Crystal-facet-dependent surface transformation dictates the oxygen evolution reaction activity in lanthanum nickelate

Electrocatalysts are the cornerstone in the transition to sustainable energy technologies and chemical processes. Surface transformations under operation conditions dictate the activity and stability. However, the dependence of the surface structure and transformation on the exposed crystallographic facet remains elusive, impeding rational catalyst design. We investigate the (001), (110) and (111) facets of a LaNiO3−δ electrocatalyst for water oxidation using electrochemical measurements, X-ray spectroscopy, and density functional theory calculations with a Hubbard U term. We reveal that the (111) overpotential is ≈ 30−60 mV lower than for the other facets. While a surface transformation into oxyhydroxide-like NiOO(H) may occur for all three orientations, it is more pronounced for (111). A structural mismatch of the transformed layer with the underlying perovskite for (001) and (110) influences the ratio of Ni2+ and Ni3+ to Ni4+ sites during the reaction and thereby the binding energy of reaction intermediates, resulting in the distinct catalytic activities of the transformed facets.</p

Electronic and Structural Disorder of the Epitaxial La_0.67Sr_0.33MnO₃ Surface

Understanding and tuning epitaxial complex oxide films are crucial in controlling the behavior of devices and catalytic processes. Substrate-induced strain, doping, and layer growth are known to influence the electronic and magnetic properties of the bulk of the film. In this study, we demonstrate a clear distinction between the bulk and surface of thin films of La0.67Sr0.33MnO3 in terms of chemical composition, electronic disorder, and surface morphology. We use a combined experimental approach of X-ray-based characterization methods and scanning probe microscopy. Using X-ray diffraction and resonant X-ray reflectivity, we uncover surface nonstoichiometry in the strontium and lanthanum alongside an accumulation of oxygen vacancies. With scanning tunneling microscopy, we observed an electronic phase separation (EPS) on the surface related to this nonstoichiometry. The EPS is likely driving the temperature-dependent resistivity transition and is a cause of proposed mixed-phase ferromagnetic and paramagnetic states near room temperature in these thin films.</p

In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film.</p

Beyond domain alignment: Revealing the effect of intrinsic magnetic order on electrochemical water splitting

To reach a long term viable green hydrogen economy, rational design of active oxygen evolution reaction (OER) catalysts is critical. An important hurdle in this reaction originates from the fact that the reactants are singlet molecules, whereas the oxygen molecule has a triplet ground state with parallel spin alignment, implying that magnetic order in the catalyst is essential. Accordingly, multiple experimentalists reported a positive effect of external magnetic fields on OER activity of ferromagnetic catalysts. However, it remains a challenge to investigate the influence of the intrinsic magnetic order on catalytic activity. Here, we tuned the intrinsic magnetic order of epitaxial La$_{0.67}$Sr$_{0.33}$MnO$_{3}$ thin film model catalysts from ferro- to paramagnetic by changing the temperature in-situ during water electrolysis. Using this strategy, we show that ferromagnetic ordering below the Curie temperature enhances OER activity. Moreover, we show a slight current density enhancement upon application of an external magnetic field and find that the dependence of magnetic field direction correlates with the magnetic anisotropy in the catalyst film. Our work thus suggests that both the intrinsic magnetic order in La$_{0.67}$Sr$_{0.33}$MnO$_{3}$ films and magnetic domain alignment increase their catalytic activity. We observe no long-range magnetic order at the catalytic surface, implying that the OER enhancement is connected to the magnetic order of the bulk catalyst. Combining the effects found with existing literature, we propose a unifying picture for the spin-polarized enhancement in magnetic oxide catalysts.Comment: The following article will be submitted to Applied Physics Reviews. Main text (incl. references) 19 pages, 8 figures. Supplementary text 9 pages, 13 figure

The effect of intrinsic magnetic order on electrochemical water splitting

To reach a long term viable green hydrogen economy, rational design of active oxygen evolution reaction (OER) catalysts is critical. An important hurdle in this reaction originates from the fact that the reactants are singlet molecules, whereas the oxygen molecule has a triplet ground state with parallel spin alignment, implying that magnetic order in the catalyst is essential. Accordingly, multiple experimentalists reported a positive effect of external magnetic fields on OER activity of ferromagnetic catalysts. However, it remains a challenge to investigate the influence of the intrinsic magnetic order on catalytic activity. Here, we tuned the intrinsic magnetic order of epitaxial La0.67Sr0.33MnO3 thin film model catalysts from ferro- to paramagnetic by changing the temperature in situ during water electrolysis. Using this strategy, we show that ferromagnetic ordering below the Curie temperature enhances OER activity. Moreover, we show a slight current density enhancement upon application of an external magnetic field and find that the dependence of magnetic field direction correlates with the magnetic anisotropy in the catalyst film. Our work, thus, suggests that both the intrinsic magnetic order in La0.67Sr0.33MnO3 films and magnetic domain alignment increase their catalytic activity. We observe no long-range magnetic order at the catalytic surface, implying that the OER enhancement is connected to the magnetic order of the bulk catalyst. Combining the effects found with existing literature, we propose a unifying picture for the spin-polarized enhancement in magnetic oxide catalysts.</p

Orbital-overlap-driven hybridization in 3d-transition metal perovskite oxides LaMO₃ (M = Ti-Ni) and La₂CuO₄

The wide tunability of strongly correlated transition metal (TM) oxides stems from their complex electronic properties and the coupled degrees of freedom. Among the perovskite oxides family, LaMO3 (M = Ti-Ni) allows an M-dependent systematic study of the electronic structure within the same-structure-family motif. While most of the studies have been focusing on the 3d TMs and oxygen sites, the role of the rare-earth site has been far less explored. In this work, we use resonant inelastic X-ray scattering (RIXS) at the lanthanum N4,5 edges and density functional theory (DFT) to investigate the hybridization mechanisms in LaMO3. We link the spatial-overlap-driven hybridization to energetic-overlap-driven hybridization by comparing the RIXS chemical shifts and the DFT band widths. The scope is extended to highly covalent Ruddlesden-Popper perovskite La2CuO4 by intercalating lanthanum atoms to rock-salt layers. Our work evidences an observable contribution of localized lanthanum 5p and 4f orbitals in the band structure.</p

In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film

High-Strain-Induced Local Modification of the Electronic Properties of VO2Thin Films

Vanadium dioxide (VO2) is a popular candidate for electronic and optical switching applications due to its well-known semiconductor-metal transition. Its study is notoriously challenging due to the interplay of long- and short-range elastic distortions, as well as the symmetry change and the electronic structure changes. The inherent coupling of lattice and electronic degrees of freedom opens the avenue toward mechanical actuation of single domains. In this work, we show that we can manipulate and monitor the reversible semiconductor-to-metal transition of VO2 while applying a controlled amount of mechanical pressure by a nanosized metallic probe using an atomic force microscope. At a critical pressure, we can reversibly actuate the phase transition with a large modulation of the conductivity. Direct tunneling through the VO2-metal contact is observed as the main charge carrier injection mechanism before and after the phase transition of VO2. The tunneling barrier is formed by a very thin but persistently insulating surface layer of the VO2. The necessary pressure to induce the transition decreases with temperature. In addition, we measured the phase coexistence line in a hitherto unexplored regime. Our study provides valuable information on pressure-induced electronic modifications of the VO2 properties, as well as on nanoscale metal-oxide contacts, which can help in the future design of oxide electronics