Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated ...Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO_(3) photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm^(−2) at 1.76 VRHE) and high selectivity to H_(2)O_(2) (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO_(3)-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO_(3)-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO_(3)-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H^(+), lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H_(2)O_(2) is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO_(3)-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.展开更多
Birnessite films on fluorine-doped tin oxide（FTO） coated glass were prepared by cathodic reduction of aqueous KMnO4. The deposited birnessite films were characterized with X-ray diffraction, Raman spectroscopy, scan...Birnessite films on fluorine-doped tin oxide（FTO） coated glass were prepared by cathodic reduction of aqueous KMnO4. The deposited birnessite films were characterized with X-ray diffraction, Raman spectroscopy, scanning electron microscopy and atomic force microscopy.The photoelectrochemical activity of birnessite films was investigated and a remarkable photocurrent in response to visible light was observed in the presence of phenol, resulting from localized manganese d–d transitions. Based on this result, the photoelectrocatalytic oxidation of phenol was investigated. Compared with phenol degradation by the electrochemical oxidation process or photocatalysis separately, a synergetic photoelectrocatalytic degradation effect was observed in the presence of the birnessite film coated FTO electrode.Photoelectrocatalytic degradation ratios were influenced by film thickness and initial phenol concentrations. Phenol degradation with the thinnest birnessite film and initial phenol concentration of 10 mg/L showed the highest efficiency of 91.4% after 8 hr. Meanwhile, the kinetics of phenol removal was fit well by the pseudofirst-order kinetic model.展开更多
An innovative photoelectrode, TiO 2/Ti mesh electrode, was prepared by galvanostaticanodisation. The morphology and the crystalline texture of the TiO 2 film on mesh electrode were examined by scanning electronic mi...An innovative photoelectrode, TiO 2/Ti mesh electrode, was prepared by galvanostaticanodisation. The morphology and the crystalline texture of the TiO 2 film on mesh electrode were examined by scanning electronic microscopy and Raman spectroscopy respectively. The examination results indicated that the structure and properties of the film depended on anodisation rate, and the anatase was the dominant component under the controlled experimental conditions. Degradation of Rose Bengal(RB) in photocatalytic(PC) and photoelectrocatalytic(PEC) reaction was investigated, the results demonstrated that electric biasing could improve the efficiency of photocatalytic reaction. The measurement results of TOC in photoelectrocatalytic degradation showed that the mineralisation of RB was complete relatively. The comparison between the degradation efficiency of RB in PEC process and that in aqueous TiO 2 dispersion was conducted. The results showed that the apparent first order rate constant of RB degradation in PEC process was larger than that in aqueous dispersion with 0 1%—0 3% TiO 2 powder, but was smaller than that in aqueous dispersion with 1 0% TiO 2展开更多
An innovative photoelectrode, TiO_2/Ti mesh electrode, was prepared by anodisation. In anodisation, 0.5 mol/L H_2SO_4 was used as electrolytic solution, the current had been constantly 1A from the beginning of the oxi...An innovative photoelectrode, TiO_2/Ti mesh electrode, was prepared by anodisation. In anodisation, 0.5 mol/L H_2SO_4 was used as electrolytic solution, the current had been constantly 1A from the beginning of the oxidation until reaching a designed voltage. Results showed that the photocatalytic activity of electrode was better when the designed voltage was 160 V. The morphology and the crystalline texture of the TiO_2 film on mesh electrode were examined by scanning electronic microscopy and Raman spectroscopy respectively. The examination results indicated that the structure and properties of the film depended on anodisation rate, and the anatase was the dominant component under the controlled experimental conditions. Degradation of Rhodamine B in photocatalytic (PC) and photoelectrocatalytic (PEC) reaction was investigated.展开更多
基金supported by the National Natural Science Foundation of China(22478211,22179067)the Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10).
文摘Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO_(3) photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm^(−2) at 1.76 VRHE) and high selectivity to H_(2)O_(2) (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO_(3)-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO_(3)-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO_(3)-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H^(+), lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H_(2)O_(2) is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO_(3)-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.
基金supported by the National Basic Research Program(973)of China(No.2014CB846001)the NationalNatural Science Foundation of China(Nos.41230103,41402032&41402301)
文摘Birnessite films on fluorine-doped tin oxide（FTO） coated glass were prepared by cathodic reduction of aqueous KMnO4. The deposited birnessite films were characterized with X-ray diffraction, Raman spectroscopy, scanning electron microscopy and atomic force microscopy.The photoelectrochemical activity of birnessite films was investigated and a remarkable photocurrent in response to visible light was observed in the presence of phenol, resulting from localized manganese d–d transitions. Based on this result, the photoelectrocatalytic oxidation of phenol was investigated. Compared with phenol degradation by the electrochemical oxidation process or photocatalysis separately, a synergetic photoelectrocatalytic degradation effect was observed in the presence of the birnessite film coated FTO electrode.Photoelectrocatalytic degradation ratios were influenced by film thickness and initial phenol concentrations. Phenol degradation with the thinnest birnessite film and initial phenol concentration of 10 mg/L showed the highest efficiency of 91.4% after 8 hr. Meanwhile, the kinetics of phenol removal was fit well by the pseudofirst-order kinetic model.
文摘An innovative photoelectrode, TiO 2/Ti mesh electrode, was prepared by galvanostaticanodisation. The morphology and the crystalline texture of the TiO 2 film on mesh electrode were examined by scanning electronic microscopy and Raman spectroscopy respectively. The examination results indicated that the structure and properties of the film depended on anodisation rate, and the anatase was the dominant component under the controlled experimental conditions. Degradation of Rose Bengal(RB) in photocatalytic(PC) and photoelectrocatalytic(PEC) reaction was investigated, the results demonstrated that electric biasing could improve the efficiency of photocatalytic reaction. The measurement results of TOC in photoelectrocatalytic degradation showed that the mineralisation of RB was complete relatively. The comparison between the degradation efficiency of RB in PEC process and that in aqueous TiO 2 dispersion was conducted. The results showed that the apparent first order rate constant of RB degradation in PEC process was larger than that in aqueous dispersion with 0 1%—0 3% TiO 2 powder, but was smaller than that in aqueous dispersion with 1 0% TiO 2
基金TheScientificResearchFoundationofHarbinInstituteofTechnology (No .HIT .2 0 0 1.5 6)
文摘An innovative photoelectrode, TiO_2/Ti mesh electrode, was prepared by anodisation. In anodisation, 0.5 mol/L H_2SO_4 was used as electrolytic solution, the current had been constantly 1A from the beginning of the oxidation until reaching a designed voltage. Results showed that the photocatalytic activity of electrode was better when the designed voltage was 160 V. The morphology and the crystalline texture of the TiO_2 film on mesh electrode were examined by scanning electronic microscopy and Raman spectroscopy respectively. The examination results indicated that the structure and properties of the film depended on anodisation rate, and the anatase was the dominant component under the controlled experimental conditions. Degradation of Rhodamine B in photocatalytic (PC) and photoelectrocatalytic (PEC) reaction was investigated.
