Metal-oxide Interface Research Articles

Influence of composition and temperature on oxide film formation for Fe-Cr-Ni alloys in simulated PWR primary water

ABSTRACT The growth of oxide films on Fe-Cr-Ni alloys in simulated pressurized water reactor (PWR) primary system environments was investigated, with focus on the influence of alloy composition and temperature. Oxide film thicknesses were measured for 90 specimens prepared from compact tension (CT) test pieces. Cross-sectional observations were also conducted on coupon specimens using scanning transmission electron microscopy (STEM). The behavior of Ni-based alloys, specifically Alloy 600, and Fe-based alloys, specifically Type 316 stainless steel, were compared. Ni-based alloys exhibit superior corrosion resistance due to slower Fe diffusion kinetics compared to Fe-based alloys, leading to the formation of a nickel-enriched protective layer at the metal-oxide interface. The oxidation rates of Ni-based alloys follow an Arrhenius-type temperature dependence. In contrast, Fe-based alloys show a more complex temperature-dependent behavior, with reduced oxidation rates at higher temperatures that are likely due to changes in oxide dissolution. Higher chromium concentrations in both alloy types improve the protectiveness of the oxide film towards corrosion by forming a more compact inner oxide layer. The study identifies three primary factors influencing oxide film growth: reactions at the metal-oxide interface, diffusion within the oxide layer, and processes at the oxide-solution interface. The relative significance of these processes varies depending on the alloy composition and temperature.

Comparative studies of the long-term corrosion behavior of Zr-Sn-Fe-Cr-Ni alloys in pure water at 360°C/18.6 MPa with high and low dissolved oxygen content

This study compared the uniform corrosion behavior of Zr-Sn-Fe-Cr-Ni alloys in deionized water at 360°C/18.6 MPa with high and low concentration of dissolved oxygen (DO). It was found that high concentration of DO accelerated the corrosion rate of the Zr-Sn-Fe-Cr-Ni alloys and led to an earlier corrosion transition. Increased DO concentration resulted in a higher content of t-ZrO2 near the metal-oxide interface, which induced greater in-plane compressive stress in the oxide film and a high-level phase transformation from t-ZrO2 to m-ZrO2. This, in turn, led to an earlier occurrence of corrosion transition.

Ni-Doped Pr0.7Ba0.3MnO3-δ Cathodes for Enhancing Electrolysis of CO2 in Solid Oxide Electrolytic Cells.

Solid Oxide Electrolysis Cells (SOECs) can electro-reduce carbon dioxide to carbon monoxide, which not only effectively utilizes greenhouse gases, but also converts excess electrical energy into chemical energy. Perovskite-based oxides with exsolved metal nanoparticles are promising cathode materials for direct electrocatalytic reduction of CO2 through SOECs, and have thus received increasing attention. In this work, we doped Pr0.7Ba0.3MnO3-δ at the B site, and after reduction treatment, metal nanoparticles exsolved and precipitated on the surface of the cathode material, thereby establishing a stable metal-oxide interface structure and significantly improving the electrocatalytic activity of the SOEC cathode materials. Through research, among the Pr0.7Ba0.3Mn1-xNixO3-δ (PBMNx = 0-1) cathode materials, it has been found that the Pr0.7Ba0.3Mn0.9Ni0.1O3-δ (PBMN0.1) electrode material exhibits greater catalytic activity, with a CO yield of 5.36 mL min-1 cm-2 and a Faraday current efficiency of ~99%. After 100 h of long-term testing, the current can still remain stable and there is no significant change in performance. Therefore, the design of this interface has increasing potential for development.

Post irradiation examinations of FeCrAl cladding in PWR conditions

FeCrAl alloys have been one of the prominent Accident Tolerant Fuel (ATF) cladding material candidates, primarily due to their excellent oxidation resistance in high-temperature steam conditions when compared to Zr-based alloys. Prototypic irradiation of fueled FeCrAl rods is a fundamental step in confirming the integral performance behavior during in-pile conditions. Early generation C26M cladding, fabricated through wrought metallurgy techniques, was fueled with UO2 fuel pellets and irradiated in a pressurized water loop in the Advanced Test Reactor (ATR) at the Idaho National Lab (INL) to a burnup (BU) of ∼25 GWd/tHM. After irradiation, the rodlets were nondestructively and destructively examined. Nondestructive examinations included visual exams, profilometry, and gamma scanning. These examinations highlight the unique deposits, BU profile of the rodlets as well as the migration path of fission gases within the rodlet, and typical diametrical morphology of fuel rodlets. During handling, brittle failure of one end cap on one pin occurred. Destructive examinations included microscopy and mechanical testing. Radial cross sections of the cladding were analyzed metallographically through light optical microscopy (LOM), scanning electron microscopy (SEM) highlighting a unique corrosion morphology and micro-cracking (∼20–30 μm past the main oxide layer) at the metal-oxide interface. Ring compression testing (RCT) was used to elucidate the mechanical property change of the FeCrAl cladding after neutron irradiation. In contrast to the non-irradiated material, which remained ductile at all test temperatures between 25 °C and 250 °C, the irradiated cladding fractured in a brittle manner at 50 °C and below. The results of the tests show that some challenges remain in the development of FeCrAl cladding for LWR cladding applications including improvement of in-reactor waterside corrosion performance and the retention of ductility after neutron irradiation.

Three-dimensional atomic insights into the metal-oxide interface in Zr-ZrO2 nanoparticles

Metal-oxide interfaces with poor coherency have specific properties comparing to bulk materials and offer broad applications in heterogeneous catalysis, battery, and electronics. However, current understanding of the three-dimensional (3D) atomic metal-oxide interfaces remains limited because of their inherent structural complexity and the limitations of conventional two-dimensional imaging techniques. Here, we determine the 3D atomic structure of metal-oxide interfaces in zirconium-zirconia nanoparticles using atomic-resolution electron tomography. We quantitatively analyze the atomic concentration and the degree of oxidation, and find the coherency and translational symmetry of the interfaces are broken. Atoms at the interface have low structural ordering, low coordination, and elongated bond length. Moreover, we observe porous structures such as Zr vacancies and nano-pores, and investigate their distribution. Our findings provide a clear 3D atomic picture of metal-oxide interface with direct experimental evidence. We anticipate this work could encourage future studies on fundamental problems of oxides, such as interfacial structures in semiconductor and atomic motion during oxidation process.

Intensified O2 activation and lattice O supply at inverse oxide-metal interface for catalytic oxidation reactions: A case study in alcohol oxidation

Inverse oxide/metal catalysts are recently employed and of great importance in catalytic oxidation reactions, due to the high activity and sintering-resistance. However, the investigations for identification of active-site structure, adsorption-activation of O2, and insight into interface-enhanced mechanism are relatively scare. Herein, the inverse “CoOx-Au” ensemble (∼10 nm CoOx nanoparticles onto ∼30 nm Au particles) for gas-phase alcohol oxidation was exampled to investigate above issues, under the premise of delivering 92 % benzyl alcohol conversion with 98 % benzaldehyde selectivity at 240 °C and atmospheric pressure. It is revealed that O2 is activated at CoOx-Au interface. The “CoO-Au ↔ Co3O4-Au” redox cycle at CoOx-Au interface proceeds over the “CoO↔Co3O4” cycle on CoOx surface, due to the weakened interfacial Co-O bond. And the enhanced redox cycle intensifies O2 activation and lattice O supply. The O2 activation at inverse oxide-metal interface provides promising clue for rational design of inverse catalysts for catalytic oxidation reactions.

Hydrogen spillover enhances the selective hydrogenation of α,β-unsaturated aldehydes on the Cu–O–Ce interface

The industrially important selective hydrogenation of α,β-unsaturated aldehydes to allyl alcohol is still challenging to realize using heterogenous hydrogenation catalysts. Supported Cu catalysts have shown moderate selectivity, yet low activity for the reaction, due to the electronic structure of Cu. By anchoring atomically dispersed Pd atoms onto the exposed Cu surface of Cu@CeO2, we report in this work that hydrogen spillover activates the inert metal-oxide interfaces of Cu@CeO2 into highly effective and selective catalytic sites for hydrogenation under mild reaction conditions. The as-prepared catalysts exhibit much higher catalytic activity in the selective hydrogenation of acrolein than Cu@CeO2. Comprehensive studies reveal that atomically dispersed Pd species are critical for the activation and homolytic splitting of H2. The activated H atoms easily spill to the Cu–O–Ce interfaces as Cu–Hδ– and interfacial Ce–O–Hδ+ species, making them the active sites for hydrogenation of polar C=O bonds. Moreover, the weak adsorption of allyl alcohol on the Pd and Cu–O–Ce interfacial sites prevents deep hydrogenation, leading to selective hydrogenation of several α,β-unsaturated aldehydes. Overall, we demonstrate here a synergic effect between single atom alloy and the support for activation of an inert metal-oxide interface into selective catalytic sites.

Electronic Oxide-Metal Strong Interactions (EOMSI) Localized at CeOx-Ag Interface.

Electronic oxide-metal strong interactions (EOMSI) refer to the electronic oxide-metal interactions (EOMI) between oxide adlayers and underlying metal substrate that is strong enough to stabilize supported oxide adlayers in a low-oxidation state, which individually is not stable under an ambient condition, from high temperature oxidation in air to a certain extent. Herein we report the deposition and electronic structure of CeOx adlayers on capping ligand-free cubic Ag nanocrystals, i.e., CeOx/Ag inverse catalysts. The EOMI occur via the charge transfer from Ag substrate to CeOx adlayers in the CeOx/Ag inverse catalyst, and the EOMSI are observed in the CeOx/Ag inverse catalyst with the average thickness of CeOx adlayers about 0.9 nm to exclusively form Ce2O3 adlayers stable against oxidation at 400 °C. As the thickness of CeOx adlayers increases, ceria adlayers with oxygen vacancies (CeO2-x) emerge and grow in the CeOx/Ag inverse catalysts, and the Ce3+/Ce4+ ratio decreases. Catalytic performance of CeOx/Ag inverse catalysts in the CO oxidation reaction is closely linked with the thickness and electronic structure of CeOx adlayers. These results demonstrate that the EOMSI and EOMI in the oxide/metal inverse catalysts are localized at the oxide-metal interface and sensitively vary with the thickness of oxide adlayers, offering a strategy of thickness engineering to tune electronic structures of oxide adlayers in oxide/metal inverse catalysts.

Electrochemical oxidative dehydrogenation of ethane to ethylene in a solid oxide electrolysis cell with in situ grown metal-oxide interface active electrodes

The shale gas revolution bolsters ethane supply, thereby enhancing the economic viability of ethylene production from ethane. Presently, catalytic ethane dehydrogenation technology exhibits immense potential in the realm of ethylene production. This study achieves the electrochemical oxidative dehydrogenation conversion of ethane to ethylene via a solid oxide electrolysis cell (SOEC), effectively circumventing the issue of excessive oxidation during the ethane oxidative dehydrogenation process. An active electrode with an in situ grown metal-oxide interface significantly promotes the activation of the ethane C–H bond, leading to efficient ethylene production. Under the co-electrolysis mode of ethane with CO2, the Co@CeO2 electrode demonstrates exceptional performance, achieving an ethane conversion rate of 33.1% and an ethylene selectivity of 88.9% at an applied voltage of 1.0 V. Moreover, the metal-oxide interface constructed via an in situ exsolved method effectively prevents the agglomeration of nanoparticles at high temperatures, thus enhancing the catalyst's resistance to coking and stability. Notably, the electrode's performance does not exhibit significant degradation even after 100 h of electrochemical reaction.

Phenomenology of Intermediate Molecular Dynamics at Metal-Oxide Interfaces.

Reaction intermediates buried within a solid-liquid interface are difficult targets for physiochemical measurements. They are inherently molecular and locally dynamic, while their surroundings are extended by a periodic lattice on one side and the solvent dielectric on the other. Challenges compound on a metal-oxide surface of varied sites and especially so at its aqueous interface of many prominent reactions. Recently, phenomenological theory coupled with optical spectroscopy has become a more prominent tool for isolating the intermediates and their molecular dynamics. The following article reviews three examples of the SrTiO3-aqueous interface subject to the oxygen evolution from water: reaction-dependent component analyses of time-resolved intermediates, a Fano resonance of a mode at the metal-oxide-water interface, and reaction isotherms of metastable intermediates. The phenomenology uses parameters to encase what is unknown at a microscopic level to then circumscribe the clear and macroscopically tuned trends seen in the spectroscopic data.

Theoretical insights into interface effects on CO2 hydrogenation to methanol over In4O6/ZrO2(1 1 1) catalyst

Methanol synthesis from CO2 hydrogenation on the defective In4O6/ZrO2(111) surface with surface oxygen vacancies has been investigated by using periodic density functional theory calculations. The calculated oxygen vacancy formation energies indicate that the D1 surface with Ov1 defective sites on the surface of the In4O6 clusters is thermodynamically the most favorable for the adsorbed CO2 to generate methanol along the HCOO pathway. In contrast, the D4 surface with Ov4 defect sites at the interface is the most unstable, reacting along the RWGS path on clusters near the Ov4 defects, and hydrogenating along the HCOO path at the interfacial position to generate methanol. The differential charge density curves further reveal the close relationship between the electronic structure of the metal oxide interface and the CO2 hydrogenation mechanism to methanol.

General Method for Predicting Interface Bonding at Various Oxide–Metal Interfaces

Interface termination bonding between metal oxide and metals is discussed from the viewpoint of thermodynamics. The method of interface termination prediction proposed by the authors for Al2O3–metal and ZnO–metal interfaces is extended to a general interface between metal-oxide and metals. The extension of the prediction method to the interface between metal oxides and elemental semiconductors is also discussed. Information on interface bonding was extracted by carefully examining the experimental results and first-principles calculations in the references. The extracted information on interface bonding from references is compared with the results obtained via the proposed prediction method. It is demonstrated that interface termination bonding can be predicted by extending the method to oxide–metal interfaces in general, when there is no interface reaction such as the reduction of oxide, oxidation of metal, or mixed oxide formation. The method uses only basic quantities of pure elements and the formation enthalpy of oxides. Therefore, it can be applied to most of the metals (including elemental semiconductors) in the periodic table and metal oxides with one stable valence. The method is implemented as a software, “InterChemBond”, and can be used free of charge.

CO2 reforming of ethane using Ni-La intermetallic sites within a nanocapsule framework

CO2 reforming of light alkanes from unconventional gas resources (shale gas/coalbed gas) presents an attractive route to achieve CO2 utilization and valuable chemical production. However, it remains challenging in both high stability and product selectivity due to the inevitable strong competition between dry reforming and oxidative dehydrogenation pathways. We report here a La modified Ni@SiO2 nanocapsule as the thermal-catalyst for CO2 reforming of ethane, achieving complete ethane conversion and remarkable CO2 conversion of 86.5 %, with stability for more than 200 h experiencing no carbon deposition. Detailed kinetic study, in situ characterizations and DFT calculation results revealed that the formation of NiLa intermetallic sites improved the adsorption of active oxygen species and activation of C2H6, which stabilized the key intermediate CH3CH2O* as well as the subsequent C2* cracking to CHx(O)*, leading to high selectivity toward syngas. Meanwhile, the removal of carbon deposits on Ni-La2O3 interfaces are faster than Ni surface. The synergism of spatial confinement structure provided by the nanocapsule with sufficient mechanical strength together with the chemical Ni-La2O3 interface of the enwrapped Ni-La mixed metal (oxide) NPs can timely eliminate C2* intermediates, which results in the most effective anti-coking ability during ethane reforming. This work highlights a tangible process towards unconventional (C2+) gas utilization with fine-tunable nanoreactor catalysts.

Decoding the oxidation mechanism of Zircaloy-4 via in situ synchrotron X-ray diffraction and computational elucidation

Comprehensive understanding of the oxidation behavior of Zr alloys, a vital cladding material in nuclear power plants, is essential for developing improved materials and enhancing the safety and performance of nuclear systems. Herein, the bulk oxidation behavior in ambient air atmosphere of Zircaloy-4 were revisited through in situ synchrotron X-ray diffraction and DFT computation. The results reveal the phase transition sequences at a representative 900 °C oxidation temperature: hcp Zr recrystallizes rapidly and then transforms into bcc Zr while reaching the α+β transus, followed by speedy appearance of textured tetragonal (t-)ZrO2, monoclinic (m-)ZrO2 and ZrN that consume oxygen and nitrogen. Continuous air ingress favors t-ZrO2 and m-ZrO2 dominance, accompanied by re-oxidation of ZrN into t-ZrO2 due to its low thermodynamic stability revealed by experiment-informed DFT calculation and low oxygen activity at the oxide-metal interface. Ensemble-averaged lattice volume expansions during phase transitions have been quantified. This expansion-induced compressive stress promotes the presence of a significant fraction of t-ZrO2 at elevated temperature that eventually transforms into m-ZrO2 during cooling.

Numerical analysis of Al2O3 and TiO2 growth and oxygen dissolution in a metal substrate during the isothermal oxidation of an α-Ti alloy at 973 K

Oxide growth of Al2O3 and TiO2 as well as O dissolution during the oxidation of an α-Ti alloy at 973 K were simulated using the finite volume method coupled with the calculation of phase diagrams (CALPHAD) method. The results indicated that the addition of 11.02 at.% Al to a Ti–O system resulted in the formation of an 18-nm-thick Al2O3 layer, which decelerated TiO2 growth and O dissolution in the substrate. An increase in the O concentration at the oxide–metal interface was also inhibited by Al2O3 formation. A thin Al-depletion zone was formed at the oxide–metal interface. Furthermore, Al2O3 formation was restricted by the low concentration and diffusivity of Al in the substrate.

Harnessing Interlayer Magnetic Coupling for Efficient, Field‐Free Current‐Induced Magnetization Switching in a Magnetic Insulator

Owing to the unique features of low Gilbert damping, long spin‐diffusion lengths, and zero Ohmic losses, magnetic insulators are promising candidate materials for next‐generation spintronic applications. However, due to the localized magnetic moments and the complex metal–oxide interface between magnetic insulators and heavy metals, spin‐functional Dzyaloshinskii–Moriya interactions or spin Hall and Edelstein effects are weak, which diminishes the performance of these typical building blocks for spintronic devices. Herein, the exchange coupling between metallic and insulating magnets is exploited for efficient electrical manipulation of heavy metal/magnetic insulator heterostructures. By inserting a thin Co layer, the spin‐orbit torque efficiency is enhanced by more than 20 times, which significantly reduces the switching current density. Moreover, field‐free current‐induced magnetization switching caused by a symmetry‐breaking non‐collinear magnetic texture is demonstrated. This work launches magnetic insulators as an alternative platform for low‐power spintronic devices.

Exploring the Influence of Nanocrystalline Structure and Aluminum Content on High-Temperature Oxidation Behavior of Fe-Cr-Al Alloys.

The present study examines the high-temperature (500-800 °C) oxidation behavior of Fe-10Cr-(3,5) Al alloys and studies the effect of nanocrystalline structure and Al content on their resistance to oxidation. The nanocrystalline (NC) alloy powder was synthesized via planetary ball milling. The prepared NC alloy powder was consolidated using spark plasma sintering to form NC alloys. Subsequently, an annealing of the NC alloys was performed to transform them into microcrystalline (MC) alloys. It was observed that the NC alloys exhibit superior resistance to oxidation compared to their MC counterparts at high temperatures. The superior resistance to oxidation of the NC alloys is attributed to their considerably finer grain size, which enhances the diffusion of those elements to the metal-oxide interface that forms the protective oxide layer. Conversely, the coarser grain size in MC alloys limits the diffusion of the oxide-forming components. Furthermore, the Fe-10Cr-5Al alloy showed greater resistance to oxidation than the Fe-10Cr-3Al alloy.

Insight into the Synergistic Effect of the Oxide–Metal Interface on Hot Electron Excitation

Insight into the Synergistic Effect of the Oxide–Metal Interface on Hot Electron Excitation

Atomic-Level Tailoring of the Electronic Metal-Support Interaction Between Pt-Co3O4 Interfaces for High Hydrogen Evolution Performance.

Atomic-level modulation of the metal-oxide interface is considered an effective approach to optimize the electronic structure and catalytic activity of metal catalysts but remains highly challenging. Here, we employ the atomic layer deposition (ALD) technique together with a heteroatom doping strategy to effectively tailor the electronic metal-support interaction (EMSI) at the metal-oxide interface on the atomic level, thereby achieving high hydrogen evolution performance and Pt utilization. Theoretical calculations reveal that the doping of N atoms in Co3O4 significantly adjusts the EMSI between Pt-Co3O4 interfaces and, consequently, alters the d-band center of Pt and optimizes the adsorption/desorption of reaction intermediates. This work sheds light on the atomic-level regulation and mechanistic understanding of the EMSI in metal-oxide, while providing guidance for the development of advanced EMSI electrocatalysts for various future energy applications.

Interfacial Thermal Resistive Switching in (Pt,Cr)/SrTiO3 Devices.

The operation of oxide-based memristive devices relies on the fast accumulation and depletion of oxygen vacancies by an electric field close to the metal-oxide interface. Here, we show that the reversible change of the local concentration of oxygen vacancies at this interface also produces a change in the thermal boundary resistance (TBR), i.e., a thermal resistive switching effect. We used frequency domain thermoreflectance to monitor the interfacial metal-oxide TBR in (Pt,Cr)/SrTiO3 devices, showing a change of ≈20% under usual SET/RESET operation voltages, depending on the structure of the device. Time-dependent thermal relaxation experiments suggest ionic rearrangement along the whole area of the metal/oxide interface, apart from the ionic filament responsible for the electrical conductivity switching. The experiments presented in this work provide valuable knowledge about oxide ion dynamics in redox-based memristive devices.