Home Contact Links Jobs
Introduction Admissions Programs People Research Community Outreach News & Seminars
PhD Thesis Presentation
In-Situ Transmission Electron Microscopy Study of Thermal Stability and Structural Transformation of Metal Nanocatalysts
Speaker Mr. Zhehan YING
Department of Physics, The Hong Kong University of Science and Technology
Date 20 August 2021 (Friday)
Time 14:30 (Hong Kong time)
Venue Online (Zoom)

As great importance has been attached to the development of thermal catalysis, some determining factors that always affect metal nanocatalysts from being sustainable and active remain to be explored: thermal stability and structural transformation. Therefore, the real-time insights into their feasible working-temperature range and microstructural reconstruction at thermocatalytic conditions will further greatly extend our knowledge of their physicochemical properties and provide valuable guidance for the designs and applications of metal nanocatalysts. With the aids of in-situ thermal transmission electron microscopy (TEM), the target nanocatalysts can be visually revealed for their temperature-dependent effects and microstructural transformation of nanoparticles with high resolution and a wide operating temperature range. In this thesis, the in-situ TEM was conducted to investigate some innovative thermocatalytic nanocatalysts: platinum nanoparticles deposited on the pristine graphene oxide (PtNPs/GO), platinum nanoparticles deposited on the water-etched graphene oxide (PtNPs/GO-H2O), reduced graphene oxide-based platinum nanoparticle (Pt/rGO), Pd nanoparticles supported on carbon-coated ZnO nanowires (PdNPs/C&ZnO-NWs), Pd nanocatalysts deposited on defective-rich nanodiamond-graphene core-shell structure (Pd/ND@G) and Pd nanocatalysts deposited on onion-like carbon (Pd/OLC) under real-time and real-temperature conditions that perfectly recreated the actual thermal catalysis.

PtNPs/GO-H2O exhibited significantly higher temperature stability (700 °C) than PtNPs/GO. The time-lapsed statistical data of TEM images verified that the size variation of sintering Pt nanoparticles on GO was in accordance with the Ostwald ripening process. The tendency towards the preferential exposure of high-index Pt nanocrystal facets was discovered to accelerate nanoparticle aggregations, providing microscopic evidence of the catalyst instability at high-temperature ranges.

PtNPs exhibited better thermal stability on the rGO flat surface than on the wrinkle surface. The time-resolved analysis demonstrated that the thermal-induced microstructural transformation (graphitization) of the rGO support caused the discrepancy of PtNPs coarsening from the Ostwald ripening model. In-situ high-resolution TEM images further visualized the process of coalescing microstructures of PtNPs on graphitized rGO.

The excellent thermal stability of PdNPs/C&ZnO-NWs was verified to satisfy the temperature requirements of Suzuki coupling reaction. The PdNPs aggregations were not observed until reaching 300 °C and carbon-coated layers could functionally prevent PdNPs from sintering even when ZnO-NWs experienced melting at 500 °C. The ZnO encapsulation behaviors (the surface reconstruction of C&ZnO-NWs supports) were subsequently shown to offer the potential microscopic evidence of PdNPs/C&ZnO-NWs deactivation in thermal catalysis.

PdNPs performed superior thermal stability and catalytic performance on the defective ND@G with core-shell sp3-sp2 structure than on the OLC with pure sp2 graphitic structure. In comparison with Pd/OLC, the coarsening and aggregation of PdNPs cannot be detected on ND@G even at 600 °C. The in-situ high-resolution investigations of microstructural transformation of OLC supports at 600–1000 °C elucidated the detailed process of OLC structural transformation to polygonal hollow carbon via hexagonal hollow carbon and the potential deactivation mechanism of PdNPs supported on OLCs.

Meeting Link: To request for meeting link, please write to phsywu@ust.hk.