Well-ordered TiO 2 nanotube arrays (TNAs) were fabricated by electrochemical anodization in a mixed organic electrolyte consisting of ethylene glycol and glycerol. The morphology, structure, crystalline phase, and pho...Well-ordered TiO 2 nanotube arrays (TNAs) were fabricated by electrochemical anodization in a mixed organic electrolyte consisting of ethylene glycol and glycerol. The morphology, structure, crystalline phase, and photocatalytic properties of TNAs were characterized by using TEM, SEM, XRD and photodegradation of methylene blue. It was found that the morphology and structure of TNAs could be significantly influenced by the anodization time and applied voltage. The obtained tube length was found to be proportional to anodization time, and the calculated growth rate of nanotubes was 0.6 m/h. The microstructure analysis demonstrated that the diameter and thickness of the nanotubes increased with the increase of anodization voltage. The growth mechanism of TNAs was also proposed according to the observed relationship between current density and time during anodization. As expected, the obtained TNAs showed a higher photocatalytic activity than the commercial TiO 2 P25 nanoparticles.展开更多
TNAs （Titanium dioxide nanotube arrays） were synthesized by electrochemical anodization and these TNAs were annealed in different gas atmosphere such as argon, air, hydrogen and nitrogen. This annealing in different...TNAs （Titanium dioxide nanotube arrays） were synthesized by electrochemical anodization and these TNAs were annealed in different gas atmosphere such as argon, air, hydrogen and nitrogen. This annealing in different atmosphere brought variation in crystallite size （27 - 33 nm）, which influences on electrochemical properties. The specific capacity of Ar, Air, N2 and H2-annealed TNAs was around ~165, 185, 177 and 190 mAh g~, respectively. The crystallite size of anatase TNAs seemed to be responsible for the change in lithium storage capacity, indicating that structural changes of TNAs were playing major role in electrochemical properties.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
This study aimed to construct a photoelectrocatalytic(PEC)reaction system based on the self-made reduced TiO_(2) NTAs(r-TNAs)photoanode and activated carbon/Polytetrafluoroethylene(AC/PTFE)cathode.It would be observed...This study aimed to construct a photoelectrocatalytic(PEC)reaction system based on the self-made reduced TiO_(2) NTAs(r-TNAs)photoanode and activated carbon/Polytetrafluoroethylene(AC/PTFE)cathode.It would be observed clearly that the degradation rate constant of carbamazepine(CBZ)over r-TNAs(photoanode)-AC/PTFE(cathode)PEC system(0.04961 min^(-1))was even higher than that of r-TNAs(photoanode)-Pt(cathode)PEC system(0.04602 min^(-1))with the assistance of visible light irradiation and+0.4 V external potential.Besides,in order to obtain optimized conditions,the influence of key parameters such as pH value,electric current density and electrolyte concentration were studied.Most impo rtantly,photoelectrochemical(PECH)properties,reactive oxide species contribution.OH formation rate and CBZ degradation pathway were determined.The results illustrated that the excellent PEC degradation performance depended on the excellent photocatalytic property of r-TNAs photoanode and electron transfer prope rty of photoelectrodes in r-TNAs(photoanode)-AC/PTFE(cathode)PEC system.Therefo re,the study demonstrated that the r-TNAs(photoanode)-AC/PTFE(cathode)PEC system could be expected to replace metal-catalyzed cathodes depending on its excellent PEC performance activity and low cost as well as the reaction system possessed objective and practical application prospect.展开更多
基金financially supported by the National Natural Science Foundation of China (51072189, 21003111, 21003112)Natural Science Foundation of Zhejiang Province (Y4090507)Scientific Research Foundation of Education Department of Zhejiang Province(Y201018867)
文摘Well-ordered TiO 2 nanotube arrays (TNAs) were fabricated by electrochemical anodization in a mixed organic electrolyte consisting of ethylene glycol and glycerol. The morphology, structure, crystalline phase, and photocatalytic properties of TNAs were characterized by using TEM, SEM, XRD and photodegradation of methylene blue. It was found that the morphology and structure of TNAs could be significantly influenced by the anodization time and applied voltage. The obtained tube length was found to be proportional to anodization time, and the calculated growth rate of nanotubes was 0.6 m/h. The microstructure analysis demonstrated that the diameter and thickness of the nanotubes increased with the increase of anodization voltage. The growth mechanism of TNAs was also proposed according to the observed relationship between current density and time during anodization. As expected, the obtained TNAs showed a higher photocatalytic activity than the commercial TiO 2 P25 nanoparticles.
基金Acknowledgments This work is supported by the National Natural Science Foundation of China （Grand No. 21271114） Tsinghua University independent research and development fund （20111080982） and Program for Changjiang Scholars and Innovative Research Team in University （IRT13026）.
文摘TNAs （Titanium dioxide nanotube arrays） were synthesized by electrochemical anodization and these TNAs were annealed in different gas atmosphere such as argon, air, hydrogen and nitrogen. This annealing in different atmosphere brought variation in crystallite size （27 - 33 nm）, which influences on electrochemical properties. The specific capacity of Ar, Air, N2 and H2-annealed TNAs was around ~165, 185, 177 and 190 mAh g~, respectively. The crystallite size of anatase TNAs seemed to be responsible for the change in lithium storage capacity, indicating that structural changes of TNAs were playing major role in electrochemical properties.
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National Natural Science Foundation of China(Nos.51508254,51978319)Fundamental Research Funds for the Central Universities(No.lzujblky-2017-it98)+1 种基金National College Student Innovation and Entrepreneurship Training Program of Lanzhou UniversityKey Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lake,Chinese Academy of Sciences。
文摘This study aimed to construct a photoelectrocatalytic(PEC)reaction system based on the self-made reduced TiO_(2) NTAs(r-TNAs)photoanode and activated carbon/Polytetrafluoroethylene(AC/PTFE)cathode.It would be observed clearly that the degradation rate constant of carbamazepine(CBZ)over r-TNAs(photoanode)-AC/PTFE(cathode)PEC system(0.04961 min^(-1))was even higher than that of r-TNAs(photoanode)-Pt(cathode)PEC system(0.04602 min^(-1))with the assistance of visible light irradiation and+0.4 V external potential.Besides,in order to obtain optimized conditions,the influence of key parameters such as pH value,electric current density and electrolyte concentration were studied.Most impo rtantly,photoelectrochemical(PECH)properties,reactive oxide species contribution.OH formation rate and CBZ degradation pathway were determined.The results illustrated that the excellent PEC degradation performance depended on the excellent photocatalytic property of r-TNAs photoanode and electron transfer prope rty of photoelectrodes in r-TNAs(photoanode)-AC/PTFE(cathode)PEC system.Therefo re,the study demonstrated that the r-TNAs(photoanode)-AC/PTFE(cathode)PEC system could be expected to replace metal-catalyzed cathodes depending on its excellent PEC performance activity and low cost as well as the reaction system possessed objective and practical application prospect.
