Controllable surface defect engineering on transition-metal trichalcogenide
NUS scientists have developed a method for controllable introduction of two different types of sulfur vacancies into zirconium trisulfide (ZrS3) turning it into an efficient photocatalyst for hydrogen peroxide (H2O2) generation and benzylamine oxidation.
The introduction of defects can cause unexpected changes in the physical and chemical properties of materials. As a result, defect engineering has been a versatile tool for developing more efficient photocatalysts in chemical reactions. In photocatalytic applications, the introduction of defects can have a significant impact on the optical absorption, charge carrier dynamics, and surface catalysis kinetics of the materials. Better understanding of the structure-activity relationships brought about by the introduction of these defects can result in the development of more efficient photocatalytic materials.
A research team led by Prof Chen Wei from both the Departments of Physics and Chemistry, National University of Singapore has developed a method for controllable introduction of two different types of defects, the disulfide anions (S22-) and the sulfide ion (S2-) vacancies into ZrS3 nanobelts (Figure (a) to (f)). The ZrS3 nanobelts are long one-dimensional nanostructures that look like ribbons. The researchers found that the S22- and S2- vacancies can be introduced into the nanobelt material through two different methods (Figure (g) and (h)). For S22- vacancies, this involves annealing the ZrS3 nanobelt at 700℃ under vacuum conditions. For S2- vacancies, a lithium-based hydrothermal method is used. By varying the annealing time (10, 15, and 20 mins) and amount of lithium present, defect engineered ZrS3 material with varying amount of S22- vacancies and S2- vacancies can be obtained.
The researchers found that this defect engineered ZrS3 material can enhance the photocatalytic production of H2O2 coupled with the selective oxidation of benzylamine to benzonitrile in water. They systematically investigated the effects of S22- and S2- vacancies on the charge carrier dynamics and photocatalytic performance. Their research findings show that the S22- vacancies can significantly facilitate the separation of photogenerated charge carriers. Separately, the S2- vacancies not only promote the electron conduction and hole extraction in the photocatalytic process but they also improve the kinetics of the benzylamine oxidation. These two different types of vacancies in the ZrS3 material work together to improve the performance of the photocatalytic reaction. Under illumination by a simulated sunlight, the ZrS3 material produces H2O2 and benzonitrile at a rate of 78.1 ± 1.5 and 32.0 ± 1.2 μmol h-1 respectively.
Prof Chen said, "Our research findings open up a new route for defect engineering and promise a potential strategy for the study of structure-activity relationships for the design and development of more efficient photocatalysts."