Surface and trapping energies as predictors for the photocatalytic degradation of aromatic organic pollutants

In this study, anatase samples enclosed by the majority of three different crystal facets {0 0 1}, {1 0 0}, and {1 0 1} were successfully synthesized. These materials were further studied toward photocatalytic degradation of phenol and toluene as model organic pollutants in water and gas phases. The obtained results were analyzed concerning their surface structure, reaction type, and surface development. Moreover, the regression model was created to find the correlation between the possible predictors and the photodegradation rate constants (k). From the studied factors, the trapping energy of charge carriers at the surface was found to be the most significant one, exponentially affecting the observed k. This resulted in the overall per-surface activity between the samples being in the order {1 0 1} > {1 0 0} > {0 0 1}. Further introduction of the surface energy (Esurf) to the regression model and the number of possible trapping centers per number of pollutant’s molecules (ntrap·n–1) improved the model accuracy, simultaneously showing the dependence on the reaction type. In the case of phenol photocatalytic degradation, the best accuracy was observed for the model including Esurf ·(ntrap·n–1)1/2 relation, while for the toluene degradation, it included Esurf2 and the S·n–1 ratio, where S is the simple surface area. Concerning different surface features which influence photocatalytic performance and are commonly discussed in the literature, the results presented in this study suggest that trapping is of particular importance.publishe

Crystal Facet Engineering of TiO₂ from Theory to Application

Recently, the surface structure effect on photocatalytic activity has gathered increasing attention due to its reported influence on the charge carrier trapping and separation. Detailed control over the surface structure can be achieved by exposing the specific crystal facets. As a result, the photogenerated electrons and holes can be effectively separated between the different facets of semiconductor crystals. TiO2 is the most studied photocatalyst, with the particles exposing {0 0 1}, {1 0 0}, {1 0 1}, {1 1 0}, {1 1 1}, and {1 0 5} crystal facets. The performed studies have shown that the efficiency of the photocatalytic process strongly depends on the nature of the crystal facet exposed at the photocatalyst surface. In this regard, this chapter focuses on the comparison of possible surface-related parameters and photocatalytic activity of anatase, rutile, and brookite polymorphs with exposed different crystal facets. Particularly, computational data on their different possible surface structures are summarized, focusing on the geometry, energy, and possible reconstructions. This is followed by the general description of the hypothetical Wulff constructions and existing stabilization/synthesis strategies. Such an approach could help to further design, simulate, and optimize photocatalyst surface for efficient photoreduction and photooxidation processes

The Effect of Titanium Oxyfluoride Morphology on Photocatalytic Activity of Fluorine-Doped Titanium(IV) Oxide

Titanium oxyfluoride (TiOF2) is a metastable product that can be obtained in a fluorine-rich environment. This material can also be a valuable precursor in the synthesis of titanium(IV) oxide (TiO2). However, the effect of TiOF2 morphology on the physicochemical properties of TiO2 has not been studied so far. In this work, single-phase TiOF2 was prepared by a solvothermal method. The as-synthesized samples exhibited a variety of morphologies, including different shapes and crystallite sizes. These materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDS), surface area measurements, thermal gravimetric analysis (TGA) and UV–vis diffuse reflectance spectroscopy (DR/UV–vis). Furthermore, TiOF2 samples were used as precursors in the synthesis of fluorine-doped titanium(IV) oxide and applied in photocatalytic phenol degradation under UV-vis light. The experiments showed that the crystallite size of the precursor, as well as the number of fluoride ions used in the synthesis, were the predominant factors that affected the photocatalytic activity of the final photocatalyst

Pilot-Scale Studies of WO3/S-Doped g-C3N4 Heterojunction toward Photocatalytic NOx Removal

Due to the rising concentration of toxic nitrogen oxides (NOx) in the air, effective methods of NOx removal have been extensively studied recently. In the present study, the first developed WO3/S-doped g-C3N4 nanocomposite was synthesized using a facile method to remove NOx in air efficiently. The photocatalytic tests performed in a newly designed continuous-flow photoreactor with an LED array and online monitored NO2 and NO system allowed the investigation of photocatalyst layers at the pilot scale. The WO3/S-doped-g-C3N4 nanocomposite, as well as single components, were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller surface area analysis (BET), X-ray fluorescence spectroscopy (XRF), X-ray photoemission spectroscopy method (XPS), UV–vis diffuse reflectance spectroscopy (DR/UV–vis), and photoluminescence spectroscopy with charge carriers’ lifetime measurements. All materials exhibited high efficiency in photocatalytic NO2 conversion, and 100% was reached in less than 5 min of illumination under simulated solar light. The effect of process parameters in the experimental setup together with WO3/S-doped g-C3N4 photocatalysts was studied in detail. Finally, the stability of the composite was tested in five subsequent cycles of photocatalytic degradation. The WO3/S-doped g-C3N4 was stable in time and did not undergo deactivation due to the blocking of active sites on the photocatalyst’s surface