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The novel material class of high entropy oxides with their unique and unexpected physicochemical properties is a candidate for energy applications. Herein, it is reported for the first time about the physico- and (photo-) electrochemical properties of ordered mesoporous (CoNiCuZnMg)Fe2 O4 thin films synthesized by a soft-templating and dip-coating approach. The A-site high entropy ferrites (HEF) are composed of periodically ordered mesopores building a highly accessible inorganic nanoarchitecture with large specific surface areas. The mesoporous spinel HEF thin films are found to be phase-pure and crack-free on the meso- and macroscale. The formation of the spinel structure hosting six distinct cations is verified by X-ray-based characterization techniques. Photoelectron spectroscopy gives insight into the chemical state of the implemented transition metals supporting the structural characterization data. Applied as photoanode for photoelectrochemical water splitting, the HEFs are photostable over several hours but show only low photoconductivity owing to fast surface recombination, as evidenced by intensity-modulated photocurrent spectroscopy. When applied as oxygen evolution reaction electrocatalyst, the HEF thin films possess overpotentials of 420 mV at 10 mA cm-2 in 1 m KOH. The results imply that the increase of the compositional disorder enhances the electronic transport properties, which are beneficial for both energy applications.
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Long-term stability of heterogeneous catalysts is an omnipresent and pressing concern in industrial processes. Catalysts with high activity and selectivity can be searched for by high-throughput screening methods based maybe on educated guesses provided by ab initio thermodynamics or scaling relations. However, high-throughput screening is not feasible and is hardly able to identify long-term stable catalyst so that a rational and knowledge-driven approach is called for to identify potentially stable and active catalysts. Unfortunately, our current microscopic understanding on stability issues is quite poor. We propose that this gap in knowledge can be at least partly closed by investigating dedicated model catalyst materials with well-defined morphology that allow for a tight link to theory and the application of standard characterization methods. This topic is highly interdisciplinary, combining sophisticated inorganic synthesis with catalysis research, surface chemistry, and powerful theoretical modeling. In this Account, we focus on the stability issues of Deacon catalysts (RuO2 and CeO2-based materials) for recovering Cl2 from HCl by aerobic oxidation and how to deepen our microscopic insight into the underlying processes. The main stability problems under harsh Deacon reaction conditions concomitant with a substantial loss in activity arise from deep chlorination of the catalyst, leaching of volatile chlorides and oxychlorides, and decrease in active surface area by particle sintering. In general, powder materials with undefined particle shape are not well suited for examining catalyst stability, because changes in the morphology are difficult to recognize, for instance, by electron microscopy. Rather, we focus here on model materials with well-defined starting morphologies, including electrospun nanofibers, shape-controlled nanoparticles, and well-defined ultrathin crystalline layers. CeO2 is able to stabilize shape-controlled particles, exposing a single facet orientation so that comparing activity and stability studies can reveal structure sensitive properties. We develop a quasi-steady-state kinetic approach that allows us to model the catalyst chlorination as a function of temperature and gas feed composition. For the case of pure CeO2 nanocubes, this simple approach predicts chlorination to be efficiently suppressed by addition of little amounts of water in the reaction feed or by keeping the catalyst at higher temperature. Both process parameters have great impact on the actual reactor design. Thermal stabilization of CeO2 by intermixing Zr has been known in automotive exhaust catalysis for decades, but this does not necessarily imply also chemical stabilization of CeO2 against bulk-chlorination since Zr can readily form volatile ZrCl4 and may quickly lose its stabilizing effect. Nevertheless, with model experiments the stabilizing effect of Zr in the Deacon process over mixed CexZr1-xO2 nanorods is clearly evidenced. Even higher stability can be accomplished with ultrathin CeO2 coatings on preformed ZrO2 particles, demonstrating the great promise of atomic layer deposition (ALD) in catalysis synthesis.
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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.
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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.
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While lateral interaction models for reactions at surfaces have steadily gained popularity and grown in terms of complexity, their use in chemical kinetics has been impeded by the low performance of current kinetic Monte Carlo (KMC) algorithms. The origins of the additional computational cost in KMC simulations with lateral interactions are traced back to the more elaborate cluster expansion Hamiltonian, the more extensive rate updating, and to the impracticality of rate-catalog-based algorithms for interacting adsorbate systems. Favoring instead site-based algorithms, we propose three ways to reduce the cost of KMC simulations: (1) representing the lattice energy by a smaller Supercluster Hamiltonian without loss of accuracy, (2) employing the subtraction schemes for updating key quantities in the simulation that undergo only small, local changes during a reaction event, and (3) applying efficient search algorithms from a set of established methods (supersite approach). The cost of the resulting algorithm is fixed with respect to the number of lattice sites for practical lattice sizes and scales with the square of the range of lateral interactions. The overall added cost of including a complex lateral interaction model amounts to less than a factor 3. Practical issues in implementation due to finite numerical accuracy are discussed in detail, and further suggestions for treating long-range lateral interactions are made. We conclude that, while KMC simulations with complex lateral interaction models are challenging, these challenges can be overcome by modifying the established variable step-size method by employing the supercluster, subtraction, and supersite algorithms (SSS-VSSM). © 2019 Wiley Periodicals, Inc.
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Catalytic hydrogenation of CO2 to methanol has attracted lots of attention as it makes CO2 useable as a sustainable carbon source. This study combines theoretical calculations based on the dummy catalytic cycle model with experimental studies on the performance and degradation of indium-based model catalysts for methanol synthesis. In detail, the reversibility of phase transitions in the In2 O3 /In(OH)3 system under industrial methanol synthesis conditions are investigated depending on conversion, temperature and feed ratio. The dummy catalytic cycle model predicts a peculiar degradation behavior of In(OH)3 at 275 °C depending on the water formed either by methanol synthesis or the competing reverse water-gas-shift reaction. These results were validated by dedicated experimental studies confirming the predicted trends. Moreover, X-ray diffraction and thermogravimetric analysis proved the ensuing phase transition between the indium species. Finally, the validated model is used to predict how hydrogen drop out will affect the stability of the catalyst and derive practical strategies to prevent irreversible catalyst degradation.
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First principles-based kinetic Monte Carlo (kMC) simulations are performed for the CO oxidation on RuO(2) (110) under steady-state reaction conditions. The simulations include a set of elementary reaction steps with activation energies taken from three different ab initio density functional theory studies. Critical comparison of the simulation results reveals that already small variations in the activation energies lead to distinctly different reaction scenarios on the surface, even to the point where the dominating elementary reaction step is substituted by another one. For a critical assessment of the chosen energy parameters, it is not sufficient to compare kMC simulations only to experimental turnover frequency (TOF) as a function of the reactant feed ratio. More appropriate benchmarks for kMC simulations are the actual distribution of reactants on the catalyst's surface during steady-state reaction, as determined by in situ infrared spectroscopy and in situ scanning tunneling microscopy, and the temperature dependence of TOF in the from of Arrhenius plots.
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BACKGROUND: Chemo- and radiotherapeutic responses of leukemia cells are modified by integrin-mediated adhesion to extracellular matrix. To further characterize the molecular mechanisms by which beta1 integrins confer radiation and chemoresistance, HL60 human acute promyelocytic leukemia cells stably transfected with beta1 integrin and A3 Jurkat T-lymphoma cells deficient for Fas-associated death domain protein or procaspase-8 were examined. METHODOLOGY/PRINCIPAL FINDINGS: Upon exposure to X-rays, Ara-C or FasL, suspension and adhesion (fibronectin (FN), laminin, collagen-1; 5-100 microg/cm(2) coating concentration) cultures were processed for measurement of apoptosis, mitochondrial transmembrane potential (MTP), caspase activation, and protein analysis. Overexpression of beta1 integrins enhanced the cellular sensitivity to X-rays and Ara-C, which was counteracted by increasing concentrations of matrix proteins in association with reduced caspase-3 and -8 activation and MTP breakdown. Usage of stimulatory or inhibitory anti beta1 integrin antibodies, pharmacological caspase or phosphatidylinositol-3 kinase (PI3K) inhibitors, coprecipitation experiments and siRNA-mediated beta1 integrin silencing provided further data showing an interaction between FN-ligated beta1 integrin and PI3K/Akt for inhibiting procaspase-8 cleavage. CONCLUSIONS/SIGNIFICANCE: The presented data suggest that the ligand status of beta1 integrins is critical for their antiapoptotic effect in leukemia cells treated with Ara-C, FasL or ionizing radiation. The antiapoptotic actions involve formation of a beta1 integrin/Akt complex, which signals to prevent procaspase-8-mediated induction of apoptosis in a PI3K-dependent manner. Antagonizing agents targeting beta1 integrin and PI3K/Akt signaling in conjunction with conventional therapies might effectively reduce radiation- and drug-resistant tumor populations and treatment failure in hematological malignancies.