In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successf...In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successfully grafted onto a TiO2 surface and induced the assembly of rutile TiO2 nanorods into uniform spindle-like nanobundles.The resulting TiO2 product achieved a photocatalytic hydrogen evolution rate of 402.4μmol h^?1,which is 3.1 times higher than that of Degussa P25-TiO2.It was demonstrated that nitrate group grafting caused the rutile TiO2 surface to become negatively charged,which is favorable for trapping positive protons and improving charge carrier separation,thereby enhancing photocatalytic hydrogen production.Additionally,surface charges were crucial to structural stability based on electrostatic repulsion.This study not only developed a facile surface modification strategy for fabricating efficient H2 production photocatalysts but also identified an influence mechanism of inorganic acids different from that reported in the literature.展开更多
Oxygen vacancy（VO） plays a vital role in semiconductor photocatalysis. Rutile TiO2 nanomaterials with controllable contents of VO（0–2.18%） are fabricated via an insitu solid-state chemical reduction strategy, wit...Oxygen vacancy（VO） plays a vital role in semiconductor photocatalysis. Rutile TiO2 nanomaterials with controllable contents of VO（0–2.18%） are fabricated via an insitu solid-state chemical reduction strategy, with color from white to black. The bandgap of the resultant rutile TiO2 is reduced from 3.0 to 2.56 e V, indicating the enhanced visible light absorption. The resultant rutile TiO2 with optimal contents of VO（2.07%） exhibits a high solar-driven photocatalytic hydrogen production rate of 734 μmol h-1, which is about four times as high as that of the pristine one（185 μmol h-1）. The presence of VOelevates the apparent Fermi level of rutile TiO2 and promotes the efficient electronhole separation obviously, which favor the escape of photogenerated electrons and prolong the life-time（7.6×103 ns） of photogenerated charge carriers, confirmed by scanning Kelvin probe microscopy, surface photovoltage spectroscopy and transient-state fluorescence. VO-mediated efficient photogenerated electron-hole separation strategy may provide new insight for fabricating other high-performance semiconductor oxide photocatalysts.展开更多
Titanium dioxide（TiO2） is one of the most widely studied transition metal oxides, especially for its unique performances in heterogeneous photocatalysis. Different phases of TiO2 have been found to exhibit different...Titanium dioxide（TiO2） is one of the most widely studied transition metal oxides, especially for its unique performances in heterogeneous photocatalysis. Different phases of TiO2 have been found to exhibit different photo-activities, though the origins are still not fully understood. In this work, we use the density functional theory（DFT） calculations, corrected by on-site Coulomb and long-range dispersion interactions, to study the adsorptions of nitric oxide（NO） and oxygen（O2） molecules on the clean and hydrogenated anatase TiO2（101） surfaces. We also compare the detailed calculated results regarding their structural, energetic and electronic properties with those obtained at rutile TiO2（110）. It has been found that the behaviors of the surface localized electrons being transferred from adsorbed H, as well as the adsorption behaviors of NO and O2 are quite different at the two surfaces, which can be attributed to their characteristic local bonding structures around the surface hydroxyl. These results may also help explain the different photocatalytic activities of these two main facets of anatase and rutile TiO2展开更多
基金supported by the National Natural Science Foundation of China (21771070, 21571071)the Fundamental Research Funds for the Central Universities (2018KFYYXJJ120, 2019KFYRCPY104)~~
文摘In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successfully grafted onto a TiO2 surface and induced the assembly of rutile TiO2 nanorods into uniform spindle-like nanobundles.The resulting TiO2 product achieved a photocatalytic hydrogen evolution rate of 402.4μmol h^?1,which is 3.1 times higher than that of Degussa P25-TiO2.It was demonstrated that nitrate group grafting caused the rutile TiO2 surface to become negatively charged,which is favorable for trapping positive protons and improving charge carrier separation,thereby enhancing photocatalytic hydrogen production.Additionally,surface charges were crucial to structural stability based on electrostatic repulsion.This study not only developed a facile surface modification strategy for fabricating efficient H2 production photocatalysts but also identified an influence mechanism of inorganic acids different from that reported in the literature.
基金supported by the Key Program Projects of the National Natural Science Foundation of China (21631004)the National Natural Science Foundation of China (51672073)
文摘Oxygen vacancy（VO） plays a vital role in semiconductor photocatalysis. Rutile TiO2 nanomaterials with controllable contents of VO（0–2.18%） are fabricated via an insitu solid-state chemical reduction strategy, with color from white to black. The bandgap of the resultant rutile TiO2 is reduced from 3.0 to 2.56 e V, indicating the enhanced visible light absorption. The resultant rutile TiO2 with optimal contents of VO（2.07%） exhibits a high solar-driven photocatalytic hydrogen production rate of 734 μmol h-1, which is about four times as high as that of the pristine one（185 μmol h-1）. The presence of VOelevates the apparent Fermi level of rutile TiO2 and promotes the efficient electronhole separation obviously, which favor the escape of photogenerated electrons and prolong the life-time（7.6×103 ns） of photogenerated charge carriers, confirmed by scanning Kelvin probe microscopy, surface photovoltage spectroscopy and transient-state fluorescence. VO-mediated efficient photogenerated electron-hole separation strategy may provide new insight for fabricating other high-performance semiconductor oxide photocatalysts.
基金financial support from the National Natural Science Foundation of China (Nos. 21421004, 21573067, 91545103)Program of Shanghai Academic Research Leader (No. 17XD1401400)
文摘Titanium dioxide（TiO2） is one of the most widely studied transition metal oxides, especially for its unique performances in heterogeneous photocatalysis. Different phases of TiO2 have been found to exhibit different photo-activities, though the origins are still not fully understood. In this work, we use the density functional theory（DFT） calculations, corrected by on-site Coulomb and long-range dispersion interactions, to study the adsorptions of nitric oxide（NO） and oxygen（O2） molecules on the clean and hydrogenated anatase TiO2（101） surfaces. We also compare the detailed calculated results regarding their structural, energetic and electronic properties with those obtained at rutile TiO2（110）. It has been found that the behaviors of the surface localized electrons being transferred from adsorbed H, as well as the adsorption behaviors of NO and O2 are quite different at the two surfaces, which can be attributed to their characteristic local bonding structures around the surface hydroxyl. These results may also help explain the different photocatalytic activities of these two main facets of anatase and rutile TiO2
