Anodic TiO2 nanotubes have been studied extensively for many years. However, the growth kinetics still remains unclear. The systematic study of the current transient under constant anodizing voltage has not been mentioned in the original literature. Here, a derivation and its corresponding theoretical formula are proposed to overcome this challenge. In this paper, the theoretical expressions for the time dependent ionic current and electronic current are derived to explore the anodizing process of Ti. The anodizing current-time curves under different anodizing voltages and different temperatures are experimentally investigated in the anodization of Ti. Furthermore, the quantitative relationship between the thickness of the barrier layer and anodizing time, and the relationships between the ionic/electronic current and temperatures are proposed in this paper. All of the current-transient plots can be fitted consistently by the proposed theoretical expressions. Additionally, it is the first time that the coefficient A of the exponential relationship (ionic current j(ion) = A exp(BE)) has been determined under various temperatures and voltages. And the results indicate that as temperature and voltage increase, ionic current and electronic current both increase. The temperature has a larger effect on electronic current than ionic current. These results can promote the research of kinetics from a qualitative to quantitative level.
Organosulfides have great significance and value in synthetic and biological chemistry. To establish a versatile and green methodology for C-S bond generation, we successfully developed a new aerobic cross-dehydrogenative coupling of C-H and S-H to synthesize aryl sulfides in water, utilizing CoPcS as the catalyst and O as the oxidant. This protocol shows great tolerance of a wide range of substrates. A large variety of organosulfur compounds were produced in modest to excellent yields.
Anodic TiO 2 nanotubes (ATNTs) have been studied extensively for many years. However, their mysterious formation mechanism still remains unclear. The formation of gaps and ribs around the nanotubes has not been elucidated. Here, various surface and cross-section morphologies of ATNTs obtained under different anodizing conditions and their evolution process have been investigated in detail. Based on many experimental facts, new explanations for the gaps and ribs are presented. An entire surface layer covered on the nanotubes plays a primary role on the formation of gaps and ribs. The gaps result from the radial distribution of the electric field at the pore bottom. No newly-formed oxide will exist along the gap direction, because the electric filed along the gap is the minimum. The ribs result from the electrolyte entering into the wider gaps among the ATNTs due to the rupture of the entire surface layer. The rings or ribs on the outer wall of ATNTs are formed at the electrolyte/Ti interface due to the discontinuous existence of a small amount of electrolyte within the gap base. The present viewpoint was demonstrated by an original micro-dam, which can block the electrolyte entering into the gaps and avoid the formation of ribs.
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