Photoelectrochemical measurements Photoelectrochemical experiments were monitored by an electrochemical workstation (IM6ex, Zahner, Germany). V, N co-doped TNAs (an active learn more area of 4 cm2) and platinum foil electrode were used as working electrode and counter electrode, and saturated calomel electrode (SCE) acted as reference electrode, respectively. 1 M KOH aqueous solution was used as the supporting electrolyte and purged with N2 for 20 min before measurement to remove the dissolved oxygen. A 300-W Hg lamp was used as the light source. Photocurrent measurements
were carried out under UV-vis irradiation at an applied bias voltage of 0.4 V (vs. SCE) in ambient conditions at room temperature. Photocatalytic reduction
of CO2 Photocatalytic reduction of CO2 was performed in a 358-mL cylindrical glass vessel containing 20 mL 0.1 mol/L KHCO3 solution with a 300-W Hg lamp fixed parallel to the glass reactor as light source. TNAs films were placed in the center of the reactor before sealing the reactor. Prior to reduction experiment under irradiation, ultra-pure gaseous CO2 and water vapor were flowed through the reactor for 2 h to reach adsorption equilibrium within the reactor. Each experiment was followed for 6 h. The analysis of CH4 was online conducted with a gas chromatography (GC). Results and discussion Morphology Figure 1 shows FESEM images of N-TiO2 and V, N co-doped TNAs with various doping amounts. N-TiO2 nanotube arrays before hydrothermal AZD1152 treatment are uniformly stacked with tubular structures with an average diameter of 130 nm and an average wall thickness of 20 nm (Figure 1a). The side view image in Figure 1b also reveals that the vertically orientated nanotubes have an average length of 11 μm. According to SEM observations in Figure 1c,d, the VN0 sample after hydrothermal treatment in pure water presents no apparent structural transformation. The side view image in Figure 1d also shows the highly ordered nanotube arrays with
similar diameter and wall thickness of N-TiO2 sample before hydrothermal reaction. Yu et al. had reported that the nanotube Ixazomib mouse array structures were completely destroyed after 180°C hydrothermal treatments with TNAs samples due to the enhanced Torin 1 ic50 anatase crystallinity and phase transformation from amorphous to anatase [13]. In our experiments, oxidized TNAs samples were calcinated at 500°C to realize phase transformation from amorphous to anatase before hydrothermal process. By this way, the reported hydrothermally induced collapse was prevented with a simple calcination step. All hydrothermal-treated TNAs samples including the V, N co-doped TNAs show no apparent morphology change after hydrothermal co-doping process. Figure 1e,f presents the top and side view images of the V, N co-doped TNAs with maximal doping amounts of 5% in our experiments.