Using systematic experiments, researchers have investigated how surface diffusion – a process in which atoms move from one site to another on nanoscale surfaces – affects the final shape of the particles. The issue is important for a wide range of applications that use specific shapes to optimize the activity and selectivity of nanoparticles, including catalytic converters, fuel cell technology, chemical catalysis and plasmonics.
Results of the research could lead to a better understanding of how to manage the diffusion process by controlling the reaction temperature and deposition rate, or by introducing structural barriers designed to hinder the surface movement of atoms.
Though the importance of particle shape at the nanoscale has been well known, researchers hadn’t before understood the importance of surface diffusion in creating the final particle shape. Adding atoms to the corners of platinum cubes, for instance, can create particles with protruding “arms” that increase the catalytic activity. Convex surfaces on cubic particles may also provide better performance. But those advantageous shapes must be created and maintained.
Natural energetic preferences related to the arrangement of atoms on the tiny structures favor a spherical shape that is not ideal for most catalysts, fuel cells and other applications.
In their research, the research team varied the temperature of the process used to deposit atoms onto metallic nanocrystals that acted as seeds for the nanoparticles. They also varied the rates at which atoms were deposited onto the surfaces, which were determined by the injection rate at which a chemical precursor material was introduced. The diffusion rate is determined by the temperature, with higher temperatures allowing the atoms to move around faster on the nanoparticle surfaces. In the research, bromide ions were used to limit the movement of the added atoms from one portion of the particle to another.
Using transmission electron microscopy, the researchers observed the structures that were formed under different conditions. Ultimately, they found that the ratio of the deposition rate to the diffusion rate determines the final shape. When the ratio is greater than one, the adsorbed atoms tend to stay where they are placed. If the ratio is less than one, they tend to move.
Xia’s research team also studied the impact of diffusion on bi-metallic particles composed of both palladium and platinum. The combination can enhance certain properties, and because palladium is currently less expensive than platinum, using a core of palladium covered by a thin layer of platinum provides the catalytic activity of platinum while reducing cost.
In that instance, surface diffusion can be helpful in covering the palladium surface with a single monolayer of the platinum. Only the surface platinum atoms will be able to provide the catalytic properties, while the palladium core only serves as a support.
The research is part of a long-term study of catalytic nanoparticles being conducted by Xia’s research group. Other aspects of the team’s work addresses biomedical uses of nanoparticles in such areas as cancer therapy.
This story is reprinted from material from Georgia Tech, with editorial changes made by Materials Today. The views expressed in this article do not necessarily represent those of Elsevier. Link to original source.