Crystalline TiO(P25) and isolated titanate species in a ZSM-5 structure(TS-1) were modified with Au and Ag, respectively, and tested in the gas-phase photocatalytic COreduction under high purity conditions. The no...Crystalline TiO(P25) and isolated titanate species in a ZSM-5 structure(TS-1) were modified with Au and Ag, respectively, and tested in the gas-phase photocatalytic COreduction under high purity conditions. The noble metal modification was performed by photodeposition. Light absorbance properties of the catalysts are examined with UV–Vis spectroscopy before and after the activity test. In the gas-phase photocatalytic COreduction, it was observed that the catalysts with Ag nanostructures are more active than those with Au nanostructures. It is thus found that the energetic difference between the band gap energy of the semiconductor and the position of the plasmon is influencing the photocatalytic activity.Potentially, plasmon excitation due to visible light absorption results in plasmon resonance energy, which affects the excitation of the semiconductor positively. Therefore, an overlap between band gap energy of the semiconductor and metal plasmon is needed.展开更多
Photocatalytic CO2 reduction on metal-oxide-based catalysts is promising for solving the energy and environmental crises faced by mankind. The oxygen vacancy (Vo) on metal oxides is expected to be a key factor affec...Photocatalytic CO2 reduction on metal-oxide-based catalysts is promising for solving the energy and environmental crises faced by mankind. The oxygen vacancy (Vo) on metal oxides is expected to be a key factor affecting the efficiency of photocatalytic CO2 reduction on metal-oxide-based catalysts. Yet, to date, the question of how an Vo influences photocatalytic CO2 reduction is still unanswered. Herein, we report that, on Vo-rich gallium oxide coated with Pt nanoparticles (Vo-rich Pt/Ga203), CO2 is photocatalytically reduced to CO, with a highly enhanced CO evolution rate (21.0umol.h-1) compared to those on Vo-poor Pt/Ga2O3 (3.9 gmol-h-1) and Pt/TiO2(P25) (6.7 gmol.h-1). We demonstrate that the Vo leads to improved CO2 adsorption and separation of the photoinduced charges on Pt/Ga203, thus enhancing the photocatalytic activity of Pt/Ga203. Rational fabrication of an Vo is thereby an attractive strategy for developing efficient catalysts for photocatalytic CO2 reduction.展开更多
Metal nanoparticle (NP) co-catalysts on metal oxide semiconductor supports are attracting attention as photocatalysts for a variety of chemical reactions. Related efforts seek to make and use Pt-free catalysts. In t...Metal nanoparticle (NP) co-catalysts on metal oxide semiconductor supports are attracting attention as photocatalysts for a variety of chemical reactions. Related efforts seek to make and use Pt-free catalysts. In this regard, we report here enhanced CH4 formation rates of 25 and 60 μmol·g^-1·h^-1 by photocatalytic CO2 reduction using hitherto unused ZnPd NPs as well as Au and Ru NPs. The NPs are formed by colloidal synthesis and grafted onto short n-type anatase TiO2 nanotube arrays (TNAs), grown anodically on transparent glass substrates. The interfacial electric fields in the NP-grafted TiO2 nanotubes were probed by ultraviolet photoelectron spectroscopy (UPS). Au NP-grafted TiO2 nanotubes (Au-TNAs) showed no band bending, but a depletion region was detected in Ru NP-grafted TNAs (Ru-TNAs) and an accumulation layer was observed in ZnPd NP-grafted TNAs (ZnPd-TNAs). Temperature programmed desorption (TPD) experiments showed significantly greater CO2 adsorption on NP-grafted TNAs. TNAs with grafted NPs exhibit broader and more intense UV-visible absorption bands than bare TNAs. We found that CO2 photoreduction by nanoparticle-grafted TNAs was driven not only by ultraviolet photons with energies greater than the TiO2 band gap, but also by blue photons close to and below the anatase band edge. The enhanced rate of CO2 reduction is attributed to superior use of blue photons in the solar spectrum, excellent reactant adsorption, efficient charge transfer to adsorbates, and low recombination losses.展开更多
Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow micro...Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow microspheres(HS),were dedicatedly designed to boost overall photocatalytic efficiency.TiO_(2) nanoparticles were in-situ decorated on the inside and outside the shell of Cd S HS,ensuring close contact between TiO_(2) and CdS.The CdS/TiO2 HS with abundant mesopores inside of the shell boost the light absorption via multiscattering effect as well as accessible to reactions in all directions.The heterojunction was scrutinized and the charge transfer across it was revealed by in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS).Ultimately,the charge transfer in this composite was determined to follow stepscheme mechanism,which not only facilitates the separation of charge carriers but also preserves strong redox ability.Benefited from the intimate linkage between Cd S and TiO_(2) and the favorable step-scheme heterojunction,enhanced photocatalytic CO_(2) reduction activity was accomplished.The CH4 yield rate of CdS/TiO_(2) reaches 27.85μmol g^(–1) h^(–1),which is 145.6 and 3.8 times higher than those of pristine CdS and TiO_(2),respectively.This work presents a novel insight into constructing step-scheme photocatalytic system with desirable performance.展开更多
A rare-earth free upconversion luminescent material, 10BaF2:NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light (550 nm-610 nm) into ...A rare-earth free upconversion luminescent material, 10BaF2:NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light (550 nm-610 nm) into ultraviolet light (290 nm 350 nm), and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2:NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation (λ〉 515 nm). The results show that 10BaF2:NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2:NaF, Na3AIF6/TiO2 is proposed.展开更多
文摘Crystalline TiO(P25) and isolated titanate species in a ZSM-5 structure(TS-1) were modified with Au and Ag, respectively, and tested in the gas-phase photocatalytic COreduction under high purity conditions. The noble metal modification was performed by photodeposition. Light absorbance properties of the catalysts are examined with UV–Vis spectroscopy before and after the activity test. In the gas-phase photocatalytic COreduction, it was observed that the catalysts with Ag nanostructures are more active than those with Au nanostructures. It is thus found that the energetic difference between the band gap energy of the semiconductor and the position of the plasmon is influencing the photocatalytic activity.Potentially, plasmon excitation due to visible light absorption results in plasmon resonance energy, which affects the excitation of the semiconductor positively. Therefore, an overlap between band gap energy of the semiconductor and metal plasmon is needed.
文摘Photocatalytic CO2 reduction on metal-oxide-based catalysts is promising for solving the energy and environmental crises faced by mankind. The oxygen vacancy (Vo) on metal oxides is expected to be a key factor affecting the efficiency of photocatalytic CO2 reduction on metal-oxide-based catalysts. Yet, to date, the question of how an Vo influences photocatalytic CO2 reduction is still unanswered. Herein, we report that, on Vo-rich gallium oxide coated with Pt nanoparticles (Vo-rich Pt/Ga203), CO2 is photocatalytically reduced to CO, with a highly enhanced CO evolution rate (21.0umol.h-1) compared to those on Vo-poor Pt/Ga2O3 (3.9 gmol-h-1) and Pt/TiO2(P25) (6.7 gmol.h-1). We demonstrate that the Vo leads to improved CO2 adsorption and separation of the photoinduced charges on Pt/Ga203, thus enhancing the photocatalytic activity of Pt/Ga203. Rational fabrication of an Vo is thereby an attractive strategy for developing efficient catalysts for photocatalytic CO2 reduction.
文摘Metal nanoparticle (NP) co-catalysts on metal oxide semiconductor supports are attracting attention as photocatalysts for a variety of chemical reactions. Related efforts seek to make and use Pt-free catalysts. In this regard, we report here enhanced CH4 formation rates of 25 and 60 μmol·g^-1·h^-1 by photocatalytic CO2 reduction using hitherto unused ZnPd NPs as well as Au and Ru NPs. The NPs are formed by colloidal synthesis and grafted onto short n-type anatase TiO2 nanotube arrays (TNAs), grown anodically on transparent glass substrates. The interfacial electric fields in the NP-grafted TiO2 nanotubes were probed by ultraviolet photoelectron spectroscopy (UPS). Au NP-grafted TiO2 nanotubes (Au-TNAs) showed no band bending, but a depletion region was detected in Ru NP-grafted TNAs (Ru-TNAs) and an accumulation layer was observed in ZnPd NP-grafted TNAs (ZnPd-TNAs). Temperature programmed desorption (TPD) experiments showed significantly greater CO2 adsorption on NP-grafted TNAs. TNAs with grafted NPs exhibit broader and more intense UV-visible absorption bands than bare TNAs. We found that CO2 photoreduction by nanoparticle-grafted TNAs was driven not only by ultraviolet photons with energies greater than the TiO2 band gap, but also by blue photons close to and below the anatase band edge. The enhanced rate of CO2 reduction is attributed to superior use of blue photons in the solar spectrum, excellent reactant adsorption, efficient charge transfer to adsorbates, and low recombination losses.
基金financially supported by the National Natural Science Foundation of China(NSFC)(Nos.51872220,51932007,51961135303,21871217,U1905215 and U1705251)the National Key Research and Development Program of China(No.2018YFB1502001)the Fundamental Research Funds for the Central Universities(No.WUT:2019IVB050)。
文摘Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow microspheres(HS),were dedicatedly designed to boost overall photocatalytic efficiency.TiO_(2) nanoparticles were in-situ decorated on the inside and outside the shell of Cd S HS,ensuring close contact between TiO_(2) and CdS.The CdS/TiO2 HS with abundant mesopores inside of the shell boost the light absorption via multiscattering effect as well as accessible to reactions in all directions.The heterojunction was scrutinized and the charge transfer across it was revealed by in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS).Ultimately,the charge transfer in this composite was determined to follow stepscheme mechanism,which not only facilitates the separation of charge carriers but also preserves strong redox ability.Benefited from the intimate linkage between Cd S and TiO_(2) and the favorable step-scheme heterojunction,enhanced photocatalytic CO_(2) reduction activity was accomplished.The CH4 yield rate of CdS/TiO_(2) reaches 27.85μmol g^(–1) h^(–1),which is 145.6 and 3.8 times higher than those of pristine CdS and TiO_(2),respectively.This work presents a novel insight into constructing step-scheme photocatalytic system with desirable performance.
基金supported by the National Natural Science Foundation of China (Grant No. 20876125)the Research Fund for the Doctoral Program of Higher Education, China (Grant No. 20096101110013)the Northwest University Graduate Interdisciplinary Funds, China (Grant Nos. 09YJC24 and 09YJC27)
文摘A rare-earth free upconversion luminescent material, 10BaF2:NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light (550 nm-610 nm) into ultraviolet light (290 nm 350 nm), and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2:NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation (λ〉 515 nm). The results show that 10BaF2:NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2:NaF, Na3AIF6/TiO2 is proposed.