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Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±Î´/La1-xSrxCoO3-δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1-ySry)2CoO4±Î´/La1-xSrxCo0.2Fe0.8O3-δ. Sr enrichment in many electrocatalysts, such as La1-xSrxMO3-δ (M = Cr, Co, Mn, or Co and Fe) and Sm1-xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst's activity while maintaining stability to design efficient, cost-effective electrocatalysts.
Assuntos
Óxidos/química , Catálise , Estrutura Molecular , Propriedades de SuperfícieRESUMO
The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent in situ studies on model electrochemical components as well as operando studies performed by our groups at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory to illustrate that AP-XPS is both a chemically and an electrically specific tool since photoelectrons carry information on both the local chemistry and electrical potentials. The applications of AP-XPS to oxygen electrocatalysis shown in this Account span well-defined studies of (1) the oxide/oxygen gas interface, (2) the oxide/water vapor interface, and (3) operando measurements of half and full electrochemical cells. Using specially designed model devices, we can expose and isolate the electrode or interface of interest to the incident X-ray beam and AP-XPS analyzer to relate the electrical potentials to the composition/chemical state of the key components and interfaces. We conclude with an outlook on new developments of AP-XPS end stations, which may provide significant improvement in the observation of dynamics over a wide range of time scales, higher spatial resolution, and improved characterization of boundary or interface layers (solid/solid and liquid/solid).
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Developing highly active and stable catalysts based on earth-abundant elements for oxygen electrocatalysis is critical to enable efficient energy storage and conversion. In this work, we took advantage of the high intrinsic oxygen reduction reaction (ORR) activity of La(0.8)Sr(0.2)MnO(3-δ) (LSMO) and the high intrinsic oxygen evolution reaction (OER) activity of Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) to develop a novel bifunctional catalyst. We used pulsed laser deposition to fabricate well-defined surfaces composed of BSCF on thin-film LSMO grown on (001)-oriented Nb-doped SrTiO3. These surfaces exhibit bifunctionality for oxygen electrocatalysis with enhanced activities and stability for both the ORR and OER that rival the state-of-the-art single- and multicomponent catalysts in the literature.
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This corrects the article DOI: 10.1038/nchem.2695.
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This corrects the article DOI: 10.1038/nchem.2695.
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Understanding how materials that catalyse the oxygen evolution reaction (OER) function is essential for the development of efficient energy-storage technologies. The traditional understanding of the OER mechanism on metal oxides involves four concerted proton-electron transfer steps on metal-ion centres at their surface and product oxygen molecules derived from water. Here, using in situ 18O isotope labelling mass spectrometry, we provide direct experimental evidence that the O2 generated during the OER on some highly active oxides can come from lattice oxygen. The oxides capable of lattice-oxygen oxidation also exhibit pH-dependent OER activity on the reversible hydrogen electrode scale, indicating non-concerted proton-electron transfers in the OER mechanism. Based on our experimental data and density functional theory calculations, we discuss mechanisms that are fundamentally different from the conventional scheme and show that increasing the covalency of metal-oxygen bonds is critical to trigger lattice-oxygen oxidation and enable non-concerted proton-electron transfers during OER.
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The performance of photoelectrodes can be modified by changing the material chemistry, geometry, and interface engineering. Specifically, nanoscale active layers can facilitate the collection of charge carriers. In heterostructure devices, the multiple material interfaces are particularly important, which at present are not well understood for oxides. Here, we report a detailed study of ultrathin (2-25 nm) LaFeO3 films grown epitaxially on Nb-doped SrTiO3. The films exhibit thickness-dependence with sensitivity to less than 10 nm in both the through-plane charge transfer conductivity and in the potential-dependent photoresponse. Supplementing photoelectrochemical measurements with X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and electrochemical impedance spectroscopy, we construct a band model that accounts for this thickness dependence via a shifting valence-band offset at the film-substrate interface and the potential-dependent overlap of the depletion regions present at both the film-substrate and film-electrolyte interfaces. These results illustrate the utility of using active layer thickness and film-substrate interactions to tune the performance of photoelectrodes, providing insight for the design of efficient heterostructure oxide photoelectrochemical devices.
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Heterostructured oxides have shown unusual electrochemical properties including enhanced catalytic activity, ion transport, and stability. In particular, it has been shown recently that the activity of oxygen electrocatalysis on the Ruddlesden-Popper/perovskite (La1-ySry)2CoO4±Î´/La1-xSrxCoO3-δ heterostructure is remarkably enhanced relative to the Ruddlesden-Popper and perovskite constituents. Here we report the first atomic-scale structure and composition of (La1-ySry)2CoO4±Î´/La1-xSrxCoO3-δ grown on SrTiO3. We observe anomalous strontium segregation from the perovskite to the interface and the Ruddlesden-Popper phase using direct X-ray methods as well as with ab initio calculations. Such Sr segregation occurred during the film growth, and no significant changes were found upon subsequent annealing in O2. Our findings provide insights into the design of highly active catalysts for oxygen electrocatalysis.
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The slow kinetics of oxygen surface exchange hinders the efficiency of high-temperature oxygen electrocatalytic devices such as solid oxide fuel cells and oxygen separation membranes. Systematic investigations of material properties that link to catalytic activity can aid in the rational design of highly active cathode materials. Here, we explore LaCoO3 thin films as a model system for tuning catalytic activity through strain-induced changes in the Co spin state. We demonstrate that Raman spectroscopy can be used to probe the Co-O bond strength at different temperatures to determine the relative spin occupancies of LaCoO3. We find that strain can be used to reduce the spin transition temperature and promote the occupation of higher spin states that weaken the Co-O bond. The decrease in Co-O bond strength and increased spin moment of the thin films result in significant enhancements of the oxygen surface exchange kinetics by up to 2 orders of magnitude.
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The electronic structure of transition metal oxides governs the catalysis of many central reactions for energy storage applications such as oxygen electrocatalysis. Here we exploit the versatility of the perovskite structure to search for oxide catalysts that are both active and stable. We report double perovskites (Ln0.5Ba0.5)CoO(3-δ) (Ln=Pr, Sm, Gd and Ho) as a family of highly active catalysts for the oxygen evolution reaction upon water oxidation in alkaline solution. These double perovskites are stable unlike pseudocubic perovskites with comparable activities such as Ba0.5Sr0.5Co0.8Fe0.2O(3-δ) which readily amorphize during the oxygen evolution reaction. The high activity and stability of these double perovskites can be explained by having the O p-band centre neither too close nor too far from the Fermi level, which is computed from ab initio studies.
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Perovskites are used to promote the kinetics of oxygen electrocatalysis in solid oxide fuel cells and oxygen permeation membranes. Little is known about the surface structure and chemistry of perovskites at high temperatures and partial oxygen pressures. Combining in situ X-ray reflectivity (XRR) and in situ ambient pressure X-ray photoelectron spectroscopy (APXPS), we report, for the first time, the evolution of the surface structure and chemistry of (001)-oriented perovskite La0.8Sr0.2CoO3-δ (LSC113) and (La0.5Sr0.5)2CoO4+δ (LSC214)-decorated LSC113 (LSC113/214) thin films as a function of temperature. Heating the (001)-oriented LSC113 surface leads to the formation of surface LSC214-like particles, which is further confirmed by ex situ Auger electron spectroscopy (AES). In contrast, the LSC113/214 surface, with activities much higher than that of LSC113, is stable upon heating. Combined in situ XRR and APXPS measurements support that Sr enrichment may occur at the LSC113 and LSC214 interface, which can be responsible for its markedly enhanced activities.