Conversion of Polyethylene to Low-Molecular-Weight Oil Products at Moderate Temperatures Using Nickel/Zeolite Nanocatalysts.

Polyethylene (PE) is the most widely used plastic, known for its high mechanical strength and affordability, rendering it responsible for ~70% of packaging waste and contributing to microplastic pollution. The cleavage of the carbon chain can induce the conversion of PE wastes into low-molecular-weight hydrocarbons, such as petroleum oils, waxes, and natural gases, but the thermal degradation of PE is challenging and requires high temperatures exceeding 400 °C due to its lack of specific chemical groups. Herein, we prepare metal/zeolite nanocatalysts by incorporating small-sized nickel nanoparticles into zeolite to lower the degradation temperature of PE. With the use of nanocatalysts, the degradation temperature can be lowered to 350 °C under hydrogen conditions, compared to the 400 °C required for non-catalytic pyrolysis. The metal components of the catalysts facilitate hydrogen adsorption, while the zeolite components stabilize the intermediate radicals or carbocations formed during the degradation process. The successful pyrolysis of PE at low temperatures yields valuable low-molecular-weight oil products, offering a promising pathway for the upcycling of PE into higher value-added products.

Small, solubilized platinum nanocrystals consist of an ordered core surrounded by mobile surface atoms.

In situ structures of Platinum (Pt) nanoparticles (NPs) can be determined with graphene liquid cell transmission electron microscopy. Atomic-scale three-dimensional structural information about their physiochemical properties in solution is critical for understanding their chemical function. We here analyze eight atomic-resolution maps of small (<3 nm) colloidal Pt NPs. Their structures are composed of an ordered crystalline core surrounded by surface atoms with comparatively high mobility. 3D reconstructions calculated from cumulative doses of 8500 and 17,000 electrons/pixel, respectively, are characterized in terms of loss of atomic densities and atomic displacements. Less than 5% of the total number of atoms are lost due to dissolution or knock-on damage in five of the structures analyzed, whereas 10-16% are lost in the remaining three. Less than 5% of the atomic positions are displaced due to the increased electron irradiation in all structures. The surface dynamics will play a critical role in the diverse catalytic function of Pt NPs and must be considered in efforts to model Pt NP function computationally.

Revealing Two Distinct Formation Pathways of 2D Wurtzite-CdSe Nanocrystals Using In Situ X-Ray Scattering.

Understanding the mechanism underlying the formation of quantum-sized semiconductor nanocrystals is crucial for controlling their synthesis for a wide array of applications. However, most studies of 2D CdSe nanocrystals have relied predominantly on ex situ analyses, obscuring key intermediate stages and raising fundamental questions regarding their lateral shapes. Herein, the formation pathways of two distinct quantum-sized 2D wurtzite-CdSe nanocrystals - nanoribbons and nanosheets - by employing a comprehensive approach, combining in situ small-angle X-ray scattering techniques with various ex situ characterization methods is studied. Although both nanostructures share the same thickness of ≈1.4 nm, they display contrasting lateral dimensions. The findings reveal the pivotal role of Se precursor reactivity in determining two distinct synthesis pathways. Specifically, highly reactive precursors promote the formation of the nanocluster-lamellar assemblies, leading to the synthesis of 2D nanoribbons with elongated shapes. In contrast, mild precursors produce nanosheets from a tiny seed of 2D nuclei, and the lateral growth is regulated by chloride ions, rather than relying on nanocluster-lamellar assemblies or Cd(halide)2 -alkylamine templates, resulting in 2D nanocrystals with relatively shorter lengths. These findings significantly advance the understanding of the growth mechanism governing quantum-sized 2D semiconductor nanocrystals and offer valuable guidelines for their rational synthesis.

Synthesis of Highly Monodisperse Nickel and Nickel Phosphide Nanoparticles.

Nickel and nickel phosphide nanoparticles are highly useful in various fields, owing to their catalytic and magnetic properties. Although several synthetic protocols to produce nickel and nickel phosphide nanoparticles have been previously proposed, controllable synthesis of nanoparticles using these methods is challenging. Herein, we synthesized highly monodisperse nickel and nickel phosphide nanoparticles via thermal decomposition of nickel-oleylamine-phosphine complexes in organic solvents. The size and composition of the nickel and nickel phosphide nanoparticles were easily controlled by changing the aging temperature, precursor concentration, and phosphine surfactant type. Large-sized monodisperse nickel nanoparticles obtained using our method were successfully applied for the purification of histidine-tagged proteins.

Coalescence dynamics of platinum group metal nanoparticles revealed by liquid-phase transmission electron microscopy.

Coalescence, one of the major pathways observed in the growth of nanoparticles, affects the structural diversity of the synthesized nanoparticles in terms of sizes, shapes, and grain boundaries. As coalescence events occur transiently during the growth of nanoparticles and are associated with the interaction between nanoparticles, mechanistic understanding is challenging. The ideal platform to study coalescence events may require real-time tracking of nanoparticle growth trajectories with quantitative analysis for coalescence events. Herein, we track nanoparticle growth trajectories using liquid-cell transmission electron microscopy (LTEM) to investigate the role of coalescence in nanoparticle formation and their morphologies. By evaluating multiple coalescence events for different platinum group metals, we reveal that the surface energy and ligand binding energy determines the rate of the reshaping process and the resulting final morphology of coalesced nanoparticles. The coalescence mechanism, based on direct LTEM observation explains the structures of noble metal nanoparticles that emerge in colloidal synthesis.

In Situ Liquid Phase TEM of Nanoparticle Formation and Diffusion in a Phase-Separated Medium.

Colloidal nanoparticles are synthesized in a complex reaction mixture that has an inhomogeneous chemical environment induced by local phase separation of the medium. Nanoparticle syntheses based on micelles, emulsions, flow of different fluids, injection of ionic precursors in organic solvents, and mixing the metal organic phase of precursors with an aqueous phase of reducing agents are well established. However, the formation mechanism of nanoparticles in the phase-separated medium is not well understood because of the complexity originating from the presence of phase boundaries as well as nonuniform chemical species, concentrations, and viscosity in different phases. Herein, we investigate the formation mechanism and diffusion of silver nanoparticles in a phase-separated medium by using liquid phase transmission electron microscopy and many-body dissipative particle dynamics simulations. A quantitative analysis of the individual growth trajectories reveals that a large portion of silver nanoparticles nucleate and grow rapidly at the phase boundaries, where metal ion precursors and reducing agents from the two separated phases react to form monomers. The results suggest that the motion of the silver nanoparticles at the interfaces is highly affected by the interaction with polymers and exhibits superdiffusive dynamics because of the polymer relaxation.

Structural Insights into Multi-Metal Spinel Oxide Nanoparticles for Boosting Oxygen Reduction Electrocatalysis.

Multi-metal oxide (MMO) materials have significant potential to facilitate various demanding reactions by providing additional degrees of freedom in catalyst design. However, a fundamental understanding of the (electro)catalytic activity of MMOs is limited because of the intrinsic complexity of their multi-element nature. Additional complexities arise when MMO catalysts have crystalline structures with two different metal site occupancies, such as the spinel structure, which makes it more challenging to investigate the origin of the (electro)catalytic activity of MMOs. Here, uniform-sized multi-metal spinel oxide nanoparticles composed of Mn, Co, and Fe as model MMO electrocatalysts are synthesized and the contributions of each element to the structural flexibility of the spinel oxides are systematically studied, which boosts the electrocatalytic oxygen reduction reaction (ORR) activity. Detailed crystal and electronic structure characterizations combined with electrochemical and computational studies reveal that the incorporation of Co not only increases the preferential octahedral site occupancy, but also modifies the electronic state of the ORR-active Mn site to enhance the intrinsic ORR activity. As a result, nanoparticles of the optimized catalyst, Co0.25 Mn0.75 Fe2.0 -MMO, exhibit a half-wave potential of 0.904 V (versus RHE) and mass activity of 46.9 A goxide -1 (at 0.9 V versus RHE) with promising stability.

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

Thermal motion of colloidal nanoparticles and their cohesive interactions are of fundamental importance in nanoscience but are difficult to access quantitatively, primarily due to the lack of the appropriate analytical tools to investigate the dynamics of individual particles at nanoscales. Here, we directly monitor the stochastic thermal motion and coalescence dynamics of gold nanoparticles smaller than 5 nm, using graphene liquid cell (GLC) transmission electron microscopy (TEM). We also present a novel model of nanoparticle dynamics, providing a unified, quantitative explanation of our experimental observations. The nanoparticles in a GLC exhibit non-Gaussian, diffusive motion, signifying dynamic fluctuation of the diffusion coefficient due to the dynamically heterogeneous environment surrounding nanoparticles, including organic ligands on the nanoparticle surface. Our study shows that the dynamics of nanoparticle coalescence is controlled by two elementary processes: diffusion-limited encounter complex formation and the subsequent coalescence of the encounter complex through rotational motion, where surface-passivating ligands play a critical role.

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

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 (Six Ny ). 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.

Role of the Precursor Composition in the Synthesis of Metal Ferrite Nanoparticles.

Ternary oxide nanoparticles have attracted much interest because of their intriguing properties, which are not exhibited by binary oxide nanoparticles. However, the synthesis of ternary oxide nanoparticles is not trivial and requires a fundamental understanding of the complicated precursor chemistry that governs the formation mechanism. Herein, we investigate the role of the chemical composition of precursors in the formation of ternary oxide nanoparticles via a combination of mass spectrometry, electron microscopy with elemental mapping, and thermogravimetric analysis. Mn2+, Co2+, and Ni2+ ions easily form bimetallic-oxo clusters with Fe3+ ions with a composition of MFe2O(oleate)6 (M = Mn, Co, Ni). The use of clusters as precursors leads to the successful synthesis of monodisperse metal ferrite nanoparticles (MFe2O4). On the contrary, zinc- or copper-containing complexes are formed independently from iron-oxo clusters in the precursor synthesis. The mixture of complexes without a bimetallic-oxo core yields a mixture of two different nanoparticles. This study reveals the importance of the precursor composition in the synthesis of ternary oxide nanoparticles.

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

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 (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 CN_ 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.

SINGLE: Atomic-resolution structure identification of nanocrystals by graphene liquid cell EM.

Analysis of the three-dimensional (3D) structures of nanocrystals with solution-phase transmission electron microscopy is beginning to reveal their unique physiochemical properties. We developed a "one-particle Brownian 3D reconstruction method" based on imaging of ensembles of colloidal nanocrystals using graphene liquid cell electron microscopy. Projection images of differently rotated nanocrystals are acquired using a direct electron detector with high temporal (<2.5 ms) resolution and analyzed to obtain an ensemble of 3D reconstructions. Here, we introduce computational methods required for successful atomic-resolution 3D reconstruction: (i) tracking of the individual particles throughout the time series, (ii) subtraction of the interfering background of the graphene liquid cell, (iii) identification and rejection of low-quality images, and (iv) tailored strategies for 2D/3D alignment and averaging that differ from those used in biological cryo-electron microscopy. Our developments are made available through the open-source software package SINGLE.

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

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 in situ 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.

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

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.

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.

Unraveling the mystery of ultrafine bubbles: Establishment of thermodynamic equilibrium for sub-micron bubbles and its implications.

HYPOTHESIS: We test the validity of the Young-Laplace equation and Henry's law for sub-micron bubble suspensions, which has long been a questionable issue. Application of the two theories allows characterization of bubble diameter and gas molecule partitioning between gaseous and dissolved phases using two easily measurable variables: total gas content (CT) and bubble volume concentration (BVC). EXPERIMENTS: We measure CT and BVC for sub-micron bubble suspensions generated from three pure gases, which allows calculation of bubble diameter for each suspension using the Young-Laplace equation and Henry's law. Uncertainties involved in the experimental measurements are assessed. Bubble size for each suspension is also directly measured using a dynamic light scattering (DLS) technique for comparison. FINDINGS: Applying the two theories we calculate that the bubble diameters are in the range of 304-518 nm, which correspond very well with the DLS-measured diameters. Sensitivity analyses demonstrate that the correspondence of the calculated and DLS-measured bubble diameters should take place only if the two theories are valid. The gas molecule partitioning analysis shows that >96% of gas molecules in the suspension exist as dissolved phase, which suggests the significance of the dissolved phase for applications of the bubble suspensions.

Redox-Sensitive Facet Dependency in Etching of Ceria Nanocrystals Directly Observed by Liquid Cell TEM.

Defining the redox activity of different surface facets of ceria nanocrystals is important for designing an efficient catalyst. Especially in liquid-phase reactions, where surface interactions are complicated, direct investigation in a native environment is required to understand the facet-dependent redox properties. Using liquid cell TEM, we herein observed the etching of ceria-based nanocrystals under the control of redox-governing factors. Direct nanoscale observation reveals facet-dependent etching kinetics, thus identifying the specific facet ({100} for reduction and {111} for oxidation) that governs the overall etching under different chemical conditions. Under each redox condition, the contribution of the predominant facet increases as the etching reactivity increases.

Molecular-Level Understanding of Continuous Growth from Iron-Oxo Clusters to Iron Oxide Nanoparticles.

The formation of inorganic nanoparticles has been understood based on the classical crystallization theory described by a burst of nucleation, where surface energy is known to play a critical role, and a diffusion-controlled growth process. However, this nucleation and growth model may not be universally applicable to the entire nanoparticle systems because different precursors and surface ligands are used during their synthesis. Their intrinsic chemical reactivity can lead to a formation pathway that deviates from a classical nucleation and growth model. The formation of metal oxide nanoparticles is one such case because of several distinct chemical aspects during their synthesis. Typical carboxylate surface ligands, which are often employed in the synthesis of oxide nanoparticles, tend to continuously remain on the surface of the nanoparticles throughout the growth process. They can also act as an oxygen source during the growth of metal oxide nanoparticles. Carboxylates are prone to chemical reactions with different chemical species in the synthesis such as alcohol or amine. Such reactions can frequently leave reactive hydroxyl groups on the surface. Herein, we track the entire growth process of iron oxide nanoparticles synthesized from conventional iron precursors, iron-oleate complexes, with strongly chelating carboxylate moieties. Mass spectrometry studies reveal that the iron-oleate precursor is a cluster comprising a tri-iron-oxo core and carboxylate ligands rather than a mononuclear complex. A combinatorial analysis shows that the entire growth, regulated by organic reactions of chelating ligands, is continuous without a discrete nucleation step.

Amorphous-Phase-Mediated Crystallization of Ni Nanocrystals Revealed by High-Resolution Liquid-Phase Electron Microscopy.

Nonclassical features of crystallization in solution have been recently identified both experimentally and theoretically. In particular, an amorphous-phase-mediated pathway is found in various crystallization systems as an important route, different from the classical nucleation and growth model. Here, we utilize high-resolution in situ transmission electron microscopy with graphene liquid cells to study amorphous-phase-mediated formation of Ni nanocrystals. An amorphous phase is precipitated in the initial stage of the reaction. Within the amorphous particles, crystalline domains nucleate and eventually form nanocrystals. In addition, unique crystallization behaviors, such as formation of multiple domains and dislocation relaxation, are observed in amorphous-phase-mediated crystallization. Theoretical calculations confirm that surface interactions can induce amorphous precipitation of metal precursors, which is analogous to the surface-induced amorphous-to-crystalline transformation occurring in biomineralization. Our results imply that an unexplored nonclassical growth mechanism is important for the formation of nanocrystals.