Intensive research has been focused on the synthesis of N-modified TiO₂ materials having visible light absorption in order to get higher solar photocatalytic degradation rates of pollutants in water. However, an exhaustive revision of the topic underlines several controversial issues related to N-modified TiO₂ materials; these issues concern (a) the methodology used for preparation, (b) the assessment of the structural characteristics, (c) the mechanistic action modes and (d) the raisons argued to explain the limited performances of the prepared materials for organic and biological targets photodegradation in water. Taking advantage of last year's progress in analytical chemistry and in material characterization methods, the authors show, for example, that some works in the literature controversially attribute the term nitrogen doping without enough analytical evidence. Additionally, some papers describe N-modified TiO₂ photocatalysts as being able to generate holes with enough oxidative potential to form hydroxyl radicals under visible light. This last assertion often derives from a no pertinent use of illumination sources, light filters, or targets or a limited understanding of the thermodynamic aspects of the studied systems. None of N-containing materials prepared by herein presented methods leads, under solar light, to a significant enhancement in pollutants degradation and microorganism's inactivation kinetics.

Under air atmosphere, the photocatalytic discoloration of malachite green (MG) aqueous solutions (a triphenylmethane dye) in the presence of TiO₂ and UV light followed an oxidative pathway, involving an N-demethylation process evidenced by a blue shifting of the main absorption band with a maximum at 618 nm. This oxidative process was affected by the nature of the dye counter-ion and the pH of the solution. At pH 6.0, the oxidation was found to be faster than at pH 3.0, perhaps due to the poor interactions between MG and the semiconductor surface. Furthermore, with the presence of oxalate as counter-ion, the oxidative photocatalytic discoloration was negatively affected mainly at acidic pH. Under nitrogen atmosphere, some evidence was found about the double behaviour of MG when involved in the photocatalytic discoloration reactions pertaining to TiO₂ under these conditions. MG could be simultaneously oxidized, forming N-demethlyated by-products, or reduced, thus leading to leuco-malachite green (LMG) (a colorless and toxic substance) as the main product. The LMG formation is favoured at low pH in the presence of oxalate as counter-ion.