Measuring local polar ordering is key to understanding ferroelectricity in thin films, especially for systems with small domains or significant disorder. Scanning nanobeam electron diffraction (NBED) provides an effective local probe of lattice parameters, local fields, polarization directions, and charge densities, which can be analyzed using a relatively low beam dose over large fields of view. However, quantitatively extracting the magnitudes and directions of polarization vectors from NBED remains challenging. Here, we use a cepstral approach, similar to a pair distribution function, to determine local polar displacements that drive ferroelectricity from NBED patterns. Because polar distortions generate asymmetry in the diffraction pattern intensity, we can efficiently recover the underlying displacements from the imaginary part of the cepstrum transform. We investigate the limits of this technique using analytical and simulated data and give experimental examples, achieving the order of 1.1 pm precision and mapping of polar displacements with nanometer resolution.
Adlayers on C-plane (0001) and R-plane ( 1 1 â 02 ) terminated surfaces of corundum phase aluminum oxide were synthesized by annealing mixtures of two oxide powders, aluminum oxide with an additive. Using high-angle annular dark field scanning transmission electron microscopy, the adsorbed layers were characterized, and image simulations aided interpretation of the results. The adlayers were pseudomorphic, one atomic layer thick and with a fractional site occupancy. Atomic positions of the adlayer atoms relaxed and changed relative to the bulk structure, where there is evidence that the magnitude of the relaxation is sensitive to the ionic radius of the adsorbate. The pseudomorphic adlayer structure formed for different elements including, but not limited to, the lanthanides (i.e., Ge, Ba and Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm).
Defects may display high reactivity because the specific arrangement of atoms differs from crystalline surfaces. We demonstrate that high-temperature steam pretreatment of palladium catalysts provides a 12-fold increase in the mass-specific reaction rate for carbon-hydrogen (CH) activation in methane oxidation compared with conventional pretreatments. Through a combination of experimental and theoretical methods, we demonstrate that an increase in the grain boundary density through crystal twinning is achieved during the steam pretreatment and oxidation and is responsible for the increased reactivity. The grain boundaries are highly stable during reaction and show specific rates at least two orders of magnitude higher than other sites on the palladium on alumina (Pd/Al2O3) catalysts. Theoretical calculations show that strain introduced by the defective structure can enhance CH bond activation. Introduction of grain boundaries through laser ablation led to further rate increases.
Supported metal nanoparticles are essential components of high-performing catalysts, and their structures are intensely researched. In comparison, nanoparticle spatial distribution in powder catalysts is conventionally not quantified, and the influence of this collective property on catalyst performance remains poorly investigated. Here, we demonstrate a general colloidal self-assembly method to control uniformity of nanoparticle spatial distribution on common industrial powder supports. We quantify distributions on the nanoscale using image statistics and show that the type of nanospatial distribution determines not only the stability, but also the activity of heterogeneous catalysts. Widely investigated systems (Au-TiO2 for CO oxidation thermocatalysis and Pd-TiO2 for H2 evolution photocatalysis) were used to showcase the universal importance of nanoparticle spatial organization. Spatially and temporally resolved microkinetic modeling revealed that nonuniformly distributed Au nanoparticles suffer from local depletion of surface oxygen, and therefore lower CO oxidation activity, as compared to uniformly distributed nanoparticles. Nanoparticle spatial distribution also determines the stability of Pd-TiO2 photocatalysts, because nonuniformly distributed nanoparticles sinter while uniformly distributed nanoparticles do not. This work introduces new tools to evaluate and understand catalyst collective (ensemble) properties in powder catalysts, which thereby pave the way to more active and stable heterogeneous catalysts.
Carbon Monoxide/chemistry , Gold/chemistry , Hydrogen/chemistry , Nanoparticles/chemistry , Palladium/chemistry , Titanium/chemistry , Catalysis , Oxidation-Reduction , Particle Size , Photochemical Processes , Powders , Surface Properties
Light-driven synthesis of plasmonic metal nanostructures has garnered broad scientific interests. Although it has been widely accepted that surface plasmon resonance (SPR)-generated energetic electrons play an essential role in this photochemical process, the exact function of plasmon-generated hot holes in regulating the morphology of nanostructures has not been fully explored. Herein, we discover that those hot holes work with surface adsorbates collectively to control the anisotropic growth of gold (Au) nanostructures. Specifically, it is found that hot holes stabilized by surface adsorbed iodide enable the site-selective oxidative etching of Au0, which leads to nonuniform growths along different lateral directions to form six-pointed Au nanostars. Our studies establish a molecular-level understanding of the mechanism behind the plasmon-driven synthesis of Au nanostars and illustrate the importance of cooperation between charge carriers and surface adsorbates in regulating the morphology evolution of plasmonic nanostructures.
Understanding the structure transformation of engineered nanomaterials (ENMs) is a grand measurement challenge, which impacts many aspects of ENMs applications, such as their efficacy, safety, and environmental consequence. To address the significant knowledge gap regarding the fundamental kinetic rate and extent of ENM transformation in the environment, we present a comprehensive and mechanistic structural investigation of the transformation, aggregation, and dissolution behavior of a polyvinylpyrrolidone-coated silver nanoparticle (AgNP) suspension upon sulfidation in moderately reduced hard water with fulvic acid and dissolved Na2S. This reaction is among the most prevalent and industrially and environmentally relevant ENMs transformation. Using ex situ transmission electron microscopy (TEM) and both in situ and ex situ synchrotron-based small angle X-ray scattering (SAXS) and X-ray diffraction (XRD), we find that sulfidation of faceted AgNPs strongly depends on the crystallographic orientation of the facets, with nanometer-scale passivation layers developed on {111} and {100} facets and continuous nucleation and growth on {110} facets. Nanobeam electron diffraction and atomic resolution imaging show Ag and Ag2S domains both possess a high degree of crystalline order, contradicting amorphous structures as previously reported. In situ SAXS/XRD allowed simultaneous determination of the morphological changes and extent of sulfidation of AgNPs. SAXS/XRD results strongly indicate sulfidation follows first-order reaction kinetics without any aggregation. Aided by their size monodispersity, for the first time, using direct, in situ morphology and atomic-structure probes whose results mutually corroborate, we unequivocally determined the sulfidation rate constant of AgNPs under an environmentally relevant condition (~0.013 min-1 for 68 nm diameter AgNPs). A rigorous analysis of the long-term sulfidation product of the AgNPs under different S/Ag ratios using ex situ SAXS/XRD clearly demonstrates that the silver mass in the original AgNP and transformed Ag/Ag2S NP is preserved. This result has important environmental implications, strongly suggesting that Ag+ ions, a known highly effective antimicrobial agent, are not leached into the solution during sulfidation of AgNPs. The combined nondestructive methodology can be extended to unfold the structure transformation pathway and kinetics in a broad range of ENM systems.
Cerium oxide nanomaterials (nanoceria, CNMs) are receiving increased attention from the research community due to their unique chemical properties, most prominent of which is their ability to alternate between the Ce3+ and Ce4+ oxidation states. While many analytical techniques and methods have been employed to characterize the amounts of Ce3+ and Ce4+ present (Ce3+/Ce4+ ratio) within nanoceria materials, to-date no studies have used multiple complementary analytical tools (orthogonal analysis) with technique-independent oxidation state controls for quantitative determinations of the Ce3+/Ce4+ ratio. Here, we describe the development of analytical methods measuring the oxidation states of nanoceria analytes using technique-independent Ce3+ (CeAlO3:Ge) and Ce4+ (CeO2) control materials, with a particular focus on x-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS) approaches. The developed methods were demonstrated in characterizing a suite of commercial nanoceria products, where the two techniques (XPS and EELS) were found to be in good agreement with respect to Ce3+/Ce4+ ratio. Potential sources of artifacts and discrepancies in the measurement results were also identified and discussed, alongside suggestions for interpreting oxidation state results using the different analytical techniques. The results should be applicable towards producing more consistent and reproducible oxidation state analyses of nanoceria materials.
In the high-temperature environments needed to perform catalytic processes, supported precious metal catalysts severely lose their activity over time. Even brief exposure to high temperatures can lead to significant losses in activity, which forces manufacturers to use large amounts of noble metals to ensure effective catalyst function for a required lifetime. Generally, loss of catalytic activity is attributed to nanoparticle sintering, or processes by which larger particles grow at the expense of smaller ones. Here, by independently controlling particle size and particle loading using colloidal nanocrystals, we reveal the opposite process as a novel deactivation mechanism: nanoparticles rapidly lose activity by high-temperature nanoparticle decomposition into inactive single atoms. This deactivation route is remarkably fast, leading to severe loss of activity in as little as ten minutes. Importantly, this deactivation pathway is strongly dependent on particle density and concentration of support defect sites. A quantitative statistical model explains how for certain reactions, higher particle densities can lead to more stable catalysts.
Reported reaction kinetics of metal nanoparticles in natural and engineered systems commonly have used proxy measurements to infer chemical transformations, but extension of these methods to complex media has proven difficult. Here, we compare the sulfidation rate of AgNPs using two ion selective electrode (ISE)-based methods, which rely on either (i) direct measurement of free sulfide, or (ii) monitor the free Ag+ available in solution over time in the presence of sulfide species. Most experiments were carried out in moderately hard reconstituted water at pH 7 containing fulvic acid or humic acid, which represented a broad set of known interferences in ISE. Distinct differences in the measured rates were observed between the two proxy-based methods and details of the divergent results are discussed. The two ISE based methods were then compared to direct monitoring of AgNP chemical conversion to Ag2S using synchrotron-based in situ X-ray diffraction (XRD). Using XRD, distinct rates from both ISE-based technique were observed, which demonstrated that ISE measurements alone are inadequate to discriminate both the rate and extent of AgNP sulfidation. XRD rate data elucidated previously unidentified reaction regimes that were associated with AgNP coating (PVP and citrate acid) and NOM components, which provided new mechanistic insight into metallic NP processing. In general, the extent of Ag2S formation was inversely proportional to surface coverage of the initial AgNP. Overall, methods to determine reaction kinetics of nanomaterials in increasingly complex media and heterogeneous size distributions to improve NP-based design and performance will require similar approaches.
Cerium dioxide nanocubes and truncated octahedra were reduced and oxidized in the scanning transmission electron microscope. The reduction process was stimulated by the electron beam and oxidation was supported by background gases in the microscope environment. High-angle annular dark field imaging is sensitive to local lattice distortions that arise as oxygen vacancies are created and cerium cations reduce enabling high spatial resolution characterization of this process with temporal resolution on the order of seconds. Such measurements enable us to differentiate and infer that the observed behavior between the nanocubes and truncated octahedra may be due to the difference in crystallographic termination of surfaces. In situ measurements taken with different partial pressures of oxygen reveal the cerium oxidation state and the dose rate threshold for the onset of beam reduction are influenced by the environment. Increasing oxygen partial pressure reduces the Ce3+ content and decreases susceptibility to electron beam driven reduction.
The electrochemical performance and microstructure of positive electrodes are intimately linked. As such, developing batteries resistance to capacity and voltage fade requires understanding these underlying structure-properties relationships and their evolution with operation. Epitaxial films of a Li-rich manganese-nickel- cobalt oxide cathode material were deposited on (100) and (111) orientated SrRuO3/SrTiO3 substrates. Cyclic voltammetry and impedance spectroscopy tracked the response of these positive electrode materials, while the microstructure of the pristine and cycled films was characterized using transmission electron microscopy. Energy-dispersive X-ray spectroscopy identifies compositional fluctuations in as-deposited films. Phase transformations and dissolution were observed after electrochemical testing. There is a correlation between both local composition and substrate orientation (i.e., surface faceting) and what degradation pathways are active. Regions with comparatively higher concentrations of Ni and Co were more resistant to dissolution and unfavorable phase transformations than those with relatively more Mn. As such, a global composition metric may not be an accurate predictor of degradation and performance. Rather possessing the synthetic ability to engineer the chemical profile as well as characterizing it, pose a challenge and opportunity.
Due to the directional dependence of physical properties, it is advantageous to grow and then study materials in specific orientations. Films of battery materials grown in epitaxy offers the possibility to gain new insight into the role of physical structure on electrochemical behaviors. Here we demonstrate the growth, testing, and characterization of monoclinic-phase (space group C2/m) Li-Mn-Ni-Co-O epitaxial films. The monoclinic phase is a layered structure and as such lithium diffusion is favored along specific crystallographic directions. Films were grown by pulsed laser deposition onto SrRuO3/SrTiO3 substrates with (001) and (111) orientations. Cyclic voltammetry measured the response of these positive electrode materials, while the film structure was characterized using scanning transmission electron microscopy. A combination of imaging and diffraction identifies the presence of orientational variants. Variants disrupt the orientation anisotropy expected of these layered materials when grown in epitaxy, thereby masking differences in electrochemical behavior as a function of substrate orientation. Learning to control the domain structure now presents itself as a challenge to realize the potential of low symmetry battery materials grown in epitaxy on high symmetry substrates.
A pristine Li-rich layered electrode material with composition Li1.2Mn0.55Ni0.15Co0.1O2 was characterized by X-ray diffraction, transmission electron microscopy, and scanning transmission electron microscopy to determine whether it is a coherent mixture of monoclinic C2/m Li2MO3 and trigonal [Formula: see text] LiMO2 phases or a solid solution of the monoclinic phase. Contradictory results have been previously reported which can be attributed to the complexity and structural similarity of the monoclinic and trigonal phases. We resolved this uncertainty by combining diffraction and imaging techniques that probe complimentary length scales. Our results demonstrate that the structure is primarily monoclinic, supporting the solid solution model, although near surface structural alterations were also observed.
After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. Herein, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally different from its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. These insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.
Beam damage caused by energetic electrons in the transmission electron microscope is a fundamental constraint limiting the collection of artifact-free information. Through understanding the influence of the electron beam, experimental routines may be adjusted to improve the data collection process. Investigations of CeO2 indicate that there is not a critical dose required for the accumulation of electron beam damage. Instead, measurements using annular dark field scanning transmission electron microscopy and electron energy loss spectroscopy demonstrate that the onset of measurable damage occurs when a critical dose rate is exceeded. The mechanism behind this phenomenon is that oxygen vacancies created by exposure to a 300keV electron beam are actively annihilated as the sample re-oxidizes in the microscope environment. As a result, only when the rate of vacancy creation exceeds the recovery rate will beam damage begin to accumulate. This observation suggests that dose-intensive experiments can be accomplished without disrupting the native structure of the sample when executed using dose rates below the appropriate threshold. Furthermore, the presence of an encapsulating carbonaceous layer inhibits processes that cause beam damage, markedly increasing the dose rate threshold for the accumulation of damage.
Low-angle annular dark field (LAADF) scanning transmission electron microscopy (STEM) imaging is presented as a method that is sensitive to the oxidation state of cerium ions in CeO2 nanoparticles. This relationship was validated through electron energy loss spectroscopy (EELS), in situ measurements, as well as multislice image simulations. Static displacements caused by the increased ionic radius of Ce(3+) influence the electron channeling process and increase electron scattering to low angles while reducing scatter to high angles. This process manifests itself by reducing the high-angle annular dark field (HAADF) signal intensity while increasing the LAADF signal intensity in close proximity to Ce(3+) ions. This technique can supplement STEM-EELS and in so doing, relax the experimental challenges associated with acquiring oxidation state information at high spatial resolutions.
Doping is a process in which atomic impurities are intentionally added to a host material to modify its properties. It has had a revolutionary impact in altering or introducing electronic, magnetic, luminescent, and catalytic properties for several applications, for example in semiconductors. Here we explore and demonstrate the extension of the concept of substitutional atomic doping to nanometre-scale crystal doping, in which one nanocrystal is used to replace another to form doped self-assembled superlattices. Towards this goal, we show that gold nanocrystals act as substitutional dopants in superlattices of cadmium selenide or lead selenide nanocrystals when the size of the gold nanocrystal is very close to that of the host. The gold nanocrystals occupy random positions in the superlattice and their density is readily and widely controllable, analogous to the case of atomic doping, but here through nanocrystal self-assembly. We also show that the electronic properties of the superlattices are highly tunable and strongly affected by the presence and density of the gold nanocrystal dopants. The conductivity of lead selenide films, for example, can be manipulated over at least six orders of magnitude by the addition of gold nanocrystals and is explained by a percolation model. As this process relies on the self-assembly of uniform nanocrystals, it can be generally applied to assemble a wide variety of nanocrystal-doped structures for electronic, optical, magnetic, and catalytic materials.
Ideal solar-to-fuel photocatalysts must effectively harvest sunlight to generate significant quantities of long-lived charge carriers necessary for chemical reactions. Here we demonstrate the merits of augmenting traditional photoelectrochemical cells with plasmonic nanoparticles to satisfy these daunting photocatalytic requirements. Electrochemical techniques were employed to elucidate the mechanics of plasmon-mediated electron transfer within Au/TiO2 heterostructures under visible-light (λ>515â nm) irradiation in solution. Significantly, we discovered that these transferred electrons displayed excited-state lifetimes two orders of magnitude longer than those of electrons photogenerated directly within TiO2 via UV excitation. These long-lived electrons further enable visible-light-driven H2 evolution from water, heralding a new photocatalytic paradigm for solar energy conversion.
Water reduction under two different visible-light ranges (λ > 400 nm and λ > 435 nm) was investigated in gold-loaded titanium dioxide (Au-TiO2) heterostructures with different sizes of Au nanoparticles (NPs). Our study clearly demonstrates the essential role played by Au NP size in plasmon-driven H2O reduction and reveals two distinct mechanisms to clarify visible-light photocatalytic activity under different excitation conditions. The size of the Au NP governs the efficiency of plasmon-mediated electron transfer and plays a critical role in determining the reduction potentials of the electrons transferred to the TiO2 conduction band. Our discovery provides a facile method of manipulating photocatalytic activity simply by varying the Au NP size and is expected to greatly facilitate the design of suitable plasmonic photocatalysts for solar-to-fuel energy conversion.
Size-dependent nanostructural transformations occurring during the H(2)-mediated reduction of hollow and porous NiO nanoparticles were investigated for controlled nanoparticle sizes of ~10 to 100 nm. Transmission electron microscopy reveals that the location and number of reduction sites strongly depend on the nanoparticle size and structure.
Hydrogen/chemistry , Metal Nanoparticles/chemistry , Metal Nanoparticles/ultrastructure , Nickel/chemistry , Macromolecular Substances/chemistry , Materials Testing , Molecular Conformation , Oxidation-Reduction , Porosity , Surface Properties
