Vertically aligned TiO2/SrTiO3 core–shell heterostructured nanowire arrays with different shell thicknesses(5–40 nm)were fabricated on fluorine-doped tin oxide substrate via a hydrothermal process.Microstructural ch...Vertically aligned TiO2/SrTiO3 core–shell heterostructured nanowire arrays with different shell thicknesses(5–40 nm)were fabricated on fluorine-doped tin oxide substrate via a hydrothermal process.Microstructural characterization demonstrated that the TiO2 nanowires were uniformly coated by the singlecrystal SrTiO3 shell,where continuous and large-area interface could be clearly observed.By this means,significantly enhanced photoelectrochemical water splitting properties(0.78 mA·cm^-2 at 1.23 V vs.RHE)were successfully realized in well-designed sample(with a shell thickness of 5–10 nm)compared with those of pristine TiO2(0.38 mA·cm^-2 at 1.23 V vs.RHE).The improvement of photoelectrochemical properties was attributed to the improved charge injection and charge separation,which are calculated by the results of water oxidation and sulfite oxidation measurements.Based on these results,a mechanism was proposed that SrTiO3 shell acted as an electron–hole separation layer to improve the photocurrent density.On the other hand,the sample with an over-thick SrTiO3 shell(20–40 nm)exhibited slightly reduced photoelectrochemical properties(0.66 mA·cm^-2),which could be explained by the increase of the recombination rate in thethicker SrTiO3 shell.This work provided a facile strategy to improve and modulate the photoelectrochemical performance of heterostructured photoanodes.展开更多
Perovskite BaTiO3 （BTO） nanocrystals with a size of 150-200 nm have successfully been synthesized via a facile hydrothermal method by employing titanate nanowires as synthetic precursor. Tetragonality and spontaneou...Perovskite BaTiO3 （BTO） nanocrystals with a size of 150-200 nm have successfully been synthesized via a facile hydrothermal method by employing titanate nanowires as synthetic precursor. Tetragonality and spontaneous ferroelectric polarization of BTO nanocrystals have been determined by X-ray diffraction and transmission electron microscopy investigations. BTO nanocrystals loaded with Pt nanoparticles in a size of 2-5 nm have been explored as a catalyst towards CO oxidation to CO2. It is interesting to find that CO catalytic conversion rate over Pt-BTO nanocrystals gradually decreased and further increased near 100 ℃ when the catalytic temperature keeps increasing, whereas the conversion behavior in oxides is expected to be enhanced upon the catalytic temperature grows. Using differential scanning calorimetry and first-principle calculations, the observed catalytic behavior has been discussed on the basis of the ferroelectric polarization effect and the ferroelectric-paraelectric transition of BTO nanocrystals with a Curie temperature of 110 ℃. Below Curie temperature, CO catalytic oxidation could be significantly tailored by ferroelectric polarization of BTO nanocrystals via a promoted dissociation of O2 molecules. The findings suggest that a ferroelectric polarization in perovskite oxides could be an alternative way to modify the CO catalytic oxidation.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 51232006, 51472218 and 11474249)the National Basic Research Program of China (No. 2015CB654900)
文摘Vertically aligned TiO2/SrTiO3 core–shell heterostructured nanowire arrays with different shell thicknesses(5–40 nm)were fabricated on fluorine-doped tin oxide substrate via a hydrothermal process.Microstructural characterization demonstrated that the TiO2 nanowires were uniformly coated by the singlecrystal SrTiO3 shell,where continuous and large-area interface could be clearly observed.By this means,significantly enhanced photoelectrochemical water splitting properties(0.78 mA·cm^-2 at 1.23 V vs.RHE)were successfully realized in well-designed sample(with a shell thickness of 5–10 nm)compared with those of pristine TiO2(0.38 mA·cm^-2 at 1.23 V vs.RHE).The improvement of photoelectrochemical properties was attributed to the improved charge injection and charge separation,which are calculated by the results of water oxidation and sulfite oxidation measurements.Based on these results,a mechanism was proposed that SrTiO3 shell acted as an electron–hole separation layer to improve the photocurrent density.On the other hand,the sample with an over-thick SrTiO3 shell(20–40 nm)exhibited slightly reduced photoelectrochemical properties(0.66 mA·cm^-2),which could be explained by the increase of the recombination rate in thethicker SrTiO3 shell.This work provided a facile strategy to improve and modulate the photoelectrochemical performance of heterostructured photoanodes.
基金financially supported by the National Natural Science Foundation of China(Nos.51602286,51472218,51302247,51232006,and 21102212)the Science Foundation of Zhejiang Sci-Tech University(No.15022084-Y)the Natural Science Foundation of Zhejiang province(No.LY18E010004)
文摘Perovskite BaTiO3 （BTO） nanocrystals with a size of 150-200 nm have successfully been synthesized via a facile hydrothermal method by employing titanate nanowires as synthetic precursor. Tetragonality and spontaneous ferroelectric polarization of BTO nanocrystals have been determined by X-ray diffraction and transmission electron microscopy investigations. BTO nanocrystals loaded with Pt nanoparticles in a size of 2-5 nm have been explored as a catalyst towards CO oxidation to CO2. It is interesting to find that CO catalytic conversion rate over Pt-BTO nanocrystals gradually decreased and further increased near 100 ℃ when the catalytic temperature keeps increasing, whereas the conversion behavior in oxides is expected to be enhanced upon the catalytic temperature grows. Using differential scanning calorimetry and first-principle calculations, the observed catalytic behavior has been discussed on the basis of the ferroelectric polarization effect and the ferroelectric-paraelectric transition of BTO nanocrystals with a Curie temperature of 110 ℃. Below Curie temperature, CO catalytic oxidation could be significantly tailored by ferroelectric polarization of BTO nanocrystals via a promoted dissociation of O2 molecules. The findings suggest that a ferroelectric polarization in perovskite oxides could be an alternative way to modify the CO catalytic oxidation.
