Electrochemical Oxidative Fluorination of an Oxide Perovskite
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Semi transparent three-dimensional macroporous (3DM) photoanodes based on quaternary oxynitrides have the potential to simultaneously realize superior light harvesting and efficient charge transfer in a tandem photoelectrochemical (PEC) cell. A 3DM CaTaO 2 N photoanode was prepared for the first time on a GaN/Al 2 O 3 substrate via a chemical route, and it exhibits a high transmittance of >60% in the wide solar spectrum and a photoresponse onset at −0.3 V versus the reversible hydrogen electrode (V RHE ) under simulated solar illumination. In particular, a plateau photocurrent density of 0.21 mA cm –2 was achieved at a low potential of 0.4 V RHE , which was 1.6-fold and more than 50-fold higher than a two-dimensional macroporous (2DM) CaTaO 2 N/GaN/Al 2 O 3 photoanode and a conventional particle-based CaTaO 2 N/GaN/Al 2 O 3 photoanode, respectively. The bicontinuous, interconnected pore structure within this 3DM film can improve charge carrier separation and collection by reducing the average diffusion distance for minority carriers toward the electrolyte. Optical measurements and simulations verified the enhanced sunlight harvesting in the 3DM photoanode, which was ascribed to the concentrated distribution of the electric field and multiple scattering. Furthermore, this study provides guidance for future synthesis of highly efficient semitransparent 3DM quaternary oxynitride-based photoanodes for a tandem PEC device.
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Using neutron powder diffraction and magnetic susceptibility measurements, we report on the preparation and characterization of the temperature- and field-dependent properties of CaY2ZrFe4O12, a composition closely related to the high-temperature ferrimagnet Y3Fe5O12. By diluting the concentration of paramagnetic ions on the octahedral sublattice of the garnet structure, we find temperature-dependent canting of the magnetic moments. This reflects the importance of the octahedral sublattice in mediating the magnetic interactions between the tetrahedral sites and offers insight into a large number of competing magnetic interactions in the garnet structure.
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The synthesis, luminescence, and electrochemical properties of the Ce(III) compound, [(C 5 Me 5 )2(2,6- i Pr 2 C 6 H 3 O)Ce(THF)], 1, were investigated. Based on the electrochemical data, treatment of 1 with CuX (X = Cl, Br, I) results in the formation of the corresponding Ce(IV) complexes, [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(X)]. Each complex has been characterized using NMR, IR, and UV−vis spectroscopy as well as structurally determined using X-ray crystallography. Additionally, the treatment of [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(Br)] with AgF results in the formation of the putative [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(F)]. Furthermore, the electronic structure of these Ce(IV)−X complexes was investigated by bond analyses and the Ce(IV)−F moiety using quantum chemistry NMR calculations.
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