Theoretically, lanthanum can bond with surface oxygens of ZnTiO3 to form La-O-Ti bonds, resulting in the change of both the band structure and the electron state of the surface. To verify this statement, DFT calculations were performed using a model with a dispersed lanthanum atom on the surface (101) of ZnTiO3. The negative heat segmentation values obtained suggest that the incorporation of La on the surface of ZnTiO3 is thermodynamically stable. The bandgap energy value of La/ZnTiO3 (2.92 eV) was lower than that of ZnTiO3 (3.16 eV). TDOS showed that the conduction band (CB) and the valence band (VB) energy levels of La/ZnTiO3 are denser than those of ZnTiO3 due to the participation of hybrid levels composed mainly of O2p and La5d orbitals. From the PDOSs, Bader’s charge analysis, and ELF function, it was established that the La-O bond is polar covalent. MB adsorption on La/ZnTiO3 (−200 kJ/mol) was more favorable than on ZnTiO3 (−85 kJ/mol). From the evidence of this study, it is proposed that the MB molecule first is adsorbed on the surface of La/ZnTiO3, and then the electrons in the VB of La/ZnTiO3 are photoexcited to hybrid levels, and finally, the MB molecule oxidizes into smaller molecules.

Cyanide is a highly toxic compound that can pose serious health problems to both humans and aquatic organisms. Therefore, the present comparative study focuses on the removal of total cyanide from aqueous solutions by photocatalytic adsorption and degradation methods using ZnTiO3 (ZTO), La/ZnTiO3 (La/ZTO), and Ce/ZnTiO3 (Ce/ZTO). The nanoparticles were synthesized by the sol-gel method and characterized by X-ray powder diffractometry (XRD), Scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), Diffuse reflectance spectroscopy (DRS), and Specific surface area (SSA). The adsorption equilibrium data were fitted to the Langmuir and Freundlich isotherm models. Adsorption kinetics were also evaluated using the pseudo-first-order and pseudo-second-order models and the intraparticle diffusion model. Likewise, the photodegradation of cyanide under simulated sunlight was investigated and the reusability of the synthesized nanoparticles for cyanide removal in aqueous systems was determined. The results demonstrated the effectiveness of doping with lanthanum (La) and cerium (Ce) to improve the adsorbent and photocatalytic properties of ZTO. In general, La/ZTO showed the maximum percentage of total cyanide removal (99.0%) followed by Ce/ZTO (97.0%) and ZTO (93.6%). Finally, based on the evidence of this study, a mechanism for the removal of total cyanide from aqueous solutions using the synthesized nanoparticles was proposed.

In this study, GP (geopolymer) and GTA (geopolymer/ZnTiO3/TiO2) geopolymeric materials were prepared from metakaolin (MK) and characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), energy dispersive X-rays (EDX), specific surface area (SSA), and point of zero charge (PZC). The adsorption capacity and photocatalytic activity of the compounds prepared in the form of pellets was determined by degradation of the methylene blue (MB) dye in batch reactors, at pH = 7.0 ± 0.2 and room temperature (20 °C). The results indicate that both compounds are highly efficient at adsorbing MB, with an average efficiency value of 98.5%. The Langmuir isotherm model and the pseudo second order kinetic model provided the best fits to the experimental data for both compounds. In the MB photodegradation experiments under UVB irradiation, GTA reached an efficiency of 93%, being higher than that achieved by GP (4%). Therefore, the incorporation of ZnTiO3/TiO2 in the geopolymeric matrix allowed GTA to achieve higher overall efficiency, by combining adsorption and photocatalysis, compared to the GP compound. The results indicate that the synthesized compounds could be used for up to five consecutive cycles for the removal of MB from wastewater through adsorption and/or photocatalysis processes.