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Fabrication of Micro-Patterned Chip with Controlled Thickness for High-Throughput Cryogenic Electron Microscopy

A major limitation for the efficient and high-throughput structure analysis of biomolecules using cryogenic electron microscopy (cryo-EM) is the ...

Seoul National University

Institute of Basic Science (IBS)

The formation mechanism of colloidal nanoparticles is complex because significant nonclassical pathways coexist with the conventional nucleation and growth processes. Particularly, the coalescence of the growing clusters determines the final morphology and crystallinity of the synthesized nanoparticles. However, the experimental investigation of the coalescence mechanism is a challenge because the process is highly kinetic and correlates with surface ligands that dynamically modify the surface energy and the interparticle interactions of nanoparticles. Here, we employ quantitative  TEM with multichamber graphene liquid cell to observe the coalescence processes occurring in the synthesis of gold nanoparticles in different ligand systems, thus affording us an insight into their ligand-dependent coalescence kinetics. The analyses of numerous liquid-phase TEM trajectories of the coalescence and MD simulations of the ligand shells demonstrate that enhanced ligand mobility, employing a heterogeneous ligand mixture, results in the rapid nanoparticle pairing approach and a fast post-merging structural relaxation.

Ligand-Dependent Coalescence Behaviors of Gold Nanoparticles Studied by Multichamber Graphene Liquid Cell Transmission Electron Microscopy.

Active sites and catalytic activity of heterogeneous catalysts is determined by their surface atomic structures. However, probing the surface structure at an atomic resolution is difficult, especially for solution ensembles of catalytic nanocrystals, which consist of heterogeneous particles with irregular shapes and surfaces. Here, we constructed 3D maps of the coordination number (CN) and generalized CN () for individual surface atoms of sub-3 nm Pt nanocrystals. Our results reveal that the synthesized Pt nanocrystals are enclosed by islands of atoms with nonuniform shapes that lead to complex surface structures, including a high ratio of low-coordination surface atoms, reduced domain size of low-index facets, and various types of exposed high-index facets. 3D maps of  are directly correlated to catalytic activities assigned to individual surface atoms with distinct local coordination structures, which explains the origin of high catalytic performance of small Pt nanocrystals in important reactions such as oxygen reduction reactions and CO electro-oxidation.

Correlating 3D Surface Atomic Structure and Catalytic Activities of Pt Nanocrystals.

Liquid-phase transmission electron microscopy (TEM) offers a real-time microscopic observation of the nanometer scale for understanding the underlying mechanisms of the growth, etching, and interactions of colloidal nanoparticles. Despite such unique capability and potential application in diverse fields of analytical chemistry, liquid-phase TEM studies rely on information obtained from the limited number of observed events. In this work, a novel liquid cell with a large-scale array of highly ordered nanochambers is constructed by sandwiching an anodic aluminum oxide membrane between graphene sheets. TEM analysis of colloidal gold nanoparticles dispersed in the liquid is conducted, employing the fabricated nanochamber array, to demonstrate the potential of the nanochamber array in quantitative liquid-phase TEM. The independent TEM observations in the multiple nanochambers confirm that the monomer attachment and coalescence processes universally govern the overall growth of nanoparticles, although individual nanoparticles follow different growth trajectories.

A Large-Scale Array of Ordered Graphene-Sandwiched Chambers for Quantitative Liquid-Phase Transmission Electron Microscopy.

Nucleation in atomic crystallization remains poorly understood, despite advances in classical nucleation theory. The nucleation process has been described to involve a nonclassical mechanism that includes a spontaneous transition from disordered to crystalline states, but a detailed understanding of dynamics requires further investigation. In situ electron microscopy of heterogeneous nucleation of individual gold nanocrystals with millisecond temporal resolution shows that the early stage of atomic crystallization proceeds through dynamic structural fluctuations between disordered and crystalline states, rather than through a single irreversible transition. Our experimental and theoretical analyses support the idea that structural fluctuations originate from size-dependent thermodynamic stability of the two states in atomic clusters. These findings, based on dynamics in a real atomic system, reshape and improve our understanding of nucleation mechanisms in atomic crystallization.

Reversible disorder-order transitions in atomic crystal nucleation.

A general problem when designing functional nanomaterials for energy storage is the lack of control over the stability and reactivity of metastable phases. Using the high-capacity hydrogen storage candidate LiAlH as an exemplar, we demonstrate an alternative approach to the thermodynamic stabilization of metastable metal hydrides by coordination to nitrogen binding sites within the nanopores of N-doped CMK-3 carbon (NCMK-3). The resulting LiAlH@NCMK-3 material releases H at temperatures as low as 126 °C with full decomposition below 240 °C, bypassing the usual LiAlH intermediate observed in bulk. Moreover, >80% of LiAlH can be regenerated under 100 MPa H, a feat previously thought to be impossible. Nitrogen sites are critical to these improvements, as no reversibility is observed with undoped CMK-3. Density functional theory predicts a drastically reduced Al-H bond dissociation energy and supports the observed change in the reaction pathway. The calculations also provide a rationale for the solid-state reversibility, which derives from the combined effects of nanoconfinement, Li adatom formation, and charge redistribution between the metal hydride and the host.

Reversing the Irreversible: Thermodynamic Stabilization of LiAlH Nanoconfined Within a Nitrogen-Doped Carbon Host.

Ordered mesoporous carbon materials offer robust network of organized pores for energy storage and catalysis applications, but suffer from time-consuming and intricate preparations hindering their widespread use. Here we report a new and rapid synthetic route for a N-doped ordered mesoporous carbon structure through a preferential heating of iron oxide nanoparticles by microwaves. A nanoporous covalent organic polymer is first formed in situ covering the hard templates of assembled nanoparticles, paving the way for a long-range order in a carbonaceous nanocomposite precursor. Upon removal of the template, a well-defined cubic mesoporous carbon structure was revealed. The ordered mesoporous carbon was used in solid state hydrogen storage as a host scaffold for NaAlH , where remarkable improvement in hydrogen desorption kinetics was observed. The state-of-the-art lowest activation energy of dehydrogenation as a single step was attributed to their ordered pore structure and N-doping effect.

Rapid Access to Ordered Mesoporous Carbons for Chemical Hydrogen Storage.

Cryogenic-electron microscopy (cryo-EM) is the preferred method to determine 3D structures of proteins and to study diverse material systems that intrinsically have radiation or air sensitivity. Current cryo-EM sample preparation methods provide limited control over the sample quality, which limits the efficiency and high throughput of 3D structure analysis. This is partly because it is difficult to control the thickness of the vitreous ice that embeds specimens, in the range of nanoscale, depending on the size and type of materials of interest. Thus, there is a need for fine regulation of the thickness of vitreous ice to deliver consistent high signal-to-noise ratios for low-contrast biological specimens. Herein, an advanced silicon-chip-based device is developed which has a regular array of micropatterned holes with a graphene oxide (GO) window on freestanding silicon nitride (Si N ). Accurately regulated depths of micropatterned holes enable precise control of vitreous ice thickness. Furthermore, GO window with affinity for biomolecules can facilitate concentration of the sample molecules at a higher level. Incorporation of micropatterned chips with a GO window enhances cryo-EM imaging for various nanoscale biological samples including human immunodeficiency viral particles, groEL tetradecamers, apoferritin octahedral, aldolase homotetramer complexes, and tau filaments, as well as inorganic materials.

Graphene Oxide-Supported Microwell Grids for Preparing Cryo-EM Samples with Controlled Ice Thickness.

Single-phase formation of active metal oxides on supports has been vigorously pursued in many catalytic applications to suppress undesired reactions and to determine direct structure-property relationships. However, this is difficult to achieve in nanoscale range because the effect of non-uniform metal-support interfaces becomes dominant in the overall catalyst growth, leading to the nucleation of various metastable oxides. Herein, we develop a supported single-phase corundum-Rh O (I) nanocatalyst by utilizing controlled interaction between metal oxide and h-BN support. Atomic-resolution electron microscopy and first-principle calculation reveal that single-phase formation occurs via uniform and preferential attachment of Rh O (I) (110) seed planes on well-defined h-BN surface after decomposition of rhodium precursor. By utilizing the Rh/h-BN catalyst in methane partial oxidation, syngas is successfully produced solely following the direct route with keeping a H /CO ratio of 2, which makes it ideal for most downstream chemical processes.

Single-Phase Formation of Rh O Nanoparticles on h-BN Support for Highly Controlled Methane Partial Oxidation to Syngas.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers are unit-cell thick materials with tunable physical properties according to their size, morphology, and chemical composition. Their transition of lab-scale research to industrial-scale applications requires process development for the wafer-scale growth and scalable device fabrication. Herein, we report on a new type of atmospheric pressure chemical vapor deposition (APCVD) process that utilizes colloidal nanoparticles as process-scalable precursors for the wafer-scale production of TMD monolayers. Facile uniform distribution of nanoparticle precursors on the entire substrate leads to the wafer-scale uniform synthesis of TMD monolayers with the controlled size and morphology. Composition-controlled TMD alloy monolayers with tunable bandgaps can be produced by simply mixing dual nanoparticle precursor solutions in the desired ratio. We also demonstrate the fabrication of ultrathin field-effect transistors and flexible electronics with uniformly controlled performance by using TMD monolayers.

Wafer-Scale Production of Transition Metal Dichalcogenides and Alloy Monolayers by Nanocrystal Conversion for Large-Scale Ultrathin Flexible Electronics.

Real-space imaging of nanoparticle transport and interaction dynamics by graphene liquid cell TEM.

Correction to "Wafer-Scale Production of Transition Metal Dichalcogenides and Alloy Monolayers by Nanocrystal Conversion for Large-Scale Ultrathin Flexible Electronics".

Article	Year
Ligand-Dependent Coalescence Behaviors of Gold Nanoparticles Studied by Multichamber Graphene Liquid Cell Transmission Electron Microscopy. Nano letters\| PubMed ID: 33186041	2020
Correlating 3D Surface Atomic Structure and Catalytic Activities of Pt Nanocrystals. Nano letters\| PubMed ID: 33416334	2021
A Large-Scale Array of Ordered Graphene-Sandwiched Chambers for Quantitative Liquid-Phase Transmission Electron Microscopy. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 32844520	2020
Reversible disorder-order transitions in atomic crystal nucleation. Science (New York, N.Y.)\| PubMed ID: 33510024	2021
Reversing the Irreversible: Thermodynamic Stabilization of LiAlH Nanoconfined Within a Nitrogen-Doped Carbon Host. ACS nano\| PubMed ID: 34029480	2021
Rapid Access to Ordered Mesoporous Carbons for Chemical Hydrogen Storage. Angewandte Chemie (International ed. in English)\| PubMed ID: 34383371	2021
Graphene Oxide-Supported Microwell Grids for Preparing Cryo-EM Samples with Controlled Ice Thickness. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 34510585	2021
Single-Phase Formation of Rh O Nanoparticles on h-BN Support for Highly Controlled Methane Partial Oxidation to Syngas. Angewandte Chemie (International ed. in English)\| PubMed ID: 34523792	2021
Wafer-Scale Production of Transition Metal Dichalcogenides and Alloy Monolayers by Nanocrystal Conversion for Large-Scale Ultrathin Flexible Electronics. Nano letters\| PubMed ID: 34677071	2021
Real-space imaging of nanoparticle transport and interaction dynamics by graphene liquid cell TEM. Science advances\| PubMed ID: 34860549	2021
Correction to "Wafer-Scale Production of Transition Metal Dichalcogenides and Alloy Monolayers by Nanocrystal Conversion for Large-Scale Ultrathin Flexible Electronics". Nano letters\| PubMed ID: 34878271	2021

Sungsu Kang

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