Unexpectedly high thermal stability of Au nanotriangle@mSiO2 yolk-shell nanoparticles.

The shape of Au nanoparticles (NPs) plays a crucial role for applications in, amongst others, catalysis, electronic devices, biomedicine, and sensing. Typically, the deformation of the morphology of Au NPs is the most significant cause of loss of functionality. Here, we systematically investigate the thermal stability of Au nanotriangles (NTs) coated with (mesoporous) silica shells with different morphologies (core-shell (CS): Au NT@mSiO2/yolk-shell (YS): Au NT@mSiO2) and compare these to 'bare' nanoparticles (Au NTs), by a combination of in situ and/or ex situ TEM techniques and spectroscopy methods. Au NTs with a mesoporous silica (mSiO2) coating were found to show much higher thermal stability than those without a mSiO2 coating, as the mSiO2 shell restricts the (self-)diffusion of surface atoms. For the Au NT@mSiO2 CS and YS NPs, a thicker mSiO2 shell provides better protection than uncoated Au NTs. Surprisingly, the Au NT@mSiO2 YS NPs were found to be as stable as Au NT@mSiO2 CS NPs with a core-shell morphology. We hypothesize that the only explanation for this unexpected finding was the thicker and higher density SiO2 shell of YS NPs that prevents diffusion of Au surface atoms to more thermodynamically favorable positions.

Reversible MnO to Mn3 O4 Oxidation in Manganese Oxide Nanoparticles.

Manganese is an attractive element for sustainable solutions. It is largely available in the earth's crust, making it ideal for cost-effective and large-scale applications. Especially MnO nanoparticles have recently received attention for applications in battery technology. However, manganese has many oxidation states that are energetically very similar, indicating that they may easily transform from one to the other. Herein, the reversible oxidation of MnO nanoparticles to Mn3 O4 studied with in situ transmission electron microscopy is shown. The oxygen sublattices of MnO and Mn3 O4 are found to be perfectly aligned, and an atomic mechanism where the transformation is facilitated by the migration of Mn cations on the shared O sublattice is proposed. Even when protected with an amorphous carbon layer, MnO particles are highly unstable and oxidize to Mn3 O4 in ethanol. The poor stability of MnO lacks discussion in many battery-related works, and strategies aimed at avoiding this should be developed.

Thermal Reduction of MoO3 Particles and Formation of MoO2 Nanosheets Monitored by In Situ Transmission Electron Microscopy.

Nanoscale forms of molybdenum trioxide have found widespread use in optoelectronic, sensing, and battery applications. Here, we investigate the thermal evolution of micrometer-sized molybdenum trioxide particles during in situ heating in vacuum using transmission electron microscopy and observed drastic structural and chemical changes that are strongly dependent on the heating rate. Rapid heating (flash heating) of MoO3 particles to a temperature of 600 °C resulted in large-scale formation of MoO2(001) nanosheets that were formed in a wide area around the reducing MoO3 particles, within a few minutes of time frame. In contrast, when heated more gently, the initially single-crystal MoO3 particles were reduced into hollow nanostructures with polycrystalline MoO2 shells. Using density functional theory calculations employing the DFT-D3 functional, the surface energy of MoO3(010) was calculated to be 0.187 J m-2, and the activation energy for exfoliation of the van der Waals bonded MoO3 (010) layers was calculated to be 0.478 J m-2. Ab initio molecular dynamics simulations show strong fluctuations in the distance between the (010) layers, where thermal vibrations lead to additional separations of up to 1.8 Å at 600 °C. This study shows efficient pathways for the generation of either MoO2 nanosheets or hollow MoO2 nanostructures with very high effective surface areas beneficial for applications.

Morphology-Controlled Growth of Crystalline Ag-Pt-Alloyed Shells onto Au Nanotriangles and Their Plasmonic Properties.

The surface plasmon resonance of noble-metal nanoparticles depends on nanoscale size, morphology, and composition, and provides great opportunities for applications in biomedicine, optoelectronics, (photo)catalysis, photovoltaics, and sensing. Here, we present the results of synthesizing ternary metallic or trimetallic nanoparticles, Au nanotriangles (Au NTs) with crystalline Ag-Pt alloyed shells, the morphology of which can be adjusted from a yolk-shell to a core-shell structure by changing the concentration of AgNO3 or the concentration of Au NT seeds, while the shell thickness can be precisely controlled by adjusting the concentration of K2PtCl4. By monitoring the growth process with UV-vis spectra and scanning transmission electron microscopy (STEM), the shells on the Au NT-Ag-Pt yolk-shell nanoparticles were found to grow via a galvanic replacement synergistic route. The plasmonic properties of the as-synthesized nanoparticles were investigated by optical absorbance measurements.

Thermolysis-Driven Growth of Vanadium Oxide Nanostructures Revealed by In Situ Transmission Electron Microscopy: Implications for Battery Applications.

Understanding the growth modes of 2D transition-metal oxides through direct observation is of vital importance to tailor these materials to desired structures. Here, we demonstrate thermolysis-driven growth of 2D V2O5 nanostructures via in situ transmission electron microscopy (TEM). Various growth stages in the formation of 2D V2O5 nanostructures through thermal decomposition of a single solid-state NH4VO3 precursor are unveiled during the in situ TEM heating. Growth of orthorhombic V2O5 2D nanosheets and 1D nanobelts is observed in real time. The associated temperature ranges in thermolysis-driven growth of V2O5 nanostructures are optimized through in situ and ex situ heating. Also, the phase transformation of V2O5 to VO2 was revealed in real time by in situ TEM heating. The in situ thermolysis results were reproduced using ex situ heating, which offers opportunities for upscaling the growth of vanadium oxide-based materials. Our findings offer effective, general, and simple pathways to produce versatile 2D V2O5 nanostructures for a range of battery applications.

Thermal Stability and Sublimation of Two-Dimensional Co9Se8 Nanosheets for Ultrathin and Flexible Nanoelectronic Devices.

An understanding of the structural and compositional stability of nanomaterials is significant from both fundamental and technological points of view. Here, we investigate the thermal stability of half-unit-cell thick two-dimensional (2D) Co9Se8 nanosheets that are exceptionally interesting because of their half-metallic ferromagnetic properties. By employing in situ heating in the transmission electron microscope (TEM), we find that the nanosheets show good structural and chemical stability without changes to the cubic crystal structure until sublimation of the nanosheets starts at temperatures between 460 and 520 °C. The real-time observations of the sublimation process show preferential removal at {110} type crystal facets. From an analysis of sublimation rates at various temperatures, we find that the sublimation occurs through noncontinuous and punctuated mass loss at lower temperatures while the sublimation is continuous and uniform at higher temperatures. Our findings provide an understanding of the nanoscale structural and compositional stability of 2D Co9Se8 nanosheets, which is of importance for their reliable application and sustained performance as ultrathin and flexible nanoelectronic devices.

Formation Pathways of Lath-Shaped WO3 Nanosheets and Elemental W Nanoparticles from Heating of WO3 Nanocrystals Studied via In Situ TEM.

WO3 is a versatile material occurring in many polymorphs, and is used in nanostructured form in many applications, including photocatalysis, gas sensing, and energy storage. We investigated the thermal evolution of cubic-phase nanocrystals with a size range of 5-25 nm by means of in situ heating in the transmission electron microscope (TEM), and found distinct pathways for the formation of either 2D WO3 nanosheets or elemental W nanoparticles, depending on the initial concentration of deposited WO3 nanoparticles. These pristine particles were stable up to 600 °C, after which coalescence and fusion of the nanocrystals were observed. Typically, the nanocrystals transformed into faceted nanocrystals of elemental body-centered-cubic W after annealing to 900 °C. However, in areas where the concentration of dropcast WO3 nanoparticles was high, at a temperature of 900 °C, considerably larger lath-shaped nanosheets (extending for hundreds of nanometers in length and up to 100 nm in width) were formed that are concluded to be in monoclinic WO3 or WO2.7 phases. These lath-shaped 2D particles, which often curled up from their sides into folded 2D nanosheets, are most likely formed from the smaller nanoparticles through a solid-vapor-solid growth mechanism. The findings of the in situ experiments were confirmed by ex situ experiments performed in a high-vacuum chamber.

In situ single particle characterization of the themoresponsive and co-nonsolvent behavior of PNIPAM microgels and silica@PNIPAM core-shell colloids.

Poly(N-isopropylacrylamide) (PNIPAM) microgels and PNIPAM colloidal shells attract continuous strong interest due to their thermoresponsive behavior, as their size and properties can be tuned by temperature. The direct single particle observation and characterization of pure, unlabeled PNIPAM microgels in their native aqueous environment relies on imaging techniques that operate either at interfaces or in cryogenic conditions, thus limiting the observation of their dynamic nature. Liquid Cell (Scanning) Transmission Electron Microscopy (LC-(S) TEM) imaging allows the characterization of materials and dynamic processes such as nanoparticle growth, etching, and diffusion, at nanometric resolution in liquids. Here we show that via a facile post-synthetic in situ polymer labelling step with high-contrast marker core-shell Au@SiO2 nanoparticles (NPs) it is possible to determine the full volume of PNIPAM microgels in water. The labelling allowed for the successful characterization of the thermoresponsive behavior of PNIPAM microgels and core shell silica@PNIPAM hybrid microgels, as well as the co-nonsolvency of PNIPAM in aqueous alcoholic solutions. The interplay between electron beam irradiation and PNIPAM systems in water resulted in irreversible shrinkage due to beam induced water radiolysis products, which in turn also affected the thermoresponsive behavior of PNIPAM. The addition of 2-propanol as radical scavenger improved PNIPAM stability in water under electron beam irradiation.

Solution-Mediated Inversion of SnSe to Sb2Se3 Thin-Films.

New facile and controllable approaches to fabricating metal chalcogenide thin films with adjustable properties can significantly expand the scope of these materials in numerous optoelectronic and photovoltaic devices. Most traditional and especially wet-chemical synthetic pathways suffer from a sluggish ability to regulate the composition and have difficulty achieving the high-quality structural properties of the sought-after metal chalcogenides, especially at large 2D length scales. In this effort, and for the first time, we illustrated the fast and complete inversion of continuous SnSe thin-films to Sb2Se3 using a scalable top-down ion-exchange approach. Processing in dense solution systems yielded the formation of Sb2Se3 films with favorable structural characteristics, while oxide phases, which are typically present in most Sb2Se3 films regardless of the synthetic protocols used, were eliminated. Density functional theory (DFT) calculations performed on intermediate phases show strong relaxations of the atomic lattice due to the presence of substitutional and vacancy defects, which likely enhances the mobility of cationic species during cation exchange. Our concept can be applied to customize the properties of other metal chalcogenides or manufacture layered structures.

Frequency-controlled electrophoretic mobility of a particle within a porous, hollow shell.

The unique properties of yolk-shell or rattle-type particles make them promising candidates for applications ranging from switchable photonic crystals, to catalysts, to sensors. To realize many of these applications it is important to gain control over the dynamics of the core particle independently of the shell. HYPOTHESIS: The core particle may be manipulated by an AC electric field with rich frequency-dependent behavior. EXPERIMENTS: Here, we explore the frequency-dependent dynamic electrophoretic mobility of a charged core particle within a charged, porous shell in AC electric fields both experimentally using liquid-phase electron microscopy and numerically via the finite-element method. These calculations solve the Poisson-Nernst-Planck-Stokes equations, where the core particle moves according to the hydrodynamic and electric forces acting on it. FINDINGS: In experiments the core exhibited three frequency-dependent regimes of field-driven motion: (i) parallel to the field, (ii) diffusive in a plane orthogonal to the field, and (iii) unbiased random motion. The transitions between the three observed regimes can be explained by the level of matching between the time required to establish ionic gradients in the shell and the period of the AC field. We further investigated the effect of shell porosity, ionic strength, and inner-shell radius. The former strongly impacted the core's behavior by attenuating the field inside the shell. Our results provide physical understanding on how the behavior of yolk-shell particles may be tuned, thereby enhancing their potential for use as building blocks for switchable photonic crystals.

Heating-Induced Transformation of Anatase TiO2 Nanorods into Rock-Salt TiO Nanoparticles: Implications for Photocatalytic and Gas-Sensing Applications.

Anatase TiO2 nanocrystals (NCs) play a vital role in photocatalytic applications due to their high catalytic activity and in gas-sensing applications due to their high chemical sensitivity. Here, we report the transformation at elevated temperature of anatase nanorods (NRs) with a length of 25 nm into rock-salt TiO nanoparticles with an average size of 9.2 ± 2.1 nm investigated by means of in situ heating in the transmission electron microscope. The NRs were completely transformed to titanium monoxide NCs after heating to a temperature of 1200 °C. We also identified an intermediate stage in the temperature range of 950-1200 °C, during which not only the anatase and rock-salt phases were found but also the brookite phase. Understanding of the phase and morphology evolution at high temperatures is of essence to the functionality of the NRs in various applications, as discussed in this work. Moreover, the high-temperature transformation to titanium monoxide is of interest as rock-salt TiO (γ-TiO) is known to exhibit superconducting properties. We propose the heating-induced transformation as a physical route to synthesize TiO NCs of very small size.

Tandem catalysis with double-shelled hollow spheres.

Metal-zeolite composites with metal (oxide) and acid sites are promising catalysts for integrating multiple reactions in tandem to produce a wide variety of wanted products without separating or purifying the intermediates. However, the conventional design of such materials often leads to uncontrolled and non-ideal spatial distributions of the metal inside/on the zeolites, limiting their catalytic performance. Here we demonstrate a simple strategy for synthesizing double-shelled, contiguous metal oxide@zeolite hollow spheres (denoted as MO@ZEO DSHSs) with controllable structural parameters and chemical compositions. This involves the self-assembly of zeolite nanocrystals onto the surface of metal ion-containing carbon spheres followed by calcination and zeolite growth steps. The step-by-step formation mechanism of the material is revealed using mainly in situ Raman spectroscopy and X-ray diffraction and ex situ electron microscopy. We demonstrate that it is due to this structure that an Fe2O3@H-ZSM-5 DSHSs-showcase catalyst exhibits superior performance compared with various conventionally structured Fe2O3-H-ZSM-5 catalysts in gasoline production by the Fischer-Tropsch synthesis. This work is expected to advance the rational synthesis and research of hierarchically hollow, core-shell, multifunctional catalyst materials.

Spontaneous Hetero-attachment of Single-Component Colloidal Precursors for the Synthesis of Asymmetric Au-Ag2X (X = S, Se) Heterodimers.

Finding simple, easily controlled, and flexible synthetic routes for the preparation of ternary and hybrid nanostructured semiconductors is always highly desirable, especially to fulfill the requirements for mass production to enable application to many fields such as optoelectronics, thermoelectricity, and catalysis. Moreover, understanding the underlying reaction mechanisms is equally important, offering a starting point for its extrapolation from one system to another. In this work, we developed a new and more straightforward colloidal synthetic way to form hybrid Au-Ag2X (X = S, Se) nanoparticles under mild conditions through the reaction of Au and Ag2X nanostructured precursors in solution. At the solid-solid interface between metallic domains and the binary chalcogenide domains, a small fraction of a ternary AuAg3X2 phase was observed to have grown as a consequence of a solid-state electrochemical reaction, as confirmed by computational studies. Thus, the formation of stable ternary phases drives the selective hetero-attachment of Au and Ag2X nanoparticles in solution, consolidates the interface between their domains, and stabilizes the whole hybrid Au-Ag2X systems.

Single-step coating of mesoporous SiO2 onto nanoparticles: growth of yolk-shell structures from core-shell structures.

Yolk-shell nanoparticles based on mesoporous SiO2 (mSiO2) coating of Au nanoparticles (Au NPs) hold great promise for many applications in e.g., catalysis, biomedicine, and sensing. Here, we present a single-step coating approach for synthesizing Au NP@mSiO2 yolk-shell particles with tunable size and tunable hollow space between yolk and shell. The Au NP-mSiO2 structure can be manipulated from core-shell to yolk-shell by varying the concentration of cetyltrimethylammonium chloride (CTAC), tetraethyl orthosilicate (TEOS), Au NPs, and NaOH. The growth mechanism of the yolk-shell particles was investigated in detail and consists of a concurrent process of growth, condensation, and internal etching through an outer shell. We also show by means of liquid-cell transmission electron microscopy (LC-TEM) that Au nanotriangle cores (Au NTs) in yolk-shell particles that are stuck on the mSiO2 shell, can be released by mild etching thereby making them mobile and tumbling in a liquid-filled volume. Due to the systematical investigation of the reaction parameters and understanding of the formation mechanism, the method can be scaled-up by at least an order of magnitude. This route can be generally used for the synthesis of yolk-shell structures with different Au nanoparticle shapes, e.g., nanoplatelets, nanorods, nanocubes, for yolk-shell structures with other metals at the core (Ag, Pd, and Pt), and additionally, using ligand exchange with other nanoparticles as cores and for synthesizing hollow mSiO2 spheres as well.

Tunability of Interactions between the Core and Shell in Rattle-Type Particles Studied with Liquid-Cell Electron Microscopy.

Yolk-shell or rattle-type particles consist of a core particle that is free to move inside a thin shell. A stable core with a fully accessible surface is of interest in fields such as catalysis and sensing. However, the stability of a charged nanoparticle core within the cavity of a charged thin shell remains largely unexplored. Liquid-cell (scanning) transmission electron microscopy is an ideal technique to probe the core-shell interactions at nanometer spatial resolution. Here, we show by means of calculations and experiments that these interactions are highly tunable. We found that in dilute solutions adding a monovalent salt led to stronger confinement of the core to the middle of the geometry. In deionized water, the Debye length κ-1 becomes comparable to the shell radius Rshell, leading to a less steep electric potential gradient and a reduced core-shell interaction, which can be detrimental to the stability of nanorattles. For a salt concentration range of 0.5-250 mM, the repulsion was relatively long-ranged due to the concave geometry of the shell. At salt concentrations of 100 and 250 mM, the core was found to move almost exclusively near the shell wall, which can be due to hydrodynamics, a secondary minimum in the interaction potential, or a combination of both. The possibility of imaging nanoparticles inside shells at high spatial resolution with liquid-cell electron microscopy makes rattle particles a powerful experimental model system to learn about nanoparticle interactions. Additionally, our results highlight the possibilities for manipulating the interactions between core and shell that could be used in future applications.

Transformation of Co3O4 nanoparticles to CoO monitored by in situ TEM and predicted ferromagnetism at the Co3O4/CoO interface from first principles.

Nanoparticles of Co3O4 and CoO are of paramount importance because of their chemical properties propelling their applications in catalysis and battery materials, and because of their intriguing magnetic properties. Here we elucidate the transformation of Co3O4 nanoparticles to CoO into nanoscale detail by in situ heating in the transmission electron microscope (TEM), and we decipher the energetics and magnetic properties of the Co3O4/CoO interface from first principles calculations. The transformation was found to start at a temperature of 350 °C, and full conversion of all particles was achieved after heating to 400 °C for 10 minutes. The transformation progressed from the surface to the center of the nanoparticles under the formation of dislocations, while the two phases maintained a cube-on-cube orientation relationship. Various possibilities for magnetic ordering were considered in the density functional theory (DFT) calculations and a favorable Co3O4/CoO {100}/{100} interface energy of 0.38 J m-2 is predicted for the lowest-energy ordering. Remarkably, the DFT calculations revealed a substantial net ferromagnetic moment originating from the interface between the two antiferromagnetic compounds, amounting to approximately 13.9 µ B nm-2. The transformation was reproduced ex situ when heating at a temperature of 400 °C in a high vacuum chamber.

Structural Control over Bimetallic Core-Shell Nanorods for Surface-Enhanced Raman Spectroscopy.

Bimetallic nanorods are important colloidal nanoparticles for optical applications, sensing, and light-enhanced catalysis due to their versatile plasmonic properties. However, tuning the plasmonic resonances is challenging as it requires a simultaneous control over the particle shape, shell thickness, and morphology. Here, we show that we have full control over these parameters by performing metal overgrowth on gold nanorods within a mesoporous silica shell, resulting in Au-Ag, Au-Pd, and Au-Pt core-shell nanorods with precisely tunable plasmonic properties. The metal shell thickness was regulated via the precursor concentration and reaction time in the metal overgrowth. Control over the shell morphology was achieved via a thermal annealing, enabling a transition from rough nonepitaxial to smooth epitaxial Pd shells while retaining the anisotropic rod shape. The core-shell synthesis was successfully scaled up from micro- to milligrams, by controlling the kinetics of the metal overgrowth via the pH. By carefully tuning the structure, we optimized the plasmonic properties of the bimetallic core-shell nanorods for surface-enhanced Raman spectroscopy. The Raman signal was the most strongly enhanced by the Au core-Ag shell nanorods, which we explain using finite-difference time-domain calculations.

In Situ Study of the Wet Chemical Etching of SiO2 and Nanoparticle@SiO2 Core-Shell Nanospheres.

The recent development of liquid cell (scanning) transmission electron microscopy (LC-(S)TEM) has opened the unique possibility of studying the chemical behavior of nanomaterials down to the nanoscale in a liquid environment. Here, we show that the chemically induced etching of three different types of silica-based silica nanoparticles can be reliably studied at the single particle level using LC-(S)TEM with a negligible effect of the electron beam, and we demonstrate this method by successfully monitoring the formation of silica-based heterogeneous yolk-shell nanostructures. By scrutinizing the influence of electron beam irradiation, we show that the cumulative electron dose on the imaging area plays a crucial role in the observed damage and needs to be considered during experimental design. Monte-Carlo simulations of the electron trajectories during LC-(S)TEM experiments allowed us to relate the cumulative electron dose to the deposited energy on the particles, which was found to significantly alter the silica network under imaging conditions of nanoparticles. We used these optimized LC-(S)TEM imaging conditions to systematically characterize the wet etching of silica and metal(oxide)-silica core-shell nanoparticles with cores of gold and iron oxide, which are representative of many other core-silica-shell systems. The LC-(S)TEM method reliably reproduced the etching patterns of Stöber, water-in-oil reverse microemulsion (WORM), and amino acid-catalyzed silica particles that were reported before in the literature. Furthermore, we directly visualized the formation of yolk-shell structures from the wet etching of Au@Stöber silica and Fe3O4@WORM silica core-shell nanospheres.

Symmetric and asymmetric epitaxial growth of metals (Ag, Pd, and Pt) onto Au nanotriangles: effects of reductants and plasmonic properties.

The surface plasmon resonance of noble metals can be tuned by morphology and composition, offering interesting opportunities for applications in biomedicine, optoelectronics, photocatalysis, photovoltaics, and sensing. Here, we present the results of the symmetrical and asymmetrical overgrowth of metals (Ag, Pd, and Pt) onto triangular Au nanoplates using l-ascorbic acid (AA) and/or salicylic acid (SA) as reductants. By varying the reaction conditions, various types of Au nanotriangle-metal (Au NT-M) hetero-nanostructures were easily prepared. The plasmonic properties of as-synthesized nanoparticles were investigated by a combination of optical absorbance measurements and Finite-Difference Time-Domain (FDTD) simulations. We show that specific use of these reductants enables controlled growth of different metals on Au NTs, yielding different morphologies and allowing manipulation and tuning of the plasmonic properties of bimetallic Au NT-M (Ag, Pd, and Pt) structures.

Compartmentalization of gold nanoparticle clusters in hollow silica spheres and their assembly induced by an external electric field.

Assembly of plasmonic nanoparticle clusters having hotspots in a specific space is an effective way to efficiently utilize their plasmonic properties. In the assembly, however, bulk-like aggregates of the nanoparticles are readily formed by strong van der Waals forces, inducing a decrease of the properties. The present work proposes an advanced method to avoid aggregation of the clusters by encapsulating into a confined space of hollow silica interior. Hollow spheres incorporating gold nanoparticle clusters were synthesized by a surface-protected etching process. The observation of inner nanoparticles with liquid cell transmission electron microscopy experimentally proved that the nanoparticles moved as a cluster instead of as dispersed nanoparticles within the water-filled hollow compartment. The hollow spheres incorporating the nanoparticle clusters were assembled in the vicinity of electrodes by application of an external AC electric field, resulting in the enhancement of Raman intensities of probe molecules. The nanoparticle-cluster-containing hollow spheres were redispersed when the electric field was turned off, showing that the hollow silica spheres can act as a physical barrier to avoid the cluster aggregation. The Raman intensities were reversibly changed by switching the electric field on and off to control the assembled or dispersed states of the hollow spheres.