RESUMO
Oxynitrides are promising visible-light-responsive photocatalysts, but their structures are almost confined with three-dimensional (3D) structures such as perovskites. A phase-pure Li2 LaTa2 O6 N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium-rich oxide precursor. Li2 LaTa2 O6 N exhibited high crystallinity and visible-light absorption up to 500â nm. As opposed to well-known 3D oxynitride perovskites, Li2 LaTa2 O6 N supported by a binuclear RuII complex was capable of stably and selectively converting CO2 into formate under visible light (λ>400â nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li2 LaTa2 O6 N possesses a lower density of mid-gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride.
RESUMO
An yttrium-tantalum oxynitride having a band gap of 2.1 eV (absorbing visible light at <580 nm) was applicable as a semiconductor component of a Z-scheme CO2 reduction system operable under visible light, in combination with a binuclear Ru(ii) complex that has strong absorption in the visible region (<600 nm). Excitation of this system with visible light under a CO2 atmosphere induced photocatalytic formation of formic acid with very high selectivity (>99%).