Solvothermal growth of {0 0 1} exposed anatase nanosheets and their ability to mineralize organic pollutants. The effect of alcohol type and content on the nucleation and growth of TiO2 nanostructures

Abstract

Herein, the series of {001} exposed anatase nanosheets from HF-assisted solvothermal growth synthesis were obtained. The two-dimensional TiO2 were characterized, including both bulk (XRD, DR-UV–Vis, Mott-Schottky) and surface characteristics (N2 sorption, XPS, SEM) with experimental results compiled with Density Functional Theory (DFT) calculations. The effect of alcohol amount and type was studied, demonstrating the crucial role of nucleation rate on the final material properties, which was connected with the possible ligand exchange between F− and ROH in the [TiF6]2− octahedra, leading to further TiO2 condensation through an ether elimination reaction. Highly active 2D nanoparticles were easily obtained for different reaction times when a moderate amount of n-butanol or n-hexanol was introduced to the synthesis. The photoactivity of 2D TiO2 with exposed {001} facet strongly depended on the photocatalytic available surface area with an increased amount of ortho–hydroxyphenol (catechol) formed as aby-product. Meanwhile, the rise of n-butanol or n-hexanol content during solvothermal reaction or changing it to ethanol allowed to form smaller and more crystalline anatase particles, but their activity was hindered. For these samples, the slow phenol disappearance and no catechol formation occurred due to (i) alower amount of adsorbed fluorine, (ii) band position shifting towards lower values, and (iii) the surface presence of Ti3+, which prevented the generation of OH radicals. It was also found that changing the nucleation rate by modifying the reaction environment influences the fluorine ions distribution, determining the final properties of 2D structure photocatalyst.