Liquid-phase transmission electron microscopy (TEM) has been recently applied to materials chemistry to gain fundamental understanding of various reaction and phase transition dynamics at nanometer resolution. However, quantitative extraction of physical and chemical parameters from the liquid-phase TEM videos remains bottlenecked by the lack of automated analysis methods compatible with the videos’ high noisiness and spatial heterogeneity. Here, we integrate, for the first time, liquid-phase TEM imaging with our customized analysis framework based on a machine learning model called U-Net neural network. This combination is made possible by our workflow to generate simulated TEM images as the training data with well-defined ground truth. We apply this framework to three typical systems of colloidal nanoparticles, concerning their diffusion and interaction, reaction kinetics, and assembly dynamics, all resolved in real-time and real-space by liquid-phase TEM. A diversity of properties for differently shaped anisotropic nanoparticles are mapped, including the anisotropic interaction landscape of nanoprisms, curvature-dependent and staged etching profiles of nanorods, and an unexpected kinetic law of first-order chaining assembly of concave nanocubes. These systems representing properties at the nanoscale are otherwise experimentally inaccessible. Compared to the prevalent image segmentation methods, U-Net shows a superior capability to predict the position and shape boundary of nanoparticles from highly noisy and fluctuating background—a challenge common and sometimes inevitable in liquid-phase TEM videos. We expect our framework to push the potency of liquid-phase TEM to its full quantitative level and to shed insights, in high-throughput and statistically significant fashion, on the nanoscale dynamics of synthetic and biological nanomaterials.
We apply the concept of "island formation" established for planar substrates, where ligands laterally cluster as they adsorb, to preparing nanoparticles (NPs) with precisely sized surface patches. Using gold triangular nanoprisms and 2-naphthalenethiols (2-NAT) as a prototypical system, we show that the preferential adsorption of 2-NAT on the prism tips leads to formation of tip patches. The patches are rendered visible for direct transmission electron microscopy and atomic force microscopy imaging upon attaching polystyrene-b-poly-(acrylic acid). Using this method, the shape of patchy prisms is varied from small lobed, big lobed, trefoil, Tshaped to a reuleaux triangle by increasing the 2-NAT-toprism concentration ratio. This trend matches with predictions of island formation as elucidated by our selfconsistent field theory modeling, from which we exclude Langmuir adsorption. The tip-patched prisms assemble into unexpected twisted dimers due to the patch−patch interactions. We expect the island formation as a generalizable strategy to make patchy NPs of various shapes for emergent assemblies and applications.
An emergent theme in mono-and multivalent ion batteries is to utilize nanoparticles (NPs) as electrode materials based on the phenomenological observations that their short ion diffusion length and large electrode−electrolyte interface can lead to improved ion insertion kinetics compared to their bulk counterparts. However, the understanding of how the NP size fundamentally relates to their electrochemical behaviors (e.g., charge storage mechanism, phase transition associated with ion insertion) is still primitive. Here, we employ spinel λ-MnO 2 particles as a model cathode material, which have effective Mg 2+ ion intercalation but with their size effect poorly understood to investigate their operating mechanism via a suite of electrochemical and structural characterizations. We prepare two differently sized samples, the small nanoscopic λ-MnO 2 particles (81 ± 25 nm) and big micron-sized ones (814 ± 207 nm) via postsynthesis size-selection. Analysis of the charge storage mechanisms shows that the stored charge from Mg 2+ ion intercalation dominates in both systems and is ∼10 times higher in small particles than that in the big ones. From both X-ray diffraction and atomic-resolution scanning transmission electron microscopy imaging, we reveal a fundamental difference in phase transition of the differently sized particles during Mg 2+ ion intercalation: the small NPs undergo a solid-solution-like phase transition which minimizes lattice mismatch and energy penalty for accommodating new phases, whereas the big particles follow conventional multiphase transformation. We show that this pathway difference is related to the improved electrochemical performance (e.g., rate capability, cycling performance) of small particles over the big ones which provides important insights in encoding within the particle dimension, that is, the single-phase transition pathway in high-performance electrode materials for multivalent ion batteries.
Synthesizing patchy particles with predictive control over patch size, shape, placement and number has been highly sought-after for nanoparticle assembly research, but is fraught with challenges. Here we show that polymers can be designed to selectively adsorb onto nanoparticle surfaces already partially coated by other chains to drive the formation of patchy nanoparticles with broken symmetry. In our model system of triangular gold nanoparticles and polystyrene-b-polyacrylic acid patch, single- and double-patch nanoparticles are produced at high yield. These asymmetric single-patch nanoparticles are shown to assemble into self-limited patch‒patch connected bowties exhibiting intriguing plasmonic properties. To unveil the mechanism of symmetry-breaking patch formation, we develop a theory that accurately predicts our experimental observations at all scales—from patch patterning on nanoparticles, to the size/shape of the patches, to the particle assemblies driven by patch‒patch interactions. Both the experimental strategy and theoretical prediction extend to nanoparticles of other shapes such as octahedra and bipyramids. Our work provides an approach to leverage polymer interactions with nanoscale curved surfaces for asymmetric grafting in nanomaterials engineering.
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