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1.
Nanoscale ; 12(36): 18606-18615, 2020 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-32970077

RESUMO

Liquid cell transmission electron microscopy (TEM) enables the direct observation of dynamic physical and chemical processes in liquids at the nanoscale. Quantitative investigations into reactions with fast kinetics and/or multiple reagents will benefit from further advances in liquid cell design that facilitate rapid in situ mixing and precise control over reagent volumes and concentrations. This work reports the development of inorganic-organic nanocapsules for high-resolution TEM imaging of nanoscale reactions in liquids with well-defined zeptoliter volumes. These hybrid nanocapsules, with 48 nm average diameter, consist of a thin layer of gold coating a lipid vesicle. As a model reaction, the nucleation, growth, and diffusion of nanobubbles generated by the radiolysis of water is investigated inside the nanocapsules. When the nanobubbles are sufficiently small (10-25 nm diameter), they are mobile in the nanocapsules, but their movement deviates from Brownian motion, which may result from geometric confinement by the nanocapsules. Gases and fluids can be transported between two nanocapsules when they fuse, demonstrating in situ mixing without using complex microfluidic schemes. The ability to synthesize nanocapsules with controlled sizes and to monitor dynamics simultaneously inside multiple nanocapsules provides opportunities to investigate nanoscale processes such as single nanoparticle synthesis in confined volumes and biological processes such as biomineralization and membrane dynamics.

2.
Nanoscale ; 12(3): 1414-1418, 2020 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-31903477

RESUMO

An understanding of nanoparticle growth is significant for controlled synthesis of nanomaterials with desired physical and chemical properties. Here we report the in situ study of platinum-nickel alloy nanoparticle growth using in situ liquid cell transmission electron microscopy (TEM). The observation revealed that Ni dendrites can form at the beginning and subsequently PtNi nanoparticles nucleate and grow by consumption of the Ni dendrites. The resulting PtNi alloy nanoparticles have a narrow size distribution with an average diameter of 3.7 nm, which are smaller than those obtained via classical solution growth. This work shed light on using such a unique growth pathway for the synthesis of novel nanoparticles.

3.
Nano Lett ; 2020 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-31991086

RESUMO

Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light-emitting applications. Recent studies have focused on nanoplatelets that are able to self-assemble and transform on solid substrates. However, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present a detailed analysis of the transformation of self-assembled stacks of CsPbBr3 nanoplatelets in solution over a period of a few months by using ex situ transmission electron microscopy and surface analysis. We demonstrate that the transformation mechanism can be understood as oriented attachment, proceeding through the following steps: (i) desorption of the ligands from the surfaces of the particles, causing the seamless atomic merging of nanoplatelet stacks into nanobelts; (ii) merging of neighboring nanobelts that form more extended nanoplates; and (iii) attachment of nanobelts and nanoplates, forming objects with an atomic structure that resembles a mosaic made of broken nanotiles. We reveal that aged nanobelts and nanoplates, which are mainly stabilized by amine/ammonium ions, link through a bilayer of CsBr, with the atomic columns of neighboring perovskite lattices shifted by a half-unit-cell, forming Ruddlesden-Popper planar faults. We also show, via in situ monitoring of the nanocrystal photoluminescence combined with transmission electron microscopy analysis, that the transformation is temperature driven and that it can take place within tens of minutes in solution and in spin-coated films. Understanding this process gives crucial information for the design and fabrication of perovskite materials, where control over the type and density of defects is desired, stimulating the development of perovskite nanocrystal structures with tailored electronic properties.

4.
Ultramicroscopy ; 209: 112890, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31743883

RESUMO

Nanoscale strain mapping by four-dimensional scanning transmission electron microscopy (4D-STEM) relies on determining the precise locations of Bragg-scattered electrons in a sequence of diffraction patterns, a task which is complicated by dynamical scattering, inelastic scattering, and shot noise. These features hinder accurate automated computational detection and position measurement of the diffracted disks, limiting the precision of measurements of local deformation. Here, we investigate the use of patterned probes to improve the precision of strain mapping. We imprint a "bullseye" pattern onto the probe, by using a binary mask in the probe-forming aperture, to improve the robustness of the peak finding algorithm to intensity modulations inside the diffracted disks. We show that this imprinting leads to substantially improved strain-mapping precision at the expense of a slight decrease in spatial resolution. In experiments on an unstrained silicon reference sample, we observe an improvement in strain measurement precision from 2.7% of the reciprocal lattice vectors with standard probes to 0.3% using bullseye probes for a thin sample, and an improvement from 4.7% to 0.8% for a thick sample. We also use multislice simulations to explore how sample thickness and electron dose limit the attainable accuracy and precision for 4D-STEM strain measurements.

5.
Nature ; 577(7788): 64-68, 2020 01.
Artigo em Inglês | MEDLINE | ID: mdl-31739311

RESUMO

The size-dependent and shape-dependent characteristics that distinguish nanoscale materials from bulk solids arise from constraining the dimensionality of an inorganic structure1-3. As a consequence, many studies have focused on rationally shaping these materials to influence and enhance their optical, electronic, magnetic and catalytic properties4-6. Although a select number of stable clusters can typically be synthesized within the nanoscale regime for a specific composition, isolating clusters of a predetermined size and shape remains a challenge, especially for those derived from two-dimensional materials. Here we realize a multidentate coordination environment in a metal-organic framework to stabilize discrete inorganic clusters within a porous crystalline support. We show confined growth of atomically defined nickel(II) bromide, nickel(II) chloride, cobalt(II) chloride and iron(II) chloride sheets through the peripheral coordination of six chelating bipyridine linkers. Notably, confinement within the framework defines the structure and composition of these sheets and facilitates their precise characterization by crystallography. Each metal(II) halide sheet represents a fragment excised from a single layer of the bulk solid structure, and structures obtained at different precursor loadings enable observation of successive stages of sheet assembly. Finally, the isolated sheets exhibit magnetic behaviours distinct from those of the bulk metal halides, including the isolation of ferromagnetically coupled large-spin ground states through the elimination of long-range, interlayer magnetic ordering. Overall, these results demonstrate that the pore environment of a metal-organic framework can be designed to afford precise control over the size, structure and spatial arrangement of inorganic clusters.

6.
Sci Adv ; 5(12): eaax2799, 2019 12.
Artigo em Inglês | MEDLINE | ID: mdl-31853495

RESUMO

Chemical short-range order (SRO) within a nominally single-phase solid solution is known to affect the mechanical properties of alloys. While SRO has been indirectly related to deformation, direct observation of the SRO domain structure, and its effects on deformation mechanisms at the nanoscale, has remained elusive. Here, we report the direct observation of SRO in relation to deformation using energy-filtered imaging in a transmission electron microscope (TEM). The diffraction contrast is enhanced by reducing the inelastically scattered electrons, revealing subnanometer SRO-enhanced domains. The destruction of these domains by dislocation planar slip is observed after ex situ and in situ TEM mechanical testing. These results confirm the impact of SRO in Ti-Al alloys on the scale of angstroms. The direct confirmation of SRO in relationship to dislocation plasticity in metals can provide insight into how the mechanical behavior of concentrated solid solutions by the material's thermal history.

7.
Adv Mater ; : e1906105, 2019 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-31746516

RESUMO

The operating conditions of functional materials usually involve varying stress fields, resulting in structural changes, whether intentional or undesirable. Complex multiscale microstructures including defects, domains, and new phases, can be induced by mechanical loading in functional materials, providing fundamental insight into the deformation process of the involved materials. On the other hand, these microstructures, if induced in a controllable fashion, can be used to tune the functional properties or to enhance certain performance. In situ nanomechanical tests conducted in scanning/transmission electron microscopes (STEM/TEM) provide a critical tool for understanding the microstructural evolution in functional materials. Here, select results on a variety of functional material systems in the field are presented, with a brief introduction into some newly developed multichannel experimental capabilities to demonstrate the impact of these techniques.

8.
J Chem Phys ; 151(15): 154703, 2019 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-31640349

RESUMO

Pd- and Pt-based catalysts are highly studied materials due to their widespread use in emissions control catalysis. However, claims continue to vary regarding the active phase and oxidation state of the metals. Different conclusions have likely been reached due to the heterogeneous nature of such materials containing various metal nanoparticle sizes and compositions, which may each possess unique redox features. In this work, using uniform nanocrystal catalysts, we study the effect of particle size and alloying on redox properties of Pd-based catalysts and show their contribution to methane combustion activity using operando quick extended x-ray absorption fine structure measurements. Results demonstrate that for all studied Pd sizes (3 nm-16 nm), Pd oxidation directly precedes CH4 combustion to CO2, suggesting Pd oxidation as a prerequisite step to methane combustion, and an oxidation pretreatment shows equal or better catalysis than a reduction pretreatment. Results are then extended to uniform alloyed PtxPd1-x nanoparticles, where oxidative pretreatments are shown to enhance low-temperature combustion. In these uniform alloys, we observe a composition-dependent effect with Pt-rich alloys showing the maximum difference between oxidative and reductive pretreatments. In Pt-rich alloys, we initially observe that the presence of Pt maintains Pd in a lower-activity reduced state. However, with time on stream, PdO eventually segregates under oxidizing combustion conditions, leading to a slowly increasing activity. Overall, across particle sizes and alloy compositions, we relate increased catalytic activity to Pd oxidation, thus shedding light on previous contrasting results related to the methane combustion activity of these catalysts.

9.
Nat Mater ; 18(9): 970-976, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31285617

RESUMO

Two-dimensional (2D) materials have attracted significant interest because of their large surface-to-volume ratios and electron confinement. Compared to common 2D materials such as graphene or metal hydroxides, with their intrinsic layered atomic structures, the formation mechanisms of 2D metal oxides with a rocksalt structure are not well understood. Here, we report the formation process for 2D cobalt oxide and cobalt nickel oxide nanosheets, after analysis by in situ liquid-phase transmission electron microscopy. Our observations reveal that three-dimensional (3D) nanoparticles are initially formed from the molecular precursor solution and then transform into 2D nanosheets. Ab initio calculations show that a small nanocrystal is dominated by positive edge energy, but when it grows to a certain size, the negative surface energy becomes dominant, driving the transformation of the 3D nanocrystal into a 2D structure. Uncovering these growth pathways, including the 3D-to-2D transition, provides opportunities for future material design and synthesis in solution.

10.
Nat Mater ; 18(8): 860-865, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31160799

RESUMO

The properties of organic solids depend on their structure and morphology, yet direct imaging using conventional electron microscopy methods is hampered by the complex internal structure of these materials and their sensitivity to electron beams. Here, we manage to observe the nanocrystalline structure of two organic molecular thin-film systems using transmission electron microscopy by employing a scanning nanodiffraction method that allows for full access to reciprocal space over the size of a spatially localized probe (~2 nm). The morphologies revealed by this technique vary from grains with pronounced segmentation of the structure-characterized by sharp grain boundaries and overlapping domains-to liquid-crystal structures with crystalline orientations varying smoothly over all possible rotations that contain disclinations representing singularities in the director field. The results show how structure-property relationships can be visualized in organic systems using techniques previously only available for hard materials such as metals and ceramics.

11.
Nano Lett ; 19(3): 1788-1795, 2019 03 13.
Artigo em Inglês | MEDLINE | ID: mdl-30741548

RESUMO

Two dimensional (2D) materials have found various applications because of their unique physical properties. For example, graphene has been used as the electron transparent membrane for liquid cell transmission electron microscopy (TEM) due to its high mechanical strength and flexibility, single-atom thickness, chemical inertness, etc. Here, we report using 2D MoS2 as a functional substrate as well as the membrane window for liquid cell TEM, which is enabled by our facile and polymer-free MoS2 transfer process. This provides the opportunity to investigate the growth of Pt nanocrystals on MoS2 substrates, which elucidates the formation mechanisms of such heterostructured 2D materials. We find that Pt nanocrystals formed in MoS2 liquid cells have a strong tendency to align their crystal lattice with that of MoS2, suggesting a van der Waals epitaxial relationship. Importantly, we can study its impact on the kinetics of the nanocrystal formation. The development of MoS2 liquid cells will allow further study of various liquid phenomena on MoS2, and the polymer-free MoS2 transfer process will be implemented in a wide range of applications.

12.
Commun Biol ; 2: 26, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30675524

RESUMO

Changes in lattice structure across sub-regions of protein crystals are challenging to assess when relying on whole crystal measurements. Because of this difficulty, macromolecular structure determination from protein micro and nanocrystals requires assumptions of bulk crystallinity and domain block substructure. Here we map lattice structure across micron size areas of cryogenically preserved three-dimensional peptide crystals using a nano-focused electron beam. This approach produces diffraction from as few as 1500 molecules in a crystal, is sensitive to crystal thickness and three-dimensional lattice orientation. Real-space maps reconstructed from unsupervised classification of diffraction patterns across a crystal reveal regions of crystal order/disorder and three-dimensional lattice tilts on the sub-100nm scale. The nanoscale lattice reorientation observed in the micron-sized peptide crystal lattices studied here provides a direct view of their plasticity. Knowledge of these features facilitates an improved understanding of peptide assemblies that could aid in the determination of structures from nano- and microcrystals by single or serial crystal electron diffraction.


Assuntos
Nanopartículas/química , Nanopartículas/ultraestrutura , Peptídeos/química , Modelos Teóricos
13.
Nano Lett ; 19(1): 591-597, 2019 01 09.
Artigo em Inglês | MEDLINE | ID: mdl-30582699

RESUMO

An understanding of nanocrystal shape evolution is significant for the design, synthesis, and applications of nanocrystals with surface-enhanced properties such as catalysis or plasmonics. Surface adsorbates that are selectively attached to certain facets may strongly affect the atomic pathways of nanocrystal shape development. However, it is a great challenge to directly observe such dynamic processes in situ with a high spatial resolution. Here, we report the anomalous shape evolution of Ag2O2 nanocrystals modulated by the surface adsorbates of Ag clusters during electron beam etching, which is revealed through in situ transmission electron microscopy (TEM). In contrast to the Ag2O2 nanocrystals without adsorbates, which display the near-equilibrium shape throughout the etching process, Ag2O2 nanocrystals with Ag surface adsorbates show distinct facet development during etching by electron beam irradiation. Three stages of shape changes are observed: a sphere-to-a cube transformation, side etching of a cuboid, and bottom etching underneath the surface adsorbates. We find that the Ag adsorbates modify the Ag2O2 nanocrystal surface configuration by selectively capping the junction between two neighboring facets. They prevent the edge atoms from being etched away and block the diffusion path of surface atoms. Our findings provide critical insights into the modulatory function of surface adsorbates on the shape control of nanocrystals.

14.
Chem Commun (Camb) ; 54(97): 13726-13729, 2018 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-30456398

RESUMO

Selective nitrogen-doping of graphene oxide with a high pyridinic N ratio (51%; L-GO) was achieved by laser irradiation of graphene oxide with ammonia. The resulting L-GO exhibited enhanced electrocatalytic properties; specifically, the overpotential of the hydrogen evolution reaction (HER) was improved by over 400 mV at 10 mA cm-2 compared to the pristine graphene oxide.

15.
Angew Chem Int Ed Engl ; 57(40): 13172-13176, 2018 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-30136423

RESUMO

We demonstrate the guiding principles behind simple two dimensional self-assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe3 O4 ) NCs into a uniform two-dimensional bi-layered superstructure. This self-assembly process can be controlled by the energy of ligand-ligand interactions between surface ligands on Fe3 O4 NCs and Zr6 O4 (OH)4 (fumarate)6 MOF NPs. Scanning transmission electron microscopy (TEM)/energy-dispersive X-ray spectroscopy and TEM tomography confirm the hierarchical co-assembly of Fe3 O4 NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First-principles calculations and event-driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand-surface and ligand-ligand interactions. This study opens a new avenue for design and self-assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self-assembly process, which could be a guide for designing functional materials with desired structure.

16.
Nano Lett ; 18(9): 5530-5537, 2018 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-30080050

RESUMO

Solution processing of polycrystalline compound semiconductor thin film using nanocrystals as a precursor is considered one of the most promising and economically viable routes for future large-area manufacturing. However, in polycrystalline compound semiconductor films such as Cu2ZnSnS4 (CZTS), grain size, and the respective grain boundaries play a key role in dictating the optoelectronic properties. Various strategies have been employed previously in tailoring the grain size and boundaries (such as ligand exchange) but most require postdeposition thermal annealing at high temperature in the presence of grain growth directing agents (selenium or sulfur vapor with/without Na, K, etc.) to enlarge the grains through sintering. Here, we show a different strategy of controlling grain size by tuning the kinetics of nucleation and the subsequent grain growth in CZTS nanocrystal thin films during a crystalline phase transition. We demonstrate that the activation energy for the phase transition can be varied by utilizing different shapes (spherical and nanorod) of nanocrystals with similar size, composition, and surface chemistry leading to different densities of nucleation sites and, thereby, different grain sizes in the films. Additionally, exchanging the native organic ligands for inorganic surface ligands changes the activation energy for the phase change and substantially changes the grain growth dynamics, while also compositionally modifying the resulting film. This combined approach of using nucleation and growth dynamics and surface chemistry enables us to tune the grain size of polycrystalline CZTS films and customize their electronic properties by compositional engineering.

17.
Sci Rep ; 8(1): 10239, 2018 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-29980704

RESUMO

We report quantitative characterization of the high temperature oxidation process by using electron tomography and energy-dispersive X-ray spectroscopy. As a proof of principle, we performed 3D imaging of the oxidation layer of a model system (Mo3Si) at nanoscale resolution with elemental specificity and probed the oxidation kinetics as a function of the oxidation time and the elevated temperature. Our tomographic reconstructions provide detailed 3D structural information of the surface oxidation layer of the Mo3Si system, revealing the evolution of oxidation behavior of Mo3Si from early stage to mature stage. Based on the relative rate of oxidation of Mo3Si, the volatilization rate of MoO3 and reactive molecular dynamics simulations, we propose a model to explain the mechanism of the formation of the porous silica structure during the oxidation process of Mo3Si. We expect that this 3D quantitative characterization method can be applied to other material systems to probe their structure-property relationships in different environments.

18.
ACS Nano ; 12(8): 7554-7561, 2018 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-30011187

RESUMO

With a honeycomb single-atomic-layer structure similar to those of graphene and hexagonal boron nitride (hBN), the graphitic phase of ZnO (gZnO) have been predicted to offer many advantages for engineering, including high-temperature stability in ambient conditions and great potential in heterostructure applications. However, there is little experimental data about this hexagonal phase due to the difficulty of synthesizing large-area gZnO for characterization and applications. In this work, we demonstrate a solution-based approach to realize gZnO nanoflakes with thicknesses down to a monolayer and sizes up to 20 µm. X-ray photoelectron spectroscopy, X-ray absorption near-edge spectroscopy, photoluminescence, atomic force microscopy, and electron microscopy characterizations are conducted on synthesized gZnO samples. Measurements show significant changes to the electronic band structure compared to its bulk phase, including an increase of the band gap to 4.8 eV. The gZnO nanosheets also exhibit excellent stability at temperatures as high as 800 °C in ambient environment. This wide band gap layered material provides us with a platform for harsh environment electronic devices, deep ultraviolet optical applications, and a practical alternative for hBN. Our synthesis method may also be applied to achieve other types of 2D oxides.

19.
J Am Chem Soc ; 140(27): 8569-8577, 2018 07 11.
Artigo em Inglês | MEDLINE | ID: mdl-29909616

RESUMO

The ability to predict and control the formation of bimetallic heterogeneous nanocrystals is desirable for many applications in plasmonics and catalysis. Here, we report the synthesis and characterization of stable, monodisperse, and solution-processed Cu-Ag bimetallic nanoparticles with specific but unusual elemental arrangements that are consistent with a recently developed thermodynamic model. Using air-free scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy, the distribution of Cu and Ag positions was unambiguously identified within individual nanocrystals (NCs), leading to the discovery of a Cu-Ag nanocrescent shape. A simple yet versatile thermodynamic model was applied to illustrate how the interplay between surface and interface energies determines the particle morphology. It is found that there exists a range of surface-to-interface energy ratios under which crescent-shaped nanocrystals are the thermodynamically favored products, with the morphology tunable by adjusting the Ag content. We further show the conversion of Cu-Ag nanocrescents into Ag@Cu2O upon mild oxidation, whereas fully core-shell Cu@Ag NCs are robust against oxidation up to 100 °C. The plasmonic and interband absorptions of Cu-Ag NCs depend on the composition and the degree of Cu oxidation, which may find application in light-driven catalysis.

20.
Nanoscale ; 10(24): 11281-11286, 2018 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-29881854

RESUMO

Controlling the growth, morphology and structure of nanocrystals is fundamental to achieving facet dependent physical and chemical properties. Core-shell PtNi-Ni nanoparticles' evolution was investigated using in situ liquid cell transmission electron microscopy (TEM). A two-stage growth of core-shell PtNi-Ni nanoparticles was observed. The platinum (Pt)-based binary alloy was formed initially by a thermodynamically driven process, then grown by a monomer attachment process, and then the core formed and the process was stopped by depletion of the Pt precursor, and finally the nickel (Ni) shell formed. This growth process gives a way to grow a metallic shell for novel catalysts.

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