Multi-step atomic mechanism of platinum nanocrystals nucleation and growth revealed by in-situ liquid cell STEM

The understanding of crystal growth mechanisms has broadened substantially. One significant advancement is based in the conception that the interaction between particles plays an important role in the growth of nanomaterials. This is in contrast to the classical model, which neglects this process. Direct imaging of such processes at atomic-level in liquid-phase is essential for establishing new theoretical models that encompass the full complexity of realistic scenarios and eventually allow for tailoring nanoparticle growth. Here, we investigate at atomic-scale the exact growth mechanisms of platinum nanocrystals from single atom to final crystals by in-situ liquid phase scanning transmission electron microscopy. We show that, after nucleation, the nanocrystals grow via two main stages: atomic attachment in the first stage, where the particles initially grow by attachment of the atoms until depletion of the surrounding zone. Thereafter, follows the second stage of growth, which is based on particle attachment by different atomic pathways to finally form mature nanoparticles. The atomic mechanisms underlying these growth pathways are distinctly different and have different driving forces and kinetics as evidenced by our experimental observations.

Fe3O4@Pt nanoparticles to enable combinational electrodynamic/chemodynamic therapy

Electrodynamic therapy (EDT) has recently emerged as a potential external field responsive approach for tumor treatment. While it presents a number of clear superiorities, EDT inherits the intrinsic challenges of current reactive oxygen species (ROS) based therapeutic treatments owing to the complex tumor microenvironment, including glutathione (GSH) overexpression, acidity and others. Herein for the first time, iron oxide nanoparticles are decorated using platinum nanocrystals (Fe3O4@Pt NPs) to integrate the current EDT with chemodynamic phenomenon and GSH depletion. Fe3O4@Pt NPs can effectively induce ROS generation based on the catalytic reaction on the surface of Pt nanoparticles triggered by electric field (E), and meanwhile it may catalyze intracellular H2O2 into ROS via Fenton reaction. In addition, Fe3+ ions released from Fe3O4@Pt NPs under the acidic condition in tumor cells consume GSH in a rapid fashion, inhibiting ROS clearance to enhance its antitumor efficacy. As a result, considerable in vitro and in vivo tumor inhibition phenomena are observed. This study has demonstrated an alternative concept of combinational therapeutic modality with superior efficacy.

Shape control of size-selected naked platinum nanocrystals

Controlled growth of far-from-equilibrium-shaped nanoparticles with size selection is essential for the exploration of their unique physical and chemical properties. Shape control by wet-chemistry preparation methods produces surfactant-covered surfaces with limited understanding due to the complexity of the processes involved. Here, we report the controlled production and transformation of octahedra to tetrahedra of size-selected platinum nanocrystals with clean surfaces in an inert gas environment. Molecular dynamics simulations of the growth reveal the key symmetry-breaking atomic mechanism for this autocatalytic shape transformation, confirming the experimental conditions required. In-situ heating experiments demonstrate the relative stability of both octahedral and tetrahedral Pt nanocrystals at least up to 700 °C and that the extended surface diffusion at higher temperature transforms the nanocrystals into equilibrium shape.

Critical differences in 3D atomic structure of individual ligand-protected nanocrystals in solution

Precise three-dimensional (3D) atomic structure determination of individual nanocrystals is a prerequisite for understanding and predicting their physical properties. Nanocrystals from the same synthesis batch display what are often presumed to be small but possibly important differences in size, lattice distortions, and defects, which can only be understood by structural characterization with high spatial 3D resolution. We solved the structures of individual colloidal platinum nanocrystals by developing atomic-resolution 3D liquid-cell electron microscopy to reveal critical intrinsic heterogeneity of ligand-protected platinum nanocrystals in solution, including structural degeneracies, lattice parameter deviations, internal defects, and strain. These differences in structure lead to substantial contributions to free energies, consequential enough that they must be considered in any discussion of fundamental nanocrystal properties or applications.