TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fl...TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fluorinated TiO2‐HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO4)2–NH4HF–H2O2solution at180°C.The effect of the calcination temperature on the structure and photoreactivity of the TiO2‐HMSs was systematically investigated,which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation.We found that after calcination at300°C,the photoreactivity of the TiO2‐HMSs decreases from1.39×10?3min?1(TiO2‐HMS precursor)to0.82×10?3min?1because of removal of surface‐adsorbed fluoride ions.With increasing calcination temperature from300to900°C,the building blocks of the TiO2‐HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles,and the photoreactivity of the TiO2‐HMSs steady increases from0.82×10?3to2.09×10?3min?1because of enhanced crystallization.Further increasing the calcination temperature to1000and1100°C results in a decrease of the photoreactivity,which is ascribed to a sharp decrease of the Brunauer–Emmett–Teller surface area and the beginning of the anatase–rutile phase transformation at1100°C.The effect of surface‐adsorbed fluoride ions on the thermal stability of the TiO2‐HMSs is also discussed.展开更多
The rational design and construction of novel two-dimensional(2D)carbon nitrides(CNs)beyond g-C_(3)N_(4) is a hot topic in the fields of chemistry and materials.Inspired by the polymerisation of urea,we have prepared ...The rational design and construction of novel two-dimensional(2D)carbon nitrides(CNs)beyond g-C_(3)N_(4) is a hot topic in the fields of chemistry and materials.Inspired by the polymerisation of urea,we have prepared a series of novel C-C bridged heptazine CNs UO_(x)(where x is the ratio of urea to oxamide,x=1,1.5,2,2.5,and 3),which are similar to(C_(6)N_(7))n,upon the introduction of oxamide.As predicted using density functional theory(DFT)calculations,the conjugated structure of UO_(x) was effectively extended from an individual heptazine to the entire material.Consequently,its bandgap was reduced to 2.05 eV,and its absorption band edge was significantly extended to 600 nm.Furthermore,its carrier transfer and separation were significantly enhanced,establishing its superior photocatalytic activity.The optimised UO_(2) exhibits a superior photocatalytic hydrogen production rate about 108.59 lmol h^(-1)(using 10 mg of catalyst)with an apparent quantum efficiency(AQE)of 36.12%and 0.33%at 420 and 600 nm,respectively,which is one of the most active novel CNs reported to date.Moreover,UO_(2) exhibits excellent photocatalytic activity toward the oxidation of diphenylhydrazine to azobenzene with conversion and selectivity reaching~100%,which represents a promising highly efficient 2D CN material.Regarding phenols degradation,UO_(2) also displayed significantly higher activity and durability during the degradation of phenol when compared to traditional g-C_(3)N_(4),highlighting its significant potential for application in energy,environment and photocatalytic organic reactions.展开更多
基金supported by the National Natural Science Foundation of China(51672312,21373275)the Science and Technology Program of Wuhan,China(2016010101010018,2015070504020220)the Dean’s Research Fund–04257 from the Education University of Hong Kong~~
文摘TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fluorinated TiO2‐HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO4)2–NH4HF–H2O2solution at180°C.The effect of the calcination temperature on the structure and photoreactivity of the TiO2‐HMSs was systematically investigated,which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation.We found that after calcination at300°C,the photoreactivity of the TiO2‐HMSs decreases from1.39×10?3min?1(TiO2‐HMS precursor)to0.82×10?3min?1because of removal of surface‐adsorbed fluoride ions.With increasing calcination temperature from300to900°C,the building blocks of the TiO2‐HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles,and the photoreactivity of the TiO2‐HMSs steady increases from0.82×10?3to2.09×10?3min?1because of enhanced crystallization.Further increasing the calcination temperature to1000and1100°C results in a decrease of the photoreactivity,which is ascribed to a sharp decrease of the Brunauer–Emmett–Teller surface area and the beginning of the anatase–rutile phase transformation at1100°C.The effect of surface‐adsorbed fluoride ions on the thermal stability of the TiO2‐HMSs is also discussed.
基金supported by the National Key R&D Program of China (2020YFA0406101)the National Natural Science Foundation of China (21771033 and 22071020)+4 种基金the Fundamental Research Funds for the Central Universities (2412018BJ001 and 2412018ZD007)the “Hong Kong Scholar” Programme (XJ2018021)the General Research FundResearch Grants Council of Hong Kong SAR Government (18301117)Dean’s Research Fund [04425], Ed UHK。
文摘The rational design and construction of novel two-dimensional(2D)carbon nitrides(CNs)beyond g-C_(3)N_(4) is a hot topic in the fields of chemistry and materials.Inspired by the polymerisation of urea,we have prepared a series of novel C-C bridged heptazine CNs UO_(x)(where x is the ratio of urea to oxamide,x=1,1.5,2,2.5,and 3),which are similar to(C_(6)N_(7))n,upon the introduction of oxamide.As predicted using density functional theory(DFT)calculations,the conjugated structure of UO_(x) was effectively extended from an individual heptazine to the entire material.Consequently,its bandgap was reduced to 2.05 eV,and its absorption band edge was significantly extended to 600 nm.Furthermore,its carrier transfer and separation were significantly enhanced,establishing its superior photocatalytic activity.The optimised UO_(2) exhibits a superior photocatalytic hydrogen production rate about 108.59 lmol h^(-1)(using 10 mg of catalyst)with an apparent quantum efficiency(AQE)of 36.12%and 0.33%at 420 and 600 nm,respectively,which is one of the most active novel CNs reported to date.Moreover,UO_(2) exhibits excellent photocatalytic activity toward the oxidation of diphenylhydrazine to azobenzene with conversion and selectivity reaching~100%,which represents a promising highly efficient 2D CN material.Regarding phenols degradation,UO_(2) also displayed significantly higher activity and durability during the degradation of phenol when compared to traditional g-C_(3)N_(4),highlighting its significant potential for application in energy,environment and photocatalytic organic reactions.
