RESUMEN

The growing field of two-dimensional (2D) materials has recently witnessed the emergence of heterostructures, however those combining monoelemental layered materials remain relatively unexplored. In this study, we present the chemical fabrication and characterization of a heterostructure formed by graphene and hexagonal antimonene. The interaction between these 2D materials is thoroughly examined through Raman spectroscopy and first-principles calculations, revealing that this can be considered as a van der Waals heterostructure. Furthermore, we have explored the influence of the antimonene 2D material on the reactivity of graphene by studying the laser-induced covalent functionalization of the graphene surface. Our findings indicate distinct degrees of functionalization based on the underlying material, SiO2 being more reactive than antimonene, opening the door for the development of controlled patterning in devices based on these heterostructures. This covalent functionalization implies a high control over the chemical information that can be stored but also removed on graphene surfaces, and its use as a patterned heterostructure based on antimonene and graphene. This research provides valuable insights into the antimonene-graphene interactions and their impact on the chemical reactivity during graphene covalent functionalization.

RESUMEN

Advanced oxidation processes are useful methodologies to accomplish abatement of contaminants; however, elucidation of the reaction mechanisms is hampered by the difficult detection of the short-lived primary key species involved in the photocatalytic processes. Nevertheless, herein the combined use of an organic photocatalyst such as triphenylpyrylium (TPP+) and photophysical techniques based on emission and absorption spectroscopy allowed monitoring the photocatalyst-derived short-lived intermediates. This methodology has been applied to the photocatalyzed degradation of different pollutants, such as acetaminophen, acetamiprid, caffeine and carbamazepine. First, photocatalytic degradation of a mixture of the pollutants showed that acetaminophen was the most easily photodegraded, followed by carbamazepine and caffeine, being the abatement of acetamiprid almost negligible. This process was accompanied by mineralization, as demonstrated by trapping of carbon dioxide using barium hydroxide. Then, emission spectroscopy measurements (steady-state and time-resolved fluorescence) allowed demonstrating quenching of the singlet excited state of TPP+. Laser flash photolysis experiments with absorption detection showed that oxidation of contaminants is accompanied by TPP+ reduction, with formation of a pyranyl radical (TPP), that constituted a fingerprint of the redox nature of the occurring process. The relative amounts of TPP detected was also correlated with the efficiency of the photodegradation process.

Asunto(s)

RESUMEN

Advanced oxidation processes are useful methodologies to accomplish abatement of contaminants; however, elucidation of the reaction mechanisms is hampered by the difficult detection of the short-lived primary key species involved in the photocatalytic processes. Nevertheless, herein the combined use of an organic photocatalyst such as triphenylpyrylium (TPP+) and photophysical techniques based on emission and absorption spectroscopy allowed monitoring the photocatalyst-derived short-lived intermediates. This methodology has been applied to the photocatalyzed degradation of different pollutants, such as acetaminophen, acetamiprid, caffeine and carbamazepine. First, photocatalytic degradation of a mixture of the pollutants showed that acetaminophen was the most easily photodegraded, followed by carbamazepine and caffeine, being the abatement of acetamiprid almost negligible. This process was accompanied by mineralization, as demonstrated by trapping of carbon dioxide using barium hydroxide. Then, emission spectroscopy measurements (steady-state and time-resolved fluorescence) allowed demonstrating quenching of the singlet excited state of TPP+. Laser flash photolysis experiments with absorption detection showed that oxidation of contaminants is accompanied by TPP+ reduction, with formation of a pyranyl radical (TPP), that constituted a fingerprint of the redox nature of the occurring process. The relative amounts of TPP detected was also correlated with the efficiency of the photodegradation process.