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DOE OSTI2025

Oscillatory redox behavior in oxides: Cyclic surface reconstruction and reactivity modulation via the Mars–van Krevelen mechanism

The breaking of translational symmetry at oxide surfaces gives rise to coordinatively unsaturated cations/anions and surface restructuring—key factors that govern surface reactivity. Using direct in situ environmental transmission electron microscopy (TEM) observations along with atomistic modeling, we report oscillatory redox behavior in CuO under H 2 , where cyclic surface reconstruction and reactivity modulation occur via the Mars–van Krevelen (MvK) mechanism. We observe self-switching between oxygen-rich and oxygen-deficient surface reconstructions, alternately activating and deactivating the surface for H 2 O formation. During periods of chemical inactivity, the oxygen-deficient surface undergoes slow reoxidation via lattice oxygen diffusing from subsurface and bulk reservoirs, restoring the active oxygen-rich surface termination. The inherent disparity in chemical activity among undercoordinated surface ions, along with sluggish subsurface-to-surface oxygen replenishment, drives this oscillatory redox cycle, modulating H2-induced loss of lattice oxygen at the surface and its delayed replenishment from the subsurface. This creates spatiotemporally separated redox steps at the oxide surface. The phenomena and atomistic insights presented here have significant implications for manipulating the surface reactivity of oxides by tuning the separation of these redox steps.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Redox dynamics and surface structures of an active palladium catalyst during methane oxidation

Catalysts based on palladium are among the most effective in the complete oxidation of methane. Despite extensive studies and notable advances, the nature of their catalytically active species and conceivable structural dynamics remains only partially understood. Here, we combine operando transmission electron microscopy (TEM) with near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT) calculations to investigate the active state and catalytic function of Pd nanoparticles (NPs) under methane oxidation conditions. We show that the particle size, phase composition and dynamics respond appreciably to changes in the gas-phase chemical potential. In combination with mass spectrometry (MS) conducted simultaneously with in situ observations, we uncover that the catalytically active state exhibits phase coexistence and oscillatory phase transitions between Pd and PdO. Aided by DFT calculations, we provide a rationale for the observed redox dynamics and demonstrate that the emergence of catalytic activity is related to the dynamic interplay between coexisting phases, with the resulting strained PdO having more favorable energetics for methane oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRSDate not supplied

Supercool(ed) Olivine Morphology in Shergottites Revealed Using X-ray Computed Tomography

Shergottites comprise most of the Martian meteorites and have a mafic to ultramafic bulk composition and a diversity of igneous textures [1].Olivine-phyric and poikilitic shergottites are sub-classes of shergottites and characterized by having a crystal cargo of large mafic minerals. Olivine-phyric shergottites have porphyritic textures of large olivinemegacrysts set in a fine-grained groundmass of pyroxene and maskelynite [2]. The poikilitic shergottites have assemblages of olivine chadocrysts poikilitically-enclosed by cm-sized pyroxene oikocrysts set in a coarse-grained groundmass of olivine and maskelynite [3,4]. The large crystal cargos in these samples are some of the first minerals to crystallize from their respective parent melts and have been extensively studied to understand shergottite petrogenesis. For instance, compositions of early-formed olivine and pyroxene in equilibrium with other phases (e.g. spinels) are used to establish depths, temperatures, and redox conditions of crystallization. There is increasing agreement that olivine megacrysts and poikilitic assemblages formed at or near the crust – mantle boundary (~85 km) before entrainment, ascent, and complete crystallization at or near the surface [1,3,4,6,7,8,9]. Additionally, linear olivine megacryst crystal size distribution (CSD)patterns and observations of polyhedral morphologies[8,9,10] are commonly interpreted to reflect steady-state crystallization under equilibrium conditions. However, oscillatory phosphorus zonation patterns in olivine from many samples indicate fluctuations in growth rates[10,12]. Recent studies measuring dendritic phosphorus zonation in terrestrial olivines [13] and experimental studies measuring how undercooling (undercooling is defined as the liquidus temperature minus the temperature being considered) controls changes in olivine morphology [14] have questioned the canonical view that large olivine megacrysts grow slowly and concentrically under equilibrium conditions. Here we present X-ray CT results from olivine-phyric and poikilitic shergottites that challenge the notion that early-formed minerals grew slowly under equilibrium conditions.

S A Eckley↗

DOE OSTI2026

Multifunctional electrochemical memory stabilized by phase coexistence

Our growing computing needs, especially in applications that heavily rely on artificial intelligence (AI), motivate a search for new components that could substantially augment the performance of general-purpose digital computers. Beyond ON/OFF switching, new components with linear multistate analog resistive tuning, nonlinear volatile switching, spiking, oscillatory, stochastic and other complex functionalities could enable highly efficient neuromorphic computing schemes for AI information processing. Compared to the extreme multifunctionality of biological neurons, realizing all the above characteristics in a single, scalable analog component remains a grand challenge. Here we investigate electrochemical gating combined with localized thermal activation to program and switch a single, vertically integrated and dimensionally scaled electrothermal chemical random access memory (ETCRAM) with a channel and reservoir composed of phase-separated vanadium oxide. Closely related to electrochemical RAM (ECRAM), ETCRAM uses an integrated gate-heater electrode to overcome kinetic barriers that help retain states at ambient temperatures. In addition to synapse-like stable and programmable analog resistance states arising from redox-tunable phase coexistence, a single component exhibits neuron-like nonlinear conductance switching with a tunable threshold and self-driven dynamics owing to the thermally driven metal-insulator phase transition in vanadium dioxide. More broadly, we demonstrate that electrochemically stabilized phase coexistence could unlock analog electronics with novel functionality, stability, reconfigurability, and scalability.

Oh, Sangheon [Sandia National Lab. (SNL-CA), Liver↗