogous reports.Information on the photocatalytic activity of the most active solids of both series was obtained by means of a series of techniques,including ultraviolet-visible(UV-vis)diffuse reflectance,X-ray photoelectron spectroscopy(XPS),laser flash photolysis(LFP),electron spin resonance(ESR),photoluminescence and photoelectrochemical measurements together with density functional theory(DFT)calculations.The results showed that organic acid modulators can be used to enhance the photocatalytic activity of missing linker UiO-66 defective materials in solar-powered water splitting.
