Tunable Composition Aqueous-Synthesized Mixed-Phase TiO2 Nanocrystals for Photo-Assisted Water Decontamination: Comparison of Anatase, Brookite and Rutile Photocatalysts

Abstract

Mixed-phase nanoTiO2 materials attract a lot of attention as advanced photocatalysts for water decontamination due to their intrinsic structure that allows better photo-excited e-cb-h+ vb charge separation, hence improved photocatalytic effciency. Currently, the best-known mixed-phase TiO2 photocatalyst is P25 with approximate composition 80% Anatase/20% Rutile (A/r). Apart from Anatase (A) and Rutile (R) phases, there is Brookite (B) which has been evaluated less as photocatalyst in mixed-phase nanoTiO2 systems. In this work we present a sustainable solution process to synthesize tunable composition mixed-phase nanotitania photocatalysts in a continuously stirred tank reactor (CSTR) by modulating conditions like pH, CTiCl4 and time. In particular three mixed-phase TiO2 nanomaterials were produced, namely one predominantly anatase with brookite as minor component (A/b), one predominantly brookite with minor component rutile (B/r), and one predominantly rutile with minor component brookite (R/b) and evaluated as photocatalysts in the degradation of methyl orange. The three semiconducting nanomaterials were characterized by XRD and Raman spectroscopy to quantify the phase ratios and subjected to nano-morphological characterization by FE-SEM and TEM/HR-TEM. The new mixed-phase nanoTiO2 materials are shown to be endowed with large specific surface area, ranging from 90-125 m2 g-1, double of that of P25, to be mesoporous and be surface-rich in Ti-OH molecular groups varying from 12%-20% versus 4% for P25. These properties though impact the adsorptive capacity with R/b and B/r removing > 50% of MO but not photocatalytic activity. The latter depends on nanograined mixed-phase structure and not mere assembly of different phase nanoparticles. First-order rate constants reveal essentially equivalent photocatalytic activity for anatase nanocrystals with either rutile (P25) or brookite (this work) domains.