We introduce a new type of liquid cell for in situ transmission electron microscopy (TEM) based on entrapment of a liquid film between layers of graphene. The graphene liquid cell facilitates atomic-level resolution imaging while sustaining the most realistic liquid conditions achievable under electron-beam radiation. We employ this cell to explore the mechanism of colloidal platinum nanocrystal growth. Direct atomic-resolution imaging allows us to visualize critical steps in the process, including site-selective coalescence, structural reshaping after coalescence, and surface faceting.
Transmission electron microscopy is a powerful imaging tool that has found broad application in materials science, nanoscience and biology. With the introduction of aberration-corrected electron lenses, both the spatial resolution and the image quality in transmission electron microscopy have been significantly improved and resolution below 0.5 ångströms has been demonstrated. To reveal the three-dimensional (3D) structure of thin samples, electron tomography is the method of choice, with cubic-nanometre resolution currently achievable. Discrete tomography has recently been used to generate a 3D atomic reconstruction of a silver nanoparticle two to three nanometres in diameter, but this statistical method assumes prior knowledge of the particle's lattice structure and requires that the atoms fit rigidly on that lattice. Here we report the experimental demonstration of a general electron tomography method that achieves atomic-scale resolution without initial assumptions about the sample structure. By combining a novel projection alignment and tomographic reconstruction method with scanning transmission electron microscopy, we have determined the 3D structure of an approximately ten-nanometre gold nanoparticle at 2.4-ångström resolution. Although we cannot definitively locate all of the atoms inside the nanoparticle, individual atoms are observed in some regions of the particle and several grains are identified in three dimensions. The 3D surface morphology and internal lattice structure revealed are consistent with a distorted icosahedral multiply twinned particle. We anticipate that this general method can be applied not only to determine the 3D structure of nanomaterials at atomic-scale resolution, but also to improve the spatial resolution and image quality in other tomography fields.
A promising electrocatalyst prototype of low Pt mole fraction, intermetallic nanoparticles of Cu(3)Pt, has been prepared using a simple impregnation-reduction method, followed by a post heat-treatment. Two dealloying methods (electrochemical and chemical) were implemented to control the atomic-level morphology and improve performance for the oxygen reduction reaction (ORR). The morphology and elemental composition of the dealloyed nanoparticles were characterized at angstrom resolution using an aberration-corrected scanning transmission electron microscope equipped with an electron energy loss spectrometer. We found that the electrochemical dealloying method led to the formation of a thin Pt skin of ca. 1 nm in thickness with an ordered Cu(3)Pt core structure, while chemical leaching gave rise to a "spongy" structure with no ordered structure being preserved. A three-dimensional tomographic reconstruction indicated that numerous voids were formed in the chemically dealloyed nanoparticles. Both dealloying methods yielded enhanced specific and mass activities toward the ORR and higher stability relative to Pt/C. The spongy nanoparticles exhibited better mass activity with a slightly lower specific activity than the electrochemically dealloyed nanoparticles after 50 potential cycles. In both cases, the mass activity was still enhanced after 5000 potential cycles.
Multicomponent nanocrystal superlattices represent an interesting class of material that derives emergent properties from mesoscale structure, yet their programmability can be limited by the alkyl-chain-based ligands decorating the surfaces of the constituent nanocrystals. Polymeric ligands offer distinct advantages, as they allow for more precise tuning of the effective size and ‘interaction softness' through changes to the polymer's molecular weight, chemical nature, architecture, persistence length and surrounding solvent. Here we show the formation of 10 different binary nanocrystal superlattices (BNSLs) with both two- and three-dimensional order through independent adjustment of the core size of spherical nanocrystals and the molecular weight of densely grafted polystyrene ligands. These polymer-brush-based ligands introduce new energetic contributions to the interparticle potential that stabilizes various BNSL phases across a range of length scales and interparticle spacings. Our study opens the door for nanocrystals to become modular elements in the design of functional particle brush solids with controlled nanoscale interfaces and mesostructures.
Nucleation plays a critical role in many physical and biological phenomena ranging from crystallization, melting and evaporation to the formation of clouds and the initiation of neurodegenerative diseases 1-3. However, nucleation is a challenging process to study in experiments especially in the early stage when several atoms/molecules start to form a new phase from its parent phase. Over the years, a number of experimental and computational methods have been used to investigate nucleation processes 4-17 , but it remains unachievable to experimentally determine the 3D atomic structure and dynamics of early stage nuclei. Here, we develop 4D atomic electron tomography (AET) to study early stage nucleation at atomic resolution. Using FePt nanoparticles as a model system, we reveal that early stage nuclei are irregularly shaped, each has a core of one to a few atoms 2 with the maximum order parameter, and the order parameter gradient points from the core to the boundary of the nucleus. We capture the structure and dynamics of the same nuclei undergoing growth, fluctuation, dissolution, merging and/or division, which are regulated by the order parameter distribution and its gradient. These experimental observations are corroborated by molecular dynamics simulations of heterogeneous and homogeneous nucleation in liquid-solid phase transitions of Pt. Our experimental and molecular dynamics results differ from classical nucleation theory (CNT) 1,2,18 , indicating a theory beyond CNT is needed to describe early stage nucleation at the atomic scale. Looking forward, we anticipate that 4D AET opens the door to study many fundamental problems in materials science, nanoscience, condensed matter physics and chemistry such as phase transition, atomic diffusion, grain boundary dynamics, interface motion, defect dynamics and surface reconstruction with 4D atomic resolution. AET is a powerful method to determine the 3D atomic structure of materials without the assumption of crystallinity 19 and has been applied to study dislocations, stacking faults, grain boundaries, atomic displacement, strain tensor, chemical order/disorder and point defects with unprecedented 3D detail 20-26. But all of these studies were of static structures. To probe the 4D atomic structure of early stage nucleation, we have tracked the same nuclei at different times and applied AET to determine their 3D atomic coordinates and species at each time (Methods). We used FePt nanoparticles as a model system because binary alloys have been widely used to study phase transitions 2 and FePt is a very promising material for next generation magnetic recording media 25,27. As-synthesized FePt nanoparticles form a chemically disordered face-centred cubic (fcc) structure (A1 phase) 27. With annealing, the A1 phase Author contributions J.M. conceived and directed the project; F.S. and H.Z. prepared the samples; J.Z.,
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.
The crystal phase-based heterostructures of noble metal nanomaterials are of great research interest for various applications, such as plasmonics and catalysis. However, the synthesis of unusual crystal phases of noble metals still remains a great challenge, making the construction of heterophase noble metal nanostructures difficult. Here, we report a one-pot wetchemical synthesis of well-defined heterophase fcc-2H-fcc gold nanorods (fcc: face-centred cubic; 2H: hexagonal close-packed with stacking sequence of "AB") at mild conditions. Single particle-level experiments and theoretical investigations reveal that the heterophase gold nanorods demonstrate a distinct optical property compared to that of the conventional fcc gold nanorods. Moreover, the heterophase gold nanorods possess superior electrocatalytic activity for the carbon dioxide reduction reaction over their fcc counterparts under ambient conditions. First-principles calculations suggest that the boosted catalytic performance stems from the energetically favourable adsorption of reaction intermediates, endowed by the unique heterophase characteristic of gold nanorods.
Developing routes to control the organization of one-dimensional nanomaterials, such as nanorods, with high precision is critical to generate functional materials since the collective properties depend on their spatial arrangements, interparticle ordering, and macroscopic alignment. We have systematically investigated the coassemblies of nanorods and block copolymer (BCP)-based supramolecules and showed that the energetic contributions from nanorod ligand-polymer interactions, polymer chain deformation, and rod-rod interactions are comparable and can be tailored to disperse nanorods with control over inter-rod ordering and the alignment of nanorods within BCP microdomains. By varying the supramolecular morphology and chemical nature of the nanorods, two highly sought-after morphologies, that is, nanoscopic networks of nanorods and nanorod arrays parallel to cylindrical BCP microdomains can be obtained. The supramolecular approach can be applied to achieve morphological control in nanorod-containing nanocomposites toward fabrication of optical and electronic nanodevices.
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