Identification of Nanoscale Processes Associated with the Disorder-to-Order Transformation of Carbon-Supported Alloy Nanoparticles.

ABSTRACT

Due to their ordered crystal structures and high structural stabilities, intermetallic nanoparticles often display enhanced catalytic, magnetic, and optical properties compared to their random alloy counterparts. Intermetallic nanoparticles can be achieved by thermal annealing of their disordered (random alloy) counterparts. However, high temperatures and long annealing times needed to achieve the disorder-to-order transition often lead to a loss of sample monodispersity and an increase in the average size of nanoparticles. Here, we performed ex situ powder X-ray diffraction (XRD) and in situ annealing transmission electron microscopy (TEM) experiments to elucidate nanoscale processes that contribute to the ordering of carbon-supported PdCu nanoparticles as a model system. Random alloy PdCu nanoparticles supported on carbon were thermally annealed for various lengths of time at the disorder-to-order phase transition temperature, where changes in nanoparticle size and the crystal phase were monitored. The nanoparticles were only completely transformed to the intermetallic phase by undertaking measures to deliberately increase their size by increasing the number of nanoparticles on the carbon support. In situ annealing TEM experiments reveal nanoscale processes that account for the disorder-to-order phase transformation. Five different processes were observed at 400 °C. Isolated nanoparticles remained in the random alloy phase or underwent a phase transformation to the intermetallic phase. Nanoparticles fused with neighboring nanoparticles resulting in no change in phase or conversion to the intermetallic phase. Evidence of vapor transport was also observed, as some isolated nanoparticles were found to diminish in size upon heating. These variable processes account for the heterogeneity often observed for intermetallic nanoparticle samples achieved through annealing and motivate the development of synthetic routes that suppress particle-particle coalescence, as well as investigating metal-support interactions to facilitate the disorder-to-order phase transformation under mild conditions. Overall, this work furthers our knowledge of the formation of intermetallic nanoparticles by thermal annealing approaches, which could accelerate the development of electrocatalysts and the application of intermetallic nanoparticles in magnetic storage devices.