Fast Surface Oxygen Release Kinetics Accelerate Nanoparticle Exsolution in Perovskite Oxides.

Exsolution is a recent advancement for fabricating oxide-supported metal nanoparticle catalysts via phase precipitation out of a host oxide. A fundamental understanding and control of the exsolution kinetics are needed to engineer exsolved nanoparticles to obtain higher catalytic activity toward clean energy and fuel conversion. Since oxygen release via oxygen vacancy formation in the host oxide is behind oxide reduction and metal exsolution, we hypothesize that the kinetics of metal exsolution should depend on the kinetics of oxygen release, in addition to the kinetics of metal cation diffusion. Here, we probe the surface exsolution kinetics both experimentally and theoretically using thin-film perovskite SrTi0.65Fe0.35O3 (STF) as a model system. We quantitatively demonstrated that in this system the surface oxygen release governs the metal nanoparticle exsolution kinetics. As a result, by increasing the oxygen release rate in STF, either by reducing the sample thickness or by increasing the surface reactivity, one can effectively accelerate the Fe0 exsolution kinetics. Fast oxygen release kinetics in STF not only shortened the prereduction time prior to the exsolution onset, but also increased the total quantity of exsolved Fe0 over time, which agrees well with the predictions from our analytical kinetic modeling. The consistency between the results obtained from in situ experiments and analytical modeling provides a predictive capability for tailoring exsolution, and highlights the importance of engineering host oxide surface oxygen release kinetics in designing exsolved nanocatalysts.

Charged species redistribution at electrochemical interfaces: a model system of the zirconium oxide/water interface.

Quantifying the local distribution of charged defects in the solid state and charged ions in liquid solution near the oxide/liquid interface is key to understanding a range of important electrochemical processes, including oxygen reduction and evolution, corrosion and hydrogen evolution reactions. Based on a grand canonical approach relying on the electrochemical potential of individual charged species, a unified treatment of charged defects on the solid side and ions on the water side can be established. This approach is compatible with first-principles calculations where the formation free energy of individual charged species can be calculated and modulated by imposing certain electrochemical potential. Herein, we apply this framework to a system of monoclinic ZrO2(1̄11)/water interface. The structure, defect chemistry and dynamical behavior of the electric double layer and space charge layer are analyzed with different pH values, water chemistry and doping elements in zirconium oxide. The model predicts ZrO2 solubility in water and the point of zero charge consistent with the experimentally-measured values. We reveal the effect of dopant elements on the concentrations of oxygen and hydrogen species at the surface of the ZrO2 passive layer in contact with water, uncovering an intrinsic trade-off between oxygen diffusion and hydrogen pickup during the corrosion of zirconium alloys. The solid/water interface model established here serves as the basis for modeling reaction and transport kinetics under doping and water chemistry effects.

Exsolution-Driven Surface Transformation in the Host Oxide.

Exsolution synthesizes self-assembled metal nanoparticle catalysts via phase precipitation. An overlooked aspect in this method thus far is how exsolution affects the host oxide surface chemistry and structure. Such information is critical as the oxide itself can also contribute to the overall catalytic activity. Combining X-ray and electron probes, we investigated the surface transformation of thin-film SrTi0.65Fe0.35O3 during Fe0 exsolution. We found that exsolution generates a highly Fe-deficient near-surface layer of about 2 nm thick. Moreover, the originally single-crystalline oxide near-surface region became partially polycrystalline after exsolution. Such drastic transformations at the surface of the oxide are important because the exsolution-induced nonstoichiometry and grain boundaries can alter the oxide ion transport and oxygen exchange kinetics and, hence, the catalytic activity toward water splitting or hydrogen oxidation reactions. These findings highlight the need to consider the exsolved oxide surface, in addition to the metal nanoparticles, in designing the exsolved nanocatalysts.

Controlling the Size of Au Nanoparticles on Reducible Oxides with the Electrochemical Potential.

Controlling the size of Au nanoparticles (NPs) and their interaction with the oxide support is important for their catalytic performance in chemical reactions, such as CO oxidation and water-gas shift. It is known that the oxygen vacancies at the surface of support oxides form strong chemical bonding with the Au NPs and inhibit their coarsening and deactivation. The resulting Au/oxygen vacancy interface also acts as an active site for oxidation reactions. Hence, small Au NPs are needed to increase the density of the Au/oxide interface. A dynamic way to control the size of the Au NPs on an oxide support is desirable but has been missing in the field. Here, we demonstrate an electrochemical method to control the size of the Au NPs by controlling the surface oxygen vacancy concentration of the support oxide. Oxides with different reducibilities, La0.8Ca0.2MnO3±Î´ and Pr0.1Ce0.9O2-δ, are used as model support oxides. By applying the electrochemical potential, we achieve a wide range of effective oxygen pressures, pO2 (10-37-1014 atm), in the support oxides. Applying the cathodic potential creates a high concentration of oxygen vacancies and forms finely distributed Au NPs with sizes of 7-13 nm at 700-770 °C in 10 min, while the anodic potential oxidizes the surface and increases the size of the Au NPs. The onset cathodic potential required to create small Au NPs depends strongly on the reducibility of the support oxide. The Au NPs did not undergo sintering even at 700-770 °C under the cathodic potential and also were stable in catalytically relevant conditions without potential.

Anodic Shock-Triggered Exsolution of Metal Nanoparticles from Perovskite Oxide.

Nanoparticles decorated electrodes (NDEs) are useful in fuel cells, electrolyzers, water treatment, and chemical synthesis. Here, we show that by rapidly bringing a mixed ionic-electronic conductor outside its electrochemical stability window, one can achieve uniform dispersion of metallic nanoparticles inside its bulk and at the surface and improve its electrocatalytic performance when back under normal functional conditions. Surprisingly, this can happen under anodic as well as cathodic current/voltage shocks in an ABO3 perovskite oxide, La0.4Ca0.4Ti0.88Fe0.06Ni0.06O3-δ (LCTFN), across a wide range of H2/O2 gas environments at 800 °C. One possible mechanism for bulk Fe0/Ni0 precipitation under anodic shock condition is the incomplete oxygen oxidation (O2- → Oα-, 0 < α < 2), migration and escape of oxygen to interfaces, and "whiplash" transition-metal reduction due to low electronic conductivity. We show that both cathodic and anodic shocks can produce NDEs to enhance electrocatalytic performance, potentially improving the flexibility of this approach in practical devices.

CMOS-Compatible Protonic Programmable Resistor Based on Phosphosilicate Glass Electrolyte for Analog Deep Learning.

Ion intercalation based programmable resistors have emerged as a potential next-generation technology for analog deep-learning applications. Proton, being the smallest ion, is a very promising candidate to enable devices with high modulation speed, low energy consumption, and enhanced endurance. In this work, we report on the first back-end CMOS-compatible nonvolatile protonic programmable resistor enabled by the integration of phosphosilicate glass (PSG) as the proton solid electrolyte layer. PSG is an outstanding solid electrolyte material that displays both excellent protonic conduction and electronic insulation characteristics. Moreover, it is a well-known material within conventional Si fabrication, which enables precise deposition control and scalability. Our scaled all-solid-state three-terminal devices show desirable modulation characteristics in terms of symmetry, retention, endurance, and energy efficiency. Protonic programmable resistors based on phosphosilicate glass, therefore, represent promising candidates to realize nanoscale analog crossbar processors for monolithic CMOS integration.

Bi-directional tuning of thermal transport in SrCoOx with electrochemically induced phase transitions.

Unlike the wide-ranging dynamic control of electrical conductivity, there does not exist an analogous ability to tune thermal conductivity by means of electric potential. The traditional picture assumes that atoms inserted into a material's lattice act purely as a source of scattering for thermal carriers, which can only reduce thermal conductivity. In contrast, here we show that the electrochemical control of oxygen and proton concentration in an oxide provides a new ability to bi-directionally control thermal conductivity. On electrochemically oxygenating the brownmillerite SrCoO2.5 to the perovskite SrCoO3-δ, the thermal conductivity increases by a factor of 2.5, whereas protonating it to form hydrogenated SrCoO2.5 effectively reduces the thermal conductivity by a factor of four. This bi-directional tuning of thermal conductivity across a nearly 10 ± 4-fold range at room temperature is achieved by using ionic liquid gating to trigger the 'tri-state' phase transitions in a single device. We elucidated the effects of these anionic and cationic species, and the resultant changes in lattice constants and lattice symmetry on thermal conductivity by combining chemical and structural information from X-ray absorption spectroscopy with thermoreflectance thermal conductivity measurements and ab initio calculations. This ability to control multiple ion types, multiple phase transitions and electronic conductivity that spans metallic through to insulating behaviour in oxides by electrical means provides a new framework for tuning thermal transport over a wide range.

Precipitation of dopants on acceptor-doped LaMnO3±Î´ revealed by defect chemistry from first principles.

Perovskite oxides degrade at elevated temperatures while precipitating dopant-rich particles on the surface. A knowledge-based improvement of surface stability requires a fundamental and quantitative understanding of the dopant precipitation mechanism on these materials. We propose that dopant precipitation is a consequence of the variation of dopant solubility between calcination and operating conditions in solid oxide fuel cells (SOFCs) and electrolyzer cells (SOECs). To study dopant precipitation, we use 20% (D = Ca, Sr, Ba)-doped LaMnO3+δ (LDM20) as a model system. We employ a defect model taking input from density functional theory calculations. The defect model considers the equilibration of LDM20 with a reservoir consisting of dopant oxide (DO), peroxide (DO2), and O2 in the gas phase. The equilibrated non-stoichiometry of the A-site and B-site as a function of temperature, T, and oxygen partial pressure, p(O2), reveals three regimes for LDM20: A-site deficient (oxidizing conditions), A-site rich (atmospheric conditions), and near-stoichiometric (reducing conditions). Assuming an initial A/B non-stoichiometry, we compute the dopant precipitation boundaries in a p-T phase diagram. Our model predicts precipitation both under reducing (DO) and under highly oxidizing conditions (DO2). We found precipitation under anodic, SOEC conditions to be promoted by large dopant size, while under cathodic, SOFC conditions precipitation is promoted by initial A-site excess. The main driving forces for precipitation are oxygen uptake by the condensed phase under oxidizing conditions and oxygen release assisted by B-site vacancies under reducing conditions. Possible strategies for mitigating dopant precipitation under in electrolytic and fuel cell conditions are discussed.

Strongly correlated perovskite lithium ion shuttles.

Solid-state ion shuttles are of broad interest in electrochemical devices, nonvolatile memory, neuromorphic computing, and biomimicry utilizing synthetic membranes. Traditional design approaches are primarily based on substitutional doping of dissimilar valent cations in a solid lattice, which has inherent limits on dopant concentration and thereby ionic conductivity. Here, we demonstrate perovskite nickelates as Li-ion shuttles with simultaneous suppression of electronic transport via Mott transition. Electrochemically lithiated SmNiO3 (Li-SNO) contains a large amount of mobile Li+ located in interstitial sites of the perovskite approaching one dopant ion per unit cell. A significant lattice expansion associated with interstitial doping allows for fast Li+ conduction with reduced activation energy. We further present a generalization of this approach with results on other rare-earth perovskite nickelates as well as dopants such as Na+ The results highlight the potential of quantum materials and emergent physics in design of ion conductors.

Electrochemical Polarization Dependence of the Elastic and Electrostatic Driving Forces to Aliovalent Dopant Segregation on LaMnO3.

Segregation of aliovalent dopant cations is a common degradation pathway on perovskite oxide surfaces in energy conversion and catalysis applications. Here we focus on resolving quantitatively how dopant segregation is affected by oxygen chemical potential, which varies over a wide range in electrochemical and thermochemical energy conversion reactions. We employ electrochemical polarization to tune the oxygen chemical potential over many orders of magnitude. Altering the effective oxygen chemical potential causes the oxygen nonstoichiometry to change in the electrode. This then influences the mechanisms underlying the segregation of aliovalent dopants. These mechanisms are (i) the formation of oxygen vacancies that couples to the electrostatic energy of the dopant in the perovskite lattice and (ii) the elastic energy of the dopant due to cation size mismatch, which also promotes the reaction of the dopant with O2 from the gas phase. The present study resolves these two contributions over a wide range of effective oxygen pressures. Ca-, Sr-, and Ba-doped LaMnO3 are selected as model systems, where the dopants have the same charge but different ionic sizes. We found that there is a transition between the electrostatically and elastically dominated segregation regimes, and the transition shifted to a lower oxygen pressure with increasing cation size. This behavior is consistent with the results of our ab initio thermodynamics calculations. The present study provides quantitative insights into how the elastic energy and the electrostatic energy determine the extent of segregation for a given overpotential and atmosphere relevant to the operating conditions of perovskite oxides in energy conversion applications.

Multi-Foulant-Resistant Material Design by Matching Coating-Fluid Optical Properties.

The buildup of corrosion deposits, known as fouling, seriously hinders large-scale energy production. From nuclear power plants to geothermal reservoirs, fouling increases system pressure drops, impedes heat transfer, and accelerates corrosion, leading to derating and early failure. Here, we investigate the collodial interactions between multiple foulants and coated surfaces, with the aim of discovering principles for minimizing the adhesion of foulants to them. We hypothesize that matching the full refractive index spectrum of a coating to its surrounding fluid minimizes the adhesion of all foulants entrained within and that the Lifshitz theory is sufficient to predict which materials will be multi-foulant-resistant. First-principle calculations of Hamaker constants and refractive indices of six foulants on six coatings in water correlate well to direct measurements of adhesion by atomic force microscopy (AFM)-based force spectroscopy. Amorphous 2% fluorine-doped tin oxide, crystalline SiO2, CaF2, and Na3AlF6, which all nearly match the refractive index spectrum of water, successfully resisted adhesion of six diverse foulant materials in aqueous AFM measurements. The validation of this design principle may be expanded to design multi-fouling-resistant coatings for any system in which van der Waals forces are the dominant adhesion mechanism.

Origin of fast oxide ion diffusion along grain boundaries in Sr-doped LaMnO3.

The prospect of significantly enhanced oxide ion diffusion along grain boundaries in Sr-doped LaMnO3 (LSM) was investigated by means of density functional theory calculations applied to a Σ5 (3 1 0)[0 0 1] grain boundary. The structure of the grain boundary was optimized by rigid body translation, and segregation energies were calculated for oxygen vacancies and Sr-acceptors. Two potentially fast diffusion paths were identified along the grain boundary core based on the interconnectivity between neighbouring sites with a strong tendency for segregation of oxygen vacancies. The migration barriers for these paths, obtained with the nudged elastic band method, amounted to about 0.6 eV. Based on the obtained migration barriers and concentrations of oxygen vacancies for the relevant core sites, the grain boundary diffusion coefficient was estimated to be enhanced by 3 to 5 orders of magnitude relative to the bulk in the temperature range 500-900 °C. Space-charge effects were determined to be quite insignificant for the transport properties of LSM grain boundaries.

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface.

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.

Polarizing Oxygen Vacancies in Insulating Metal Oxides under a High Electric Field.

We demonstrate a thermodynamic formulation to quantify defect formation energetics in an insulator under a high electric field. As a model system, we analyzed neutral oxygen vacancies (color centers) in alkaline-earth-metal binary oxides using density functional theory, Berry phase calculations, and maximally localized Wannier functions. The work of polarization lowers the field-dependent electric Gibbs energy of formation of this defect. This is attributed mainly to the ease of polarizing the two electrons trapped in the vacant site, and secondarily to the defect induced reduction in bond stiffness and softening of phonon modes. The formulation and analysis have implications for understanding the behavior of insulating oxides in electronic, magnetic, catalytic, and electrocaloric devices under a high electric field.

Predicting point defect equilibria across oxide hetero-interfaces: model system of ZrO2/Cr2O3.

We present a multi-scale approach to predict equilibrium defect concentrations across oxide/oxide hetero-interfaces. There are three factors that need to be taken into account simultaneously for computing defect redistribution around the hetero-interfaces: the variation of local bonding environment at the interface as epitomized in defect segregation energies, the band offset at the interface, and the equilibration of the chemical potentials of species and electrons via ionic and electronic drift-diffusion fluxes. By including these three factors from the level of first principles calculation, we build a continuum model for defect redistribution by concurrent solution of Poisson's equation for the electrostatic potential and the steady-state equilibrium drift-diffusion equation for each defect. This model solves for and preserves the continuity of the electric displacement field throughout the interfacial core zone and the extended space charge zones. We implement this computational framework to a model hetero-interface between the monoclinic zirconium oxide, m-ZrO2, and the chromium oxide Cr2O3. This interface forms upon the oxidation of zirconium alloys containing chromium secondary phase particles. The model explains the beneficial effect of the oxidized Cr particles on the corrosion and hydrogen resistance of Zr alloys. Under oxygen rich conditions, the ZrO2/Cr2O3 heterojunction depletes the oxygen vacancies and the sum of electrons and holes in the extended space charge zone in ZrO2. This reduces the transport of oxygen and electrons thorough ZrO2 and slows down the metal oxidation rate. The enrichment of free electrons in the space charge zone is expected to decrease the hydrogen uptake through ZrO2. Moreover, our analysis provides a clear anatomy of the components of interfacial electric properties; a zero-Kelvin defect-free contribution and a finite temperature defect contribution. The thorough analytical and numerical treatment presented here quantifies the rich coupling between defect chemistry, thermodynamics and electrostatics which can be used to design and control oxide hetero-interfaces.

Enhanced intermediate-temperature CO2 splitting using nonstoichiometric ceria and ceria-zirconia.

CO2 splitting via thermo-chemical or reactive redox has emerged as a novel and promising carbon-neutral energy solution. Its performance depends critically on the properties of the oxygen carriers (OC). Ceria is recognized as one of the most promising OC candidates, because of its fast chemistry, high ionic diffusivity, and large oxygen storage capacity. The fundamental surface ion-incorporation pathways, along with the role of surface defects and the adsorbates remain largely unknown. This study presents a detailed kinetics study of CO2 splitting using CeO2 and Ce0.5Zr0.5O2 (CZO) in the temperature range 600-900 °C. Given our interest in fuel-assisted reduction, we limit our study to relatively lower temperatures to avoid excessive sintering and the need for high temperature heat. Compared to what has been reported previously, we observe higher splitting kinetics, resulting from the utilization of fine particles and well-controlled experiments which ensure a surface-limited-process. The peak rates with CZO are 85.9 µmole g-1 s-1 at 900 °C and 61.2 µmole g-1 s-1 at 700 °C, and those of CeO2 are 70.6 µmole g-1 s-1 and 28.9 µmole g-1 s-1. Kinetic models are developed to describe the ion incorporation dynamics, with consideration of CO2 activation and the charge transfer reactions. CO2 activation energy is found to be -120 kJ mole-1 for CZO, half of that for CeO2, while CO desorption energetics is analogous between the two samples with a value of ∼160 kJ mole-1. The charge-transfer process is found to be the rate-limiting step for CO2 splitting. The evolution of CO32- with surface Ce3+ is examined based on the modeled kinetics. We show that the concentration of CO32- varies with Ce3+ in a linear-flattened-decay pattern, resulting from a mismatch between the kinetics of the two reactions. Our study provides new insights into the significant role of surface defects and adsorbates in determining the splitting kinetics.

Voltage-Controlled Topotactic Phase Transition in Thin-Film SrCoOx Monitored by In Situ X-ray Diffraction.

Topotactic phase transition of functional oxides induced by changes in oxygen nonstoichiometry can largely alter multiple physical and chemical properties, including electrical conductivity, magnetic state, oxygen diffusivity, and electrocatalytic reactivity. For tuning these properties reversibly, feasible means to control oxygen nonstoichiometry-dependent phase transitions in functional oxides are needed. This paper describes the use of electrochemical potential to induce phase transition in strontium cobaltites, SrCoOx (SCO) between the brownmillerite (BM) phase, SrCoO2.5, and the perovskite (P) phase, SrCoO3₋δ. To monitor the structural evolution of SCO, in situ X-ray diffraction (XRD) was performed on an electrochemical cell having (001) oriented thin-film SrCoOx as the working electrode on a single crystal (001) yttria-stabilized zirconia electrolyte in air. In order to change the effective pO2 in SCO and trigger the phase transition from BM to P, external electrical biases of up to 200 mV were applied across the SCO film. The phase transition from BM to P phase could be triggered at a bias as low as 30 mV, corresponding to an effective pO2 of 1 atm at 500 °C. The phase transition was fully reversible and the epitaxial film quality was maintained after reversible phase transitions. These results demonstrate the use of electrical bias to obtain fast and easily accessible switching between different phases as well as distinct physical and chemical properties of functional oxides as exemplified here for SCO.

Mapping strain rate dependence of dislocation-defect interactions by atomistic simulations.

Probing the mechanisms of defect-defect interactions at strain rates lower than 10(6) s(-1) is an unresolved challenge to date to molecular dynamics (MD) techniques. Here we propose an original atomistic approach based on transition state theory and the concept of a strain-dependent effective activation barrier that is capable of simulating the kinetics of dislocation-defect interactions at virtually any strain rate, exemplified within 10(-7) to 10(7) s(-1). We apply this approach to the problem of an edge dislocation colliding with a cluster of self-interstitial atoms (SIAs) under shear deformation. Using an activation-relaxation algorithm [Kushima A, et al. (2009) J Chem Phys 130:224504], we uncover a unique strain-rate-dependent trigger mechanism that allows the SIA cluster to be absorbed during the process, leading to dislocation climb. Guided by this finding, we determine the activation barrier of the trigger mechanism as a function of shear strain, and use that in a coarse-graining rate equation formulation for constructing a mechanism map in the phase space of strain rate and temperature. Our predictions of a crossover from a defect recovery at the low strain-rate regime to defect absorption behavior in the high strain-rate regime are validated against our own independent, direct MD simulations at 10(5) to 10(7) s(-1). Implications of the present approach for probing molecular-level mechanisms in strain-rate regimes previously considered inaccessible to atomistic simulations are discussed.

Dislocations in SrTiO3: easy to reduce but not so fast for oxygen transport.

The effect of dislocations on the chemical, electrical and transport properties in oxide materials is important for electrochemical devices, such as fuel cells and resistive switches, but these effects have remained largely unexplored at the atomic level. In this work, by using large-scale atomistic simulations, we uncover how a ⟨100⟩{011} edge dislocation in SrTiO3, a prototypical perovskite oxide, impacts the local defect chemistry and oxide ion transport. We find that, in the dilute limit, oxygen vacancy formation energy in SrTiO3 is lower at sites close to the dislocation core, by as much as 2 eV compared to that in the bulk. We show that the formation of a space-charge zone based on the redistribution of charged oxygen vacancies can be captured quantitatively at atomistic level by mapping the vacancy formation energies around the dislocation. Oxide-ion diffusion was studied for a low vacancy concentration regime (ppm level) and a high vacancy concentration regime (up to 2.5%). In both cases, no evidence of pipe-diffusion, i.e., significantly enhanced mobility of oxide ions, was found as determined from the calculated migration barriers, contrary to the case in metals. However, in the low vacancy concentration regime, the vacancy accumulation at the dislocation core gives rise to a higher diffusion coefficient, even though the oxide-ion mobility itself is lower than that in the bulk. Our findings have important implications for applications of perovskite oxides for information and energy technologies. The observed lower oxygen vacancy formation energy at the dislocation core provides a quantitative and direct explanation for the electronic conductivity of dislocations in SrTiO3 and related oxides studied for red-ox based resistive switching. Reducibility and electronic transport at dislocations can also be quantitatively engineered into active materials for fuel cells, catalysis, and electronics.

Improved electrochemical stability at the surface of La(0.8)Sr(0.2)CoO3 achieved by surface chemical modification.

The degradation of the surface chemistry on perovskite (ABO3) oxides is a critical issue for their performance in energy conversion systems such as solid oxide fuel/electrolysis cells and in splitting of H2O and CO2 to produce fuels. This degradation is typically in the form of segregation and phase separation of dopant cations from the A-site, driven by elastic and electrostatic energy minimization and kinetic demixing. In this study, deposition of Ti at the surface was found to hinder the dopant segregation and the corresponding electrochemical degradation on a promising SOFC cathode material, La(0.8)Sr(0.2)CoO3 (LSC). The surface of the LSC films was modified by Ti (denoted as LSC-T) deposited from a TiCl4 solution. The LSC and LSC-T thin films were investigated by electrochemical impedance spectroscopy, nano-probe Auger electron spectroscopy, and X-ray photoelectron spectroscopy (XPS), upon annealing at 420-530 °C in air up to about 90 hours. The oxygen exchange coefficient, k(q), on LSC-T cathodes was found to be up to 8 times higher than that on LSC cathodes at 530 °C and retained its stability. Sr-rich insulating particles formed at the surface of the annealed LSC and LSC-T films, but with significantly less coverage of such particles on the LSC-T. From this result, it appears that modification of the LSC surface with Ti reduces the segregation of the blocking Sr-rich particles at the surface, and a larger area on LSC surface (with a higher Sr doping level in the lattice) is available for the oxygen reduction reaction. The stabilization of the LSC surface through Ti-deposition can open a new route for designing surface modifications on perovskite oxide electrodes for high temperature electro- and thermo-chemical applications.