The chemistry of acetaldehyde (CH3CHO) adsorbed on the anatase TiO2(001)-(1×4) surface has been investigated by temperature-programmed desorption (TPD) method. Our experimental results provide the direct evidence...The chemistry of acetaldehyde (CH3CHO) adsorbed on the anatase TiO2(001)-(1×4) surface has been investigated by temperature-programmed desorption (TPD) method. Our experimental results provide the direct evidence that the perfect lattice sites on the anatase TiO2(001)-(1×4) surface are quite inert for the reaction of CH3CHO, but the reduced defect sites on the surface are active for the thermally driven reductive carbon-carbon coupling reactions of CH3CHO to produce 2-butanone and butene. We propose that the coupling reactions of CH3CHO on the anatase TiO2(001)-(1×4) surface should undergo through the adsorption of paired CH3CHO molecules at the reduced defect sites, since the existing reduced Ti pairs provide the suitable adsorption sites.展开更多
This study investigated the positive effect of surface modification with ozone on the photocatalytic performance of anatase TiO2 with dominated(001) facets for toluene degradation.The performance of photocatalyst wa...This study investigated the positive effect of surface modification with ozone on the photocatalytic performance of anatase TiO2 with dominated(001) facets for toluene degradation.The performance of photocatalyst was tested on a home-made volatile organic compounds degradation system. The ozone modification, toluene adsorption and degradation mechanism were established by a combination of various characterization methods, in situ diffuse reflectance infrared fourier transform spectroscopy, and density functional theory calculation.The surface modification with ozone can significantly enhance the photocatalytic degradation performance for toluene. The abundant unsaturated coordinated 5 c-Ti sites on(001)facets act as the adsorption sites for ozone. The formed Ti–O bonds reacted with H2O to generate a large amount of isolated Ti5 c-OH which act as the adsorption sites for toluene,and thus significantly increase the adsorption capacity for toluene. The outstanding photocatalytic performance of ozone-modified TiO2 is due to its high adsorption ability for toluene and the abundant surface hydroxyl groups, which produce very reactive OH·radicals under irradiation. Furthermore, the O2 generated via ozone dissociation could combine with the photogenerated electrons to form superoxide radicals which are also conductive to the toluene degradation.展开更多
A sample of sulfated anatase TiO2 with high‐energy(001)facets(TiO2‐001)was prepared by a simple one‐step hydrothermal route using SO42-as a morphology‐controlling agent.After doping ceria,Ce/TiO2‐001 was used as ...A sample of sulfated anatase TiO2 with high‐energy(001)facets(TiO2‐001)was prepared by a simple one‐step hydrothermal route using SO42-as a morphology‐controlling agent.After doping ceria,Ce/TiO2‐001 was used as the catalyst for selective catalytic reduction(SCR)of NO with NH3.Compared with Ce/P25(Degussa P25 TiO2)and Ce/P25‐S(sulfated P25)catalysts,Ce/TiO2‐001 was more suitable for medium‐and high‐temperature SCR of NO due to the high surface area,sulfation,and the excellent properties of the active‐energy(001)facets.All of these facilitated the generation of abundant acidity,chemisorbed oxygen,and activated NOx‐adsorption species,which were the important factors for the SCR reaction.展开更多
Anatase TiO2 with a variant percentage of exposed (001) facets was prepared under hydrothermal processes by adjusting the volume of HF, and the photocatalytic mechanism was studied from atomic-molecular scale by HRT...Anatase TiO2 with a variant percentage of exposed (001) facets was prepared under hydrothermal processes by adjusting the volume of HF, and the photocatalytic mechanism was studied from atomic-molecular scale by HRTEM and Raman spectroscopy. It was revealed that: 1) From HRTEM observations, the surface of original TiO2 with exposed (001) facets was clean without impurity, and the crystal lattice was clear and completed; however, when mixed with methylene blue (MB) solution, there were many 1 nm molecular absorbed at the surface of TiO2; after the photocatalytic experiment, MB molecules disappeared and the TiO2 lattice image became fuzzy. 2) The broken path of the MB chemical bond was obtained by Raman spectroscopy, i.e., after the irradiation of the light, the vibrational mode of C-N-C disappeared due to the chemical bond breakage, and the groups containing C-N bond and carbon rings were gradually decomposed. Accordingly, we propose that the driving force for breaking the chemical bond and the disappearance of groups is from the surface lattice distortion of TiO2 during photocatalyzation.展开更多
基金supported by the Ministry of Science and Technology of China (No.2016YFA0200603)the National Natural Science Foundation of China (No.91421313 and No.21573207)Anhui Initiative in Quantum Information Technologies (AHY090300)
文摘The chemistry of acetaldehyde (CH3CHO) adsorbed on the anatase TiO2(001)-(1×4) surface has been investigated by temperature-programmed desorption (TPD) method. Our experimental results provide the direct evidence that the perfect lattice sites on the anatase TiO2(001)-(1×4) surface are quite inert for the reaction of CH3CHO, but the reduced defect sites on the surface are active for the thermally driven reductive carbon-carbon coupling reactions of CH3CHO to produce 2-butanone and butene. We propose that the coupling reactions of CH3CHO on the anatase TiO2(001)-(1×4) surface should undergo through the adsorption of paired CH3CHO molecules at the reduced defect sites, since the existing reduced Ti pairs provide the suitable adsorption sites.
基金the National Natural Science Foundation of China (U1632273, 21673214,U1732272, U1832165).
文摘This study investigated the positive effect of surface modification with ozone on the photocatalytic performance of anatase TiO2 with dominated(001) facets for toluene degradation.The performance of photocatalyst was tested on a home-made volatile organic compounds degradation system. The ozone modification, toluene adsorption and degradation mechanism were established by a combination of various characterization methods, in situ diffuse reflectance infrared fourier transform spectroscopy, and density functional theory calculation.The surface modification with ozone can significantly enhance the photocatalytic degradation performance for toluene. The abundant unsaturated coordinated 5 c-Ti sites on(001)facets act as the adsorption sites for ozone. The formed Ti–O bonds reacted with H2O to generate a large amount of isolated Ti5 c-OH which act as the adsorption sites for toluene,and thus significantly increase the adsorption capacity for toluene. The outstanding photocatalytic performance of ozone-modified TiO2 is due to its high adsorption ability for toluene and the abundant surface hydroxyl groups, which produce very reactive OH·radicals under irradiation. Furthermore, the O2 generated via ozone dissociation could combine with the photogenerated electrons to form superoxide radicals which are also conductive to the toluene degradation.
基金supported by the National Key R&D Program of China(2016YFC0204100)the Zhejiang Provincial "151" Talents Program+1 种基金the Program for Zhejiang Leading Team of S&T Innovation(2013TD07)the Changjiang Scholar Incentive Program(2009)~~
文摘A sample of sulfated anatase TiO2 with high‐energy(001)facets(TiO2‐001)was prepared by a simple one‐step hydrothermal route using SO42-as a morphology‐controlling agent.After doping ceria,Ce/TiO2‐001 was used as the catalyst for selective catalytic reduction(SCR)of NO with NH3.Compared with Ce/P25(Degussa P25 TiO2)and Ce/P25‐S(sulfated P25)catalysts,Ce/TiO2‐001 was more suitable for medium‐and high‐temperature SCR of NO due to the high surface area,sulfation,and the excellent properties of the active‐energy(001)facets.All of these facilitated the generation of abundant acidity,chemisorbed oxygen,and activated NOx‐adsorption species,which were the important factors for the SCR reaction.
文摘Anatase TiO2 with a variant percentage of exposed (001) facets was prepared under hydrothermal processes by adjusting the volume of HF, and the photocatalytic mechanism was studied from atomic-molecular scale by HRTEM and Raman spectroscopy. It was revealed that: 1) From HRTEM observations, the surface of original TiO2 with exposed (001) facets was clean without impurity, and the crystal lattice was clear and completed; however, when mixed with methylene blue (MB) solution, there were many 1 nm molecular absorbed at the surface of TiO2; after the photocatalytic experiment, MB molecules disappeared and the TiO2 lattice image became fuzzy. 2) The broken path of the MB chemical bond was obtained by Raman spectroscopy, i.e., after the irradiation of the light, the vibrational mode of C-N-C disappeared due to the chemical bond breakage, and the groups containing C-N bond and carbon rings were gradually decomposed. Accordingly, we propose that the driving force for breaking the chemical bond and the disappearance of groups is from the surface lattice distortion of TiO2 during photocatalyzation.