In the present work, highly ordered titanium dioxide (TiO 2 ) nanotube anodes were grown using a rapid anodization process. The photoelectrochemical performances of these electrodes strongly depend on the anodization conditions. Parameters such as electrolyte composition, anodization potential and anodization time are shown to affect the geometrical parameters of TiO 2 nanotubes. The optimal anodization parameters are determined by photocurrent measurements, linear sweep voltammetry and electrochemical impedance spectroscopy. The thickness of the tube wall and its homogeneity is shown to strongly depend on the anodization potential, and the formation mechanism is discussed. This study permits the optimization of the photocurrent density and contributes to further improvement of the photoelectrochemical water-splitting performance of TiO 2 nanotube photoelectrodes.
Cobaloximes and their BF<sub>2</sub>-bridged analogues have emerged as promising non-noble metal catalysts for the photocatalytic hydrogen evolution reaction (HER). Herein we report the serendipitous discovery that double complex salts such as [Co(dmgh)<sub>2</sub>py<sub>2</sub>]<sup>+</sup>[Co(dmgBPh<sub>2</sub>)<sub>2</sub>Cl<sub>2</sub>]<sup>-</sup> can be obtained in good yields by treatment of commercially available [Co(dmgh)<sub>2</sub>pyCl] with triarylboranes. A systematic study on the use of such double complex salts and their single salts with simple counterions as photocatalysts revealed HER activities comparable or superior to existing cobaloxime catalysts and suggests ample opportunities for this compound class in catalyst/photosensitizer dyads and immobilized architectures. Preliminary electrochemical and spectroscopic studies indicate that one key advantage of these charged cobalt complexes is that the reduction potentials as well as the electrostatic interaction with charged photosensitizers can be tuned.
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