Understanding the Electronic Structure Evolution of Epitaxial LaNi1-xFexO3 Thin Films for Water Oxidation.

Rare earth nickelates including LaNiO3 are promising catalysts for water electrolysis to produce oxygen gas. Recent studies report that Fe substitution for Ni can significantly enhance the oxygen evolution reaction (OER) activity of LaNiO3. However, the role of Fe in increasing the activity remains ambiguous, with potential origins that are both structural and electronic in nature. On the basis of a series of epitaxial LaNi1-xFexO3 thin films synthesized by molecular beam epitaxy, we report that Fe substitution tunes the Ni oxidation state in LaNi1-xFexO3 and a volcano-like OER trend is observed, with x = 0.375 being the most active. Spectroscopy and ab initio modeling reveal that high-valent Fe3+δ cationic species strongly increase the transition-metal (TM) 3d bandwidth via Ni-O-Fe bridges and enhance TM 3d-O 2p hybridization, boosting the OER activity. These studies deepen our understanding of structural and electronic contributions that give rise to enhanced OER activity in perovskite oxides.

In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode-Electrolyte Interface: a SIMS Approach.

The in situ molecular characterization of reaction intermediates and products at electrode-electrolyte interfaces is central to mechanistic studies of complex electrochemical processes, yet a great challenge. The coupling of electrochemistry (EC) and mass spectrometry (MS) has seen rapid development and found broad applicability in tackling challenges in analytical and bioanalytical chemistry. However, few truly in situ and real-time EC-MS studies have been reported at electrode-electrolyte interfaces. An innovative EC-MS coupling method named in situ liquid secondary ion mass spectrometry (SIMS) was recently developed by combining SIMS with a vacuum compatible microfluidic electrochemical device. Using this novel capability, we report the first in situ elucidation of the electro-oxidation mechanism of a biologically significant organic compound, ascorbic acid (AA), at the electrode-electrolyte interface. The short-lived radical intermediate was successfully captured, which had not been detected directly before. Moreover, we demonstrated the power of this new technique in real-time monitoring of the formation and dynamic evolution of electrical double layers at the electrode-electrolyte interface. This work suggests further promising applications of in situ liquid SIMS in studying more complex chemical and biological events at the electrode-electrolyte interface.

In Situ Mass Spectrometric Determination of Molecular Structural Evolution at the Solid Electrolyte Interphase in Lithium-Ion Batteries.

Dynamic structural and chemical evolution at solid-liquid electrolyte interface is always a mystery for a rechargeable battery due to the challenge to directly probe a solid-liquid interface under reaction conditions. We describe the creation and usage of in situ liquid secondary ion mass spectroscopy (SIMS) for the first time to directly observe the molecular structural evolution at the solid-liquid electrolyte interface for a lithium (Li)-ion battery under dynamic operating conditions. We have discovered that the deposition of Li metal on copper electrode leads to the condensation of solvent molecules around the electrode. Chemically, this layer of solvent condensate tends to be depleted of the salt anions and with reduced concentration of Li(+) ions, essentially leading to the formation of a lean electrolyte layer adjacent to the electrode and therefore contributing to the overpotential of the cell. This observation provides unprecedented molecular level dynamic information on the initial formation of the solid electrolyte interphase (SEI) layer. The present work also ultimately opens new avenues for implanting the in situ liquid SIMS concept to probe the chemical reaction process that intimately involves solid-liquid interface, such as electrocatalysis, electrodeposition, biofuel conversion, biofilm, and biomineralization.

Mechanistic understanding of speciated oxide growth in high entropy alloys.

Complex multi-element alloys are gaining prominence for structural applications, supplementing steels, and superalloys. Understanding the impact of each element on alloy surfaces due to oxidation is vital in maintaining material integrity. This study investigates oxidation mechanisms in these alloys using a model five-element equiatomic CoCrFeNiMn alloy, in a controlled oxygen environment. The oxidation-induced surface changes correlate with each element's interactive tendencies with the environment, guided by thermodynamics. Initial oxidation stages follow atomic size and redox potential, with the latter becoming dominant over time, causing composition inversion. The study employs in-situ atom probe tomography, transmission electron microscopy, and X-ray absorption near-edge structure techniques to elucidate the oxidation process and surface oxide structure evolution. Our findings deconvolute the mechanism for compositional and structural changes in the oxide film and will pave the way for a predictive design of complex alloys with improved resistance to oxidation under extreme conditions.

Surface characterization of nanomaterials and nanoparticles: Important needs and challenging opportunities.

This review examines characterization challenges inherently associated with understanding nanomaterials and the roles surface and interface characterization methods can play in meeting some of the challenges. In parts of the research community, there is growing recognition that studies and published reports on the properties and behaviors of nanomaterials often have reported inadequate or incomplete characterization. As a consequence, the true value of the data in these reports is, at best, uncertain. With the increasing importance of nanomaterials in fundamental research and technological applications, it is desirable that researchers from the wide variety of disciplines involved recognize the nature of these often unexpected challenges associated with reproducible synthesis and characterization of nanomaterials, including the difficulties of maintaining desired materials properties during handling and processing due to their dynamic nature. It is equally valuable for researchers to understand how characterization approaches (surface and otherwise) can help to minimize synthesis surprises and to determine how (and how quickly) materials and properties change in different environments. Appropriate application of traditional surface sensitive analysis methods (including x-ray photoelectron and Auger electron spectroscopies, scanning probe microscopy, and secondary ion mass spectroscopy) can provide information that helps address several of the analysis needs. In many circumstances, extensions of traditional data analysis can provide considerably more information than normally obtained from the data collected. Less common or evolving methods with surface selectivity (e.g., some variations of nuclear magnetic resonance, sum frequency generation, and low and medium energy ion scattering) can provide information about surfaces or interfaces in working environments (operando or in situ) or information not provided by more traditional methods. Although these methods may require instrumentation or expertise not generally available, they can be particularly useful in addressing specific questions, and examples of their use in nanomaterial research are presented.

In situ TEM investigation of congruent phase transition and structural evolution of nanostructured silicon/carbon anode for lithium ion batteries.

It is well-known that upon lithiation, both crystalline and amorphous Si transform to an armorphous Li(x)Si phase, which subsequently crystallizes to a (Li, Si) crystalline compound, either Li(15)Si(4) or Li(22)Si(5). Presently, the detailed atomistic mechanism of this phase transformation and the degradation process in nanostructured Si are not fully understood. Here, we report the phase transformation characteristic and microstructural evolution of a specially designed amorphous silicon (a-Si) coated carbon nanofiber (CNF) composite during the charge/discharge process using in situ transmission electron microscopy and density function theory molecular dynamic calculation. We found the crystallization of Li(15)Si(4) from amorphous Li(x)Si is a spontaneous, congruent phase transition process without phase separation or large-scale atomic motion, which is drastically different from what is expected from a classic nucleation and growth process. The a-Si layer is strongly bonded to the CNF and no spallation or cracking is observed during the early stages of cyclic charge/discharge. Reversible volume expansion/contraction upon charge/discharge is fully accommodated along the radial direction. However, with progressive cycling, damage in the form of surface roughness was gradually accumulated on the coating layer, which is believed to be the mechanism for the eventual capacity fade of the composite anode during long-term charge/discharge cycling.

Conflicting roles of nickel in controlling cathode performance in lithium ion batteries.

A variety of approaches are being made to enhance the performance of lithium ion batteries. Incorporating multivalence transition-metal ions into metal oxide cathodes has been identified as an essential approach to achieve the necessary high voltage and high capacity. However, the fundamental mechanism that limits their power rate and cycling stability remains unclear. The power rate strongly depends on the lithium ion drift speed in the cathode. Crystallographically, these transition-metal-based cathodes frequently have a layered structure. In the classic wisdom, it is accepted that lithium ion travels swiftly within the layers moving out/in of the cathode during the charge/discharge. Here, we report the unexpected discovery of a thermodynamically driven, yet kinetically controlled, surface modification in the widely explored lithium nickel manganese oxide cathode material, which may inhibit the battery charge/discharge rate. We found that during cathode synthesis and processing before electrochemical cycling in the cell nickel can preferentially move along the fast diffusion channels and selectively segregate at the surface facets terminated with a mix of anions and cations. This segregation essentially can lead to a higher lithium diffusion barrier near the surface region of the particle. Therefore, it appears that the transition-metal dopant may help to provide high capacity and/or high voltage but can be located in a "wrong" location that may slow down lithium diffusion, limiting battery performance. In this circumstance, limitations in the properties of lithium ion batteries using these cathode materials can be determined more by the materials synthesis issues than by the operation within the battery itself.

Plasmonic-based sensing using an array of Au-metal oxide thin films.

An optical plasmonic-based sensing array has been developed and tested for the selective and sensitive detection of H(2), CO, and NO(2) at a temperature of 500 °C in an oxygen-containing background. The three-element sensing array used Au nanoparticles embedded in separate thin films of yttria-stabilized zirconia (YSZ), CeO(2), and TiO(2). A peak in the absorbance spectrum due to a localized surface plasmon resonance (LSPR) on the Au nanoparticles was monitored for each film during gas exposures and showed a blue shift in the peak positions for the reducing gases, H(2) and CO, and a red shift for the oxidizing gas, NO(2). A more in-depth look at the sensing response was performed using the multivariate methods of principal component analysis (PCA) and linear discriminant analysis (LDA) on data from across the entire absorbance spectrum range. Qualitative results from both methods showed good separation between the three analytes for both the full array and the Au-TiO(2) sample. Quantification of LDA cluster separation using the Mahalanobis distance showed better cluster separation for the array, but there were some instances with the lowest concentrations where the single Au-TiO(2) film had separation better than that of the array. A second method to quantify cluster separation in LDA space was developed using multidimensional volume analysis of the individual cluster volume, overlapped cluster volume, and empty volume between clusters. Compared to the individual sensing elements, the array showed less cluster overlap, smaller cluster volumes, and more space between clusters, all of which were expected for improved separability between the analytes.

Selective plasmonic gas sensing: H2, NO2, and CO spectral discrimination by a single Au-CeO2 nanocomposite film.

A Au-CeO(2) nanocomposite film has been investigated as a potential sensing element for high-temperature plasmonic sensing of H(2), CO, and NO(2) in an oxygen containing environment. The CeO(2) thin film was deposited by molecular beam epitaxy (MBE), and Au was implanted into the as-grown film at an elevated temperature followed by high temperature annealing to form well-defined Au nanoclusters. The Au-CeO(2) nanocomposite film was characterized by X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). For the gas sensing experiments, separate exposures to varying concentrations of H(2), CO, and NO(2) were performed at a temperature of 500 °C in oxygen backgrounds of 5.0, 10, and ∼21% O(2). Changes in the localized surface plasmon resonance (LSPR) absorption peak were monitored during gas exposures and are believed to be the result of oxidation-reduction processes that fill or create oxygen vacancies in the CeO(2). This process affects the LSPR peak position either by charge exchange with the Au nanoparticles (AuNPs) or by changes in the dielectric constant surrounding the particles. Spectral multivariate analysis was used to gauge the inherent selectivity of the film between the separate analytes. From principal component analysis (PCA), unique and identifiable responses were seen for each of the analytes. Linear discriminant analysis (LDA) was also used and showed separation between analytes as well as trends in gas concentration. Results indicate that the Au-CeO(2) thin film is selective to O(2), H(2), CO, and NO(2) in separate exposures. This, combined with the observed stability over long exposure periods, shows the Au-CeO(2) film has good potential as an optical sensing element for harsh environmental conditions.

In situ transmission electron microscopy observation of microstructure and phase evolution in a SnO2 nanowire during lithium intercalation.

Recently we have reported structural transformation features of SnO(2) upon initial charging using a configuration that leads to the sequential lithiation of SnO(2) nanowire from one end to the other (Huang et al. Science2010, 330, 1515). A key question to be addressed is the lithiation behavior of the nanowire when it is fully soaked into the electrolyte (Chiang Science2010, 330, 1485). This Letter documents the structural characteristics of SnO(2) upon initial charging based on a battery assembled with a single nanowire anode, which is fully soaked (immersed) into an ionic liquid based electrolyte using in situ transmission electron microscopy. It has been observed that following the initial charging the nanowire retained a wire shape, although highly distorted. The originally straight wire is characterized by a zigzag structure following the phase transformation, indicating that during the phase transformation of SnO(2) + Li ↔ Li(x)Sn + Li(y)O, the nanowire was subjected to severe deformation, as similarly observed for the case when the SnO(2) was charged sequentially from one end to the other. Transmission electron microscopy imaging revealed that the Li(x)Sn phase possesses a spherical morphology and is embedded into the amorphous Li(y)O matrix, indicating a simultaneous partitioning and coarsening of Li(x)Sn through Sn and Li diffusion in the amorphous matrix accompanied the phase transformation. The presently observed composite configuration gives detailed information on the structural change and how this change takes place on nanometer scale.

PEGylated inorganic nanoparticles.

Application of inorganic nanoparticles in diagnosis and therapy has become a critical component in the targeted treatment of diseases. The surface modification of inorganic oxides is important for providing diversity in size, shape, solubility, long-term stability, and attachment of selective functional groups. This Minireview describes the role of polyethylene glycol (PEG) in the surface modification of oxides and focuses on their biomedical applications. Such a PEGylation of surfaces provides "stealth" characteristics to nanomaterials otherwise identified as foreign materials by human body. The role of PEG as structure-directing agent in synthesis of oxides is also presented.

Role of Polysulfide Anions in Solid-Electrolyte Interphase Formation at the Lithium Metal Surface in Li-S Batteries.

Delineating intricate interactions between highly reactive Li-metal electrodes and the diverse constituents of battery electrolytes has been a long-standing scientific challenge in materials design for advanced energy storage devices. Here, we isolated lithium polysulfide anions (LiS4-) from an electrolyte solution based on their mass-to-charge ratio and deposited them on Li-metal electrodes under clean vacuum conditions using ion soft landing (ISL), a highly controlled interface preparation technique. The molecular level precision in the construction of these model interfaces with ISL, coupled with in situ X-ray photoelectron spectroscopy and ab initio theoretical calculations, allowed us to obtain unprecedented insight into the parasitic reactions of well-defined polysulfides on Li-metal electrodes. Our study revealed that the oxide-rich surface layer, which is amenable to direct electron exchange, drives multielectron sulfur oxidation (S0 → S6+) processes. Our results have substantial implications for the rational design of future Li-S batteries with improved efficiency and durability.

Self-assembly of cerium oxide nanostructures in ice molds.

The formation of nanorods, driven by the physicochemical phenomena during the freezing and after the aging of frozen ceria nanoparticle suspensions, is reported. During freezing of a dilute aqueous solution of CeO2 nanocrystals, some nuclei remain in solution while others are trapped inside micro- and nanometer voids formed within the growing ice front. Over time (2-3 weeks) the particles trapped within the nanometer-wide voids in the ice combine by an oriented attachment process to form ceria nanorods. The experimental observations are consistent with molecular dynamics simulations of particle aggregation in constrained environments. These observations suggest a possible strategy for the templated formation of nanostructures through self-assembly by exploiting natural phenomena, such as voids formed during freezing of water. This research suggests a very simple, green chemical route to guide the formation of one- and three-dimensional self-assembled nanostructures.

Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt-Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy.

A method to understand the role of interfacial chemistry on the modulation of Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. In situ X-ray photoelectron spectroscopy was used to characterize the interfacial chemistries that modulate barrier heights in this system. The primary changes were a significant chemical reduction of indium, from In3+ to In0, that occurs during deposition of Pt on to the a-IGZO surface in ultrahigh vacuum. Postannealing and controlling the background ambient O2 pressure allows further tuning of the reduction of indium and the corresponding Schottky barrier heights from 0.17 to 0.77 eV. Understanding the detailed interfacial chemistries at Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metal-semiconductor field-effect transistors.

Influence of LaFeO3 Surface Termination on Water Reactivity.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. However, the FeO2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate-adsorbate interactions may impact reactivity. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.

Uranium isotopic ratio measurements of U3O8 reference materials by atom probe tomography.

We report results of measurements of isotopic ratios obtained with atom probe tomography on U3O8 reference materials certified for their isotopic abundances of uranium. The results show good agreement with the certified values. High backgrounds due to tails from adjacent peaks complicate the measurement of the integrated peak areas as well as the fact that only oxides of uranium appear in the spectrum, the most intense of which is doubly charged. In addition, lack of knowledge of other instrumental parameters, such as the dead time, may bias the results. Isotopic ratio measurements can be performed at the nanometer-scale with the expectation of sensible results. The abundance sensitivity and mass resolving power of the mass spectrometer are not sufficient to compete with magnetic-sector instruments but are not far from measurements made by ToF-SIMS of other isotopic systems. The agreement of the major isotope ratios is more than sufficient to distinguish most anthropogenic compositions from natural.

Near-edge X-ray absorption fine structure study of disordering in Gd2(Ti1-yZry)2O7 pyrochlores.

Disorder in Gd2(Ti(1-y)Zry)2O7 pyrochlores, for y = 0.0-1.0, is investigated by Ti 2p and O 1s near-edge X-ray absorption fine structure spectroscopy. Ti(4+) ions are found to occupy octahedral sites in Gd2Ti2O7 with a tetragonal distortion induced by vacant oxygen sites. As Zr substitutes for Ti, the tetragonal distortion decreases, and Zr coordination increases from 6 to 8. The migration of oxygen ions from 48f or 8b sites to vacant 8a sites compensate for the increased Zr coordination, thereby reducing the number of vacant 8a sites, which further reduces the tetragonal distortion and introduces more disorder around Ti. This is evidence for simultaneous cation disorder with anion migration.

Instability of hydrogenated TiO2.

Hydrogenated TiO2 (H-TiO2) is touted as a viable visible light photocatalyst. We report a systematic study on the thermal stability of H-implanted TiO2 using nuclear reaction analysis (NRA), Rutherford backscattering spectrometry, ultraviolet photoelectron spectroscopy, and X-ray photoelectron spectroscopy. Protons (40 keV) implanted at a ∼2 atom % level within a ∼120 nm wide profile of rutile TiO2(110) were situated ∼300 nm below the surface. NRA revealed that this H-profile broadened toward the surface after annealing at 373 K, dissipated out of the crystal into vacuum at 473 K, and was absent within the beam sampling depth (∼800 nm) at 523 K. Photoemission showed that the surface was reduced in concert with these changes. Similar anneals had no effect on pristine TiO2(110). The facile bulk diffusivity of H in rutile at low temperatures, as well as its interfacial activity toward reduction, significantly limits the utilization of H-TiO2 as a photocatalyst.

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles.

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce(3+)/Ce(4+) ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce(3+)/Ce(4+) ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of the cells.

Understanding Atom Probe Tomography of Oxide-Supported Metal Nanoparticles by Correlation with Atomic-Resolution Electron Microscopy and Field Evaporation Simulation.

Oxide-supported metal nanoparticles are widely used in heterogeneous catalysis. The increasingly detailed design of such catalysts necessitates three-dimensional characterization with high spatial resolution and elemental selectivity. Laser-assisted atom probe tomography (APT) is uniquely suited to the task but faces challenges with the evaporation of metal/insulator systems. Correlation of APT with aberration-corrected scanning transmission electron microscopy (STEM), for Au nanoparticles embedded in MgO, reveals preferential evaporation of the MgO and an inaccurate assessment of nanoparticle composition. Finite element field evaporation modeling is used to illustrate the evolution of the evaporation front. Nanoparticle composition is most accurately predicted when the MgO is treated as having a locally variable evaporation field, indicating the importance of considering laser-oxide interactions and the evaporation of various molecular oxide ions. These results demonstrate the viability of APT for analysis of oxide-supported metal nanoparticles, highlighting the need for developing a theoretical framework for the evaporation of heterogeneous materials.