This review provides a detailed exploration of titanium dioxide (TiO₂) photocatalysts, emphasizing structural phases, heterophase junctions, and their impact on efficiency. Key points include diverse synthesis methods, with a focus on the sol-gel route and variants like low-temperature hydrothermal synthesis (LTHT). The review delves into the influence of acid-base donors on gelation, dissects crucial drying techniques for TiO₂ aerogel or xerogel catalysts, and meticulously examines mechanisms underlying photocatalytic activity. It highlights the role of physicochemical properties in charge diffusion, carrier recombination, and the impact of scavengers in photo-oxidation/reduction. Additionally, TiO₂ doping techniques and heterostructures and their potential for enhancing efficiency are briefly discussed, all within the context of environmental applications.

TiO₂ aerogels doped with Ni, Co, Cu, and Fe were prepared, and their structure and photocatalytic activity during the decomposition of a model pollutant, acid orange (AO7), were studied. After calcination at 500 °C and 900 °C, the structure and composition of the doped aerogels were evaluated and analyzed. XRD analysis revealed the presence of anatase/brookite and rutile phases in the aerogels along with other oxide phases from the dopants. SEM and TEM microscopy showed the nanostructure of the aerogels, and BET analysis showed their mesoporosity and high specific surface area of 130 to 160 m²·g⁻¹. SEM–EDS, STEM–EDS, XPS, EPR methods and FTIR analysis evaluated the presence of dopants and their chemical state. The concentration of doped metals in aerogels varied from 1 to 5 wt.%. The photocatalytic activity was evaluated using UV spectrophotometry and photodegradation of the AO7 pollutant. Ni–TiO₂ and Cu–TiO₂ aerogels calcined at 500 °C showed higher photoactivity coefficients (k_aap) than aerogels calcined at 900 °C, which were ten times less active due to the transformation of anatase and brookite to the rutile phase and the loss of textural properties of the aerogels.