Cationic (V, Mo, Nb, W) doping of TiO2-anatase: A real alternative for visible light-driven photocatalysts

摘要

In this article we investigate the structure-activity link of anatase-type Ti-M (M = V, Mo, Nb, and W) mixed oxides used for toluene photo-oxidation under sunlight-type excitation. An analysis of the local and long-range structural and electronic characteristics of the mixed oxides show that only structurally highly homogeneous anatase-type oxides with electronic properties exclusively leading to a band gap decrease drive to efficient visible light-driven photocatalysts. Within our microemulsion preparation method, this only occurs for Ti-V and Ti-W series of samples. The isoelectronic (V~(4+)) substitution of Ti~(4+) ions at the anatase lattice is characterized by a low solubility limit (ca. 2.5 at. %), and drives to a limited modification of the band gap and to a moderate enhancement of the photo-activity with respect to bare titania reference systems. W presence at anatase cation positions occurs with concomitant presence of cation vacancies derived by the charge imbalance between the W~(6+) and Ti~(4+) species. A unique W-vacancy local arrangement is detected by the structural characterization, leading to both an important band gap decrease and enhancement of the photo-activity upon sunlight excitation.