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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

A practical approach for identifying various polarization behaviors of redox-stable electrodes in symmetrical solid oxide fuel cells

In symmetrical solid oxide fuel cells, comprehensively understanding the elementary reaction processes and the polarization behaviors of redox-stable electrode materials is critical for further optimization of the electrode performance. In this work, a systematical and practical approach, based on electrochemical impedance spectroscopy technology, is applied to identify the rate-limiting elementary reactions of the redox-stable electrodes. The feasibility of this proposed method is demonstrated in symmetrical solid oxide fuel cells with Sr 2 Fe 1.5 Mo 0.5 O 6-σ -Ce 0.9 Gd 0.1 O 1.95 as electrodes. Based on the characteristic frequency ranges and the experimental results tested under various fuel gas components, operating temperatures, and discharge current densities, the rate-limiting steps of the cathode are associated with the formation of adsorbed oxygen ions and the combination of oxygen ions and oxygen vacancies, while the rate-limiting steps of the anode are ascribed to the hydrogen dissociated adsorption and the steam desorption processes. This experimental and analysis framework can be straightforwardly extended to other electrode materials to unravel their electrochemical performance in detail.

25 ENERGY STORAGE↗
DOE OSTI2021

Effect of Cu on the passivity of Ti–xCu (x = 0, 3 and 5 wt%) alloy in phosphate-buffered saline solution within the framework of PDM-II

The effect of copper content on the passivity of Ti–xCu alloys in a phosphate-buffered saline electrolyte (pH 7.4), in the steady-state condition, was examined using potentiostatic polarization, electrochemical impedance spectroscopy, and Mott-Schottky analysis. The study demonstrates that the oxide layer forms on the Ti–xCu alloys surface have n-type semiconducting character, and the steady-state thickness of the oxide layer is observed linearly and depends on the applied potential. The study observations are in line with the predictions of the Point Defect Model (PDM-II), which provides a physiochemically realistic description of the oxide layer formation on Ti–xCu alloys. The observations reveal that the Cu additions result in a decrease in the charge transfer resistance and capacitances associated with the hydroxide and barrier layer, an increase in the donor density, and reduce the electrochemical resistance of the Ti–xCu alloys. The study also exhibits that the decrease in the steady-state current density after the initial addition of 3 wt% of Cu is attributed to the progressive substitution of copper on the cation sublattice of the film resulting in enhanced electrostatic interaction between the immobilized copper $Cu^{x'}_{Ti}$, and the mobile cation interstitials $Cu^{+}_{i}$, which carries the excess current over and that conveyed by oxygen vacancies $V^{••}_o$ in the barrier layer. Moreover, it is also observed that over a hundred-year implant period, about 0.006 cm (0.06 mm) of Ti–3Cu alloy is predicted to lose due to steady-state corrosion in the PBS solution under the given set of conditions, it is further seen that, as the Cu amount increased from 3 wt% to 5 wt% in the Ti–xCu alloys, the steady-state corrosion rate decreases.

Electrochemical Impedance Spectroscopy↗
DOE OSTI2021

Electronic structure of reduced CeO 2 (111) surfaces interacting with hydrogen as revealed through electron energy loss spectroscopy in comparison with theoretical investigations

Based on both, ab-initio cluster calculations as well as periodic density functional based loss function calculations, we have assigned the origins of the valence electron excitation regime in electron energy loss spectra of well-ordered ceria films in (111) orientation at various states of reduction as well as after exposing the reduced films to hydrogen from the gas phase (Li et al, Angew. Chem. Int. Ed., 58 (2019) 14686–14693). The explicit calculation of intensity distributions using the dipole approximation allow us to draw conclusions about the nature of oxygen vacancies, which occur upon reduction and how those interact with hydrogen to form hydride species. Herein, we also reports a brief discussion of vibrational excitations of hydrogen loaded ceria and corroborates previous interpretations, based on inelastic neutron scattering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Multi-energy ion irradiation effects and distinctive features of color center generation in yttria-stabilized zirconia driven by structural discrepancy

Regarding a requirement for inert matrix fuel (IMF) to burn minor actinides and plutonium and high-level waste immobilization, Yttria-stabilized zirconia (ZrO 2 -6.5 wt% Y 2 O 3 ) (YSZ) crystals with cubic phase are selected to comprehensively evaluate the irradiation resistance by irradiation-induced structural discrepancies across multiple energy conditions. Electronic excitation and nuclear collisions reveal distinct color centers, influenced by varying component ratios that reflect their formation mechanisms. Key factors driving ultra-fast structural transitions include collision cascades, pressure waves, and energy dissipation from electronic excitation. In this work, we find that in the electronic energy loss (E ele )-dominant region, internal latent tracks with unique surface nanostructures emerge, distinct from the defect clusters seen in the nuclear energy loss (E nuc )-dominant region, while the threshold for latent track formation and melting are identified. In conclusion, structural discrepancies driven by different energy-loss mechanisms promote the generation of singly ionized and nearest-neighbor doubly ionized oxygen vacancies, which respectively dominate the formation of F⁺ and T-centers, resulting in bandgap narrowing (4.80 eV → 4.73 eV), and furthermore triggering visible light emission (2.17 eV → 2.20 eV) in irradiated YSZ crystals, thus, enabling the design of novel irradiation-tailored material functionalities.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Exploring the impact of multivalent substitution on high-temperature electrical conductivity in doped lanthanum chromite perovskites: An experimental and ab-initio study

Doped LaCrO 3 perovskites hold promise as robust materials for electrical interconnects and sensor applications in harsh environments. In this work, we investigated the high-temperature behavior of La 1–x Sr x CrO 3 , La 1–x Ca x CrO 3 and La 0.8 Sr 0.2 Cr 1-x Mn x O3 (0.1 ≤ x ≤ 0.4) through a combination of computational modeling and physical characterization up to 1500 °C. Crystalline structural properties were determined and compared with ab-initio calculations, which demonstrated excellent agreement with experimental findings. High-temperature electrical conductivity measurements were performed under different atmospheres. Calcium and strontium/manganese co-doped lanthanum chromites exhibited typical semiconductor exponential trends and conductivity showed proportional correlation with substitutions levels up to 30 %. The DFT modelling was completed up to 1500 °C, including low and high temperature chromite phases and oxygen vacancies insertion. Calculations were correlated with experimental electrical properties. This work expands the understanding of doped lanthanum chromites and paves the way for the development of materials suitable for demanding high-temperature applications.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2024

Reactive flash sintering and characterization of bulk high entropy nitrides

Over the past decade, numerous high-entropy ceramics have been synthesized, often displaying attractive properties. However, the study on facile preparation of bulk high entropy nitrides (HEN) are limited, despite its broad potential applications. This research demonstrates for the first time rapid fabrication (within ∼6 min) of bulk high-entropy nitrides, especially (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N, from binary nitride powder mixtures using a highly efficient reactive flash sintering (RFS) technique. X-ray diffraction (XRD) shows the HENs from RFS are near single-phase solid solutions with a rock salt crystal structure, while in situ synchrotron study carried out during RFS captured in real time the formation of HEN, which was preserved upon cooling, suggesting thermodynamic stability of the HEN phase, even up to extreme pressure (∼35.6 GPa). Microscopic analyses using SEM, STEM, and EDS reveal decent uniformity for HEN with no obvious segregation of elements, even to submicron scale. Some properties of the obtained bulk HENs are consistent with expectations. For example, their hardness and bulk modulus are close to estimates based on rule-of-mixture (ROM) values from the constituent binary nitrides. Meanwhile, some other measured properties seem to show surprises. For example, the fracture toughness for the HENs (e.g., 7.81 ± 1.40 MPa•m 1/2 or higher) turns out to be more than double of the expected ROM estimates. The significantly improved fracture toughness is attributed to the observed nano-layered structure of the HENs, despite the HEN’s cubic crystal structure and high hardness. In addition, the oxidation resistance shows improvement up till ∼800°C, possibly due to Ta doping that suppress oxygen vacancy formation in the oxide shell, while the 5-metal HEN of (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N displays superconductivity (T c of ∼5–7 K from magnetism and resistivity measurements, slightly lower than ROM estimate), despite insulating property of starting AlN. Furthermore, future study combining experimental investigation using larger samples to confirm the observed increase in fracture toughness and oxidation resistance, theoretical modeling at different length scale, and more detailed structural/chemical characterization, especially at the atomic scale, are all needed to fully understand the inter-relationships between composition, processing, structure, and novel properties for these HENs and the development of related new materials for different applications.

Flash sintering↗
DOE OSTI2022

Effect of iron substitution in cryptomelane on the heterogeneous reaction with isoprene

Biogenic isoprene is an important pollutant for regional air quality. Being ubiquitously distributed on the earth surface, manganese (hydr)oxides should play a vital role in the transformation of isoprene. Cryptomelane is a typical manganese oxide with isomorphous substitution of Fe for Mn, but less attention has been paid to its heterogeneous reaction with isoprene. When Fe 3+ replaces Mn 3+ , K + is depleted and Mn 3+ is oxidized to Mn 4+ . In contrast, oxygen vacancies are formed when Fe 3+ substitutes Mn 4+ . Fe substitution creates weak crystallites and abundant mesopores, resulting in the increase of isoprene adsorption. As found by theoretical calculations, the Mn 4+ –O 2- bonds at the cross sections of the tunnels is more active than that on the outer wall of the tunnels. After the adsorption of isoprene, bridging carboxylate species and hydrogen-bonding water are produced and the surface octahedra are distorted, i.e., Mn 4+ O 6 → Mn 3+ O 6-δ . As the heat facilitates the breakage of Mn 4+ –O 2- , the increase of environmental temperature enhances the oxidation of isoprene. Here the above findings shed light on the effect of Fe substitution in cryptomelane to enhance the oxidation of isoprene, and illustrates that heterogeneous reaction with isoprene impairs the transformation of other environmental substances on cryptomelane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Metal-insulator transition temperature in EuO 1−x films as a function of exposure time in air

Oxygen-deficient Europium monoxide EuO 1-x shows a metal-to-insulator transition near the Curie temperature (T C ). A systematic transport study of EuO 1-x thin films as a function of exposure time in air reveals a gradually decreased T C from 140 K to 70 K as the concentration of the oxygen vacancies decreases, which is accompanied by a drastic increase in the resistance. Here we also find an unusual enhancement of magnetic anisotropy in the transport measurements, which results from the strong spin-orbit coupling at the interface between the film and substrate and possible presence of spin-textures like skyrmions in EuO 1-x .

36 MATERIALS SCIENCE↗
DOE OSTI2020

Fission gas diffusion and release for Cr 2 O 3 -doped UO 2 : From the atomic to the engineering scale

Here, the anticipated benefits of large grains in Cr 2 O 3 -doped UO 2 pellets include improved mechanical and fission gas retention properties. To support the assessment of fission gas release (FGR) from doped pellets, the impact of doping on fission gas diffusivity for in-reactor conditions must be understood. In this work, we tackle this issue by informing the fission gas model within the BISON fuel performance code using material models developed at the atomic scale. The investigation of intra-granular fission gas diffusivity in Cr 2 O 3 -doped UO 2 is carried out by adapting a cluster dynamics model that, accounting for UO 2 thermochemistry, is capable of describing Xe diffusion under irradiation in undoped UO 2 as the starting point. Using a thermodynamic analysis, it is shown that in stoichiometric UO 2 with additions of Cr 2 O 3 the oxygen potential is defined by the Cr-Cr 2 O 3 two-phase equilibrium. Using the cluster dynamics model, the predicted Xe diffusivity in doped UO 2 was significantly increased in both the intrinsic and irradiation-enhanced regimes compared to undoped UO 2 as a result of higher concentrations of uranium and oxygen vacancies, respectively. This is a consequence of the more oxidizing conditions at high temperature, and more reducing conditions at low temperature, as a result of doping. Arrhenius functions have been fitted to the cluster dynamics results to enable implementation of the new diffusivities in the BISON fission gas behavior model. BISON simulations were carried out, showing the competing effects of the enlarged grains and the new fission gas diffusivity model, which act to suppress and enhance fission gas release, respectively. The new physics-informed model was validated against in-reactor experimental measurements under normal operation. Additionally, benchmarking was carried out for power ramp conditions. The predicted fission gas release agreed well with the experimental data, showing noticeable improvements over the standard UO 2 model.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Atomistic and cluster dynamics modeling of fission gas (Xe) diffusivity in TRISO fuel kernels

TRISO fuel particles are candidates for use in next generation reactors including gas reactors, fluoride salt-cooled high temperature reactors, and micro-reactors. The UCO fuel kernel consists of a uranium dioxide (UO) and uranium carbide mixture. The addition of UC helps suppress the formation of carbon monoxide gas, which led to failures during initial TRISO development. The addition of uranium carbide alters the chemistry of the UO kernel, which is known to influence performance parameters such as fission gas diffusivity, although the impact has not been quantified and no models exist that take the change in chemistry into account. Therefore, better understanding and more accurate models of the impact of chemistry on fuel performance are of high priority. In this paper, a first-principles density functional theory (DFT) and empirical potential based multi-scale study has been carried out to model the diffusivity of fission gas xenon (Xe) in UCO TRISO fuel kernels. The focus is on the UO component in the UCO fuel kernels, as that represents the largest volume fraction of the fuel kernels. The study relies on DFT and empirical potential calculations to determine Xe and point defect properties, which are then used in thermodynamic and kinetic models to predict diffusion for intrinsic conditions. In addition, the information is utilized in cluster dynamics simulations using the Centipede code to estimate the impact of irradiation on defect transport. Additionally, the presence of UC or UC in the UCO fuel kernels is shown to have a substantial impact on the UO non-stoichiometry by inducing oxygen vacancies and driving UO sub-stoichiometric, which causes much slower Xe diffusion in UCO compared to light water reactor UO fuel. The application of this model in fuel performance simulations using the Bison code is also demonstrated.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Enhancing the performance of the perovskite solar cells by modifying the SnO 2 electron transport layer

The tin oxide (SnO 2 ) electron transport layer (ETL) plays a vital role in the photo-conversion efficiency (PCE) and stability of organic-inorganic perovskite solar cells (PSCs). However, SnO 2 ETL-induced defects such as hydroxyl groups, oxygen vacancies, exposed Sn atoms, and dangling bonds hinder device performance. In this study, rubidium chloride (RbCl) has been used to modify the SnO 2 ETL. Perovskite film formed on the RbCl-modified SnO 2 ETL exhibits improved crystallinity with enlarged grain size and reduced grain boundaries and enhanced optical absorption. Further, the Hall-effect measurements indicate the improved carrier mobility, and the dark J-V curve shows the increment of electrical conductivity for the RbCl-modified SnO 2 ETL. X-ray photoelectron spectroscopy (XPS) results demonstrate the surface defects passivation of the perovskite layer by modifying the SnO 2 ETL. A champion PCE of 19.35% has been achieved for the RbCl-modified SnO 2 ETL-based devices with improved stability, while the control devices with unmodified SnO 2 ETL show a PCE of 17.18%.

14 SOLAR ENERGY↗
DOE OSTI2025

Effect of high scandium doping in barium zirconate on nickel diffusion and performance of proton-conducting solid oxide electrolyzer cells

Proton-conducting solid oxide electrolyzer cells (p-SOECs) are emerging but promising technologies for hydrogen production. However, due to the lack of a robust electrolyte, p-SOECs struggle simultaneously to display high performance, Faradaic efficiency, and durability. Motivated by its high proton concentrations and stability as a barium zirconate, we have investigated BaZr 0.6 Sc 0.4 O 3-δ (BZSc40) as a potential next-generation p-SOEC electrolyte. Here, we found elevated levels of NiO diffusion through BZSc40 electrolytes during high-temperature sintering, attributed to the large oxygen vacancy concentrations present in BZSc40, as revealed by first-principle computational results. Controlling NiO diffusion is critical, as it can facilitate densification and grain size growth, but it may also detrimentally impact performance by causing electronic leakage. By optimizing sintering temperature when fabricating BZSc40 cells, we successfully controlled NiO diffusion, achieving sufficient electrolyte densification along with high performance and Faradaic efficiency. BZSc40 cells reached −0.99 A/cm 2 at 1.3 V and 600 °C and exhibited enhanced durability with a 3.37 mV/kh degradation rate at −0.8 A/cm 2 over a 200-h testing period. BZSc40 electrolytes demonstrated superior performance over BaZr 0.8 Y 0.2 O 3-δ (BZY20). In addition to elevated current densities and grain sizes, BZSc40 cells achieved Faradaic efficiencies of 76 % compared to 54 % for BZY20 at −0.2 A/cm 2 and 600 °C. This work lays the foundation for BZSc40 as a potential electrolyte due to its advantages over BZY20 while demonstrating the significance of controlling NiO diffusion when fabricating p-SOECs.

Electrolyzer↗
DOE OSTI2026

The structure, composition, and performance impact of a YSZ-GDC interdiffusion layer in solid oxide electrolysis cells

This study provides a combined experimental and computational investigation into the structure and impact of the cation interdiffusion layer that appears at the gadolinium doped ceria (GDC)/yttria stabilized zirconia (YSZ) interface in solid oxide electrolysis cells (SOECs). Scanning transmission electron microscopy (STEM) illustrates that a ∼0.4 μm interdiffusion layer (IDL) with an intermixed cation distribution and fine grain size forms upon sintering. STEM identifies that the interdiffusion layer exists in the cubic fluorite structure despite changes in cation composition. The interdiffusion layer microstructure formed during sintering does not change during SOEC testing at either 1.3V or heightened voltage pulse testing. Modeling predicts that ionic conductivity may decrease in the interdiffusion layer due to Coulombic trapping between mobile oxygen vacancies and excess Gd 3+ acceptor dopants. Yet, the density and continuous nature of the layer should benefit cell stability by substantially reducing the formation of SrZrO 3 , which is corroborated by STEM and Synchrotron X-ray diffraction (XRD). We conclude that the interdiffusion layer acts as a beneficial barrier to Sr diffusion, when operating in a regime where electrolyte void formation is not observed.

organic↗
DOE OSTI2021

Oxygen-deficient ammonium vanadate for flexible aqueous zinc batteries with high energy density and rate capability at -30 °C

Aqueous zinc batteries (AZBs) have received significant attention owing to environmental friendliness, high energy density and inherent safety. However, lack of high-performance cathodes has become the main bottleneck of AZBs development. Here, oxygen-deficient NH 4 V 4 O 10–x ·nH 2 O (NVOH) microspheres are synthesized and used as cathodes for AZBs. The experimental test and theoretical calculations demonstrate that the oxygen vacancies in the lattice lower the Zn 2+ diffusion energy barrier, which enables fast Zn 2+ diffusion and good electrochemical performance in a wide temperature range. The suppressed side reactions also can help to improve the low temperature performance. NVOH shows a high energy density of 372.4 Wh kg –1 and 296 Wh kg –1 at room temperature and –30 °C, respectively. Moreover, NVOH maintains a 100% capacity retention after 100 cycles at 0.1 A g –1 and ~94% capacity retention after 2600 cycles at 2 A g –1 and –30 °C. Investigation into the mechanism of the process reveals that the capacity contribution of surface capacitive behaviors is dominant and capacity attenuation is mainly caused by the decay of diffusion-controlled capacity. As a result, flexible AZBs can steadily power portable electronics under different bending states, demonstrating its great potential in wide-temperature wearable device.

25 ENERGY STORAGE↗
DOE OSTI2022

Multicycle flash sintering of cubic Y 2 O 3 -stabilized ZrO 2 : An in situ energy dispersive synchrotron x-ray diffraction study with high temporal resolution

The current induced unit cell volume changes, (111) Bragg peak full width at half maximum (FWHM) and its integrated intensity in 8 % Y 2 O 3 stabilized ZrO 2 (8 %YSZ) solid state electrolyte was monitored during a triple-flash sintering experiment by in situ energy dispersive x-ray diffraction using a polychromatic synchrotron probe (max, photon energy 200 keV) with 2 second temporal resolution. The first spontaneous singularity in the unit cell volume (+0.54 %) was observed at 899 °C under 15 V/mm applied field intensity, which was associated with 13 mA/mm 2 current draw and an increase in density to 97 %. Following anelastic relaxation of the unit cell volume under open circuit conditions, the same applied field was applied twice in a row which resulted in additional induced singularities at 925 °C (+0.48 %) and 944 °C (+0.42 %). A floating baseline, which was above the thermal expansion baseline, was observed from 833 to 969 °C and was attributed to Joule heating. In conclusion, the singularity at 899 °C is associated with a sharp change in (111) FWHM and a 34 % decrease in integrated peak area that was attributed to changes in the distribution of oxygen vacancies and the changes in their concentration as induced by the applied field in the spontaneous transient stage of flash sintering.

36 MATERIALS SCIENCE↗
DOE OSTI2024

In-situ ionothermal synthesis of nanoporous carbon/oxide composites: A new key to functional separators for stable lithium-sulfur batteries

Lithium-sulfur batteries (LSBs) with high energy density are promising for energy storage. However, conventional polypropylene-based separator cannot avoid polysulfides shuttling which impedes the practical application of LSBs. Herein, an in-situ ionothermal synthesis strategy that concurrently applies ionic liquid as the solvent, template and high-yield carbon source is proposed for the facile preparation of nanoporous carbon/oxide composite separator modifiers. The composites exhibit features of high polarity, self doping, oxygen vacancy, heteroatom doping, abundant defects and high electronic conductivity. Theoretical and experimental studies suggest that the composites can efficiently trap and convert polysulfides for high-performance LSBs. Indeed, in the composite-modified LSBs with next-generation roll-to-roll dry-processed high-loading sulfur cathodes, enhanced performance is achieved, revealing the effectiveness of the composites as functional materials towards separator modification. Therefore, the proposed strategy and its delivered nanoporous composites exhibit excellent versatility and practicality for high-performance LSBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Nanoscale chemistry and ion segregation in zirconia-based ceramic at grain boundaries by atom probe tomography

In this work nanoscale features that are of importance in the stability of yttria-stabilized tetragonal zirconia (Y-TZP) are quantified through atom probe tomography. In-depth analysis of grain boundary chemistry revealed preferential segregation of lighter and smaller ions towards specific grain boundaries. The relationship between elemental segregation and the local atomistic structure is investigated at the sub-nanometer level to gain insights on nanoscale features associated with the tetragonal-monoclinic phase transformation in Y-TZP through grain boundary characterization. Furthermore, principal component analysis was implemented to reveal any potential biases from varied field evaporation across stabilizer-rich grain boundaries. The observed variations in ion density across different grains suggested a variation in field which was attributed to potential variations in grain crystal orientation. In order to reveal the subtle depletion of oxygen atoms within grain boundaries a new methodology to map oxygen vacancies is proposed, utilizing the relative neighborhood chemistry of individual yttrium atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2021

CO adsorption on MnO(100): Experimental benchmarks compared to DFT

In this study, CO adsorption on the MnO(100) surface was studied using temperature programmed desorption (TPD) and density functional theory (DFT). TPD results show that CO is weakly-bound on MnO(100), with an experimental adsorption energy of -35.6 ± 2.1 kJ/mol at terrace sites in the low coverage limit. PBE simulations suggest that CO adsorption causes an implausible (2 × 2) surface reconstruction. PBE+U simulations show no signs of surface reconstruction, and provide an accurate estimate of the adsorption energy (-36.4 kJ/mol) when combined with the DFT-D3 method with Becke-Jonson damping to correct for van der Waals interactions. This simulation also shows that CO adsorbs C-down onto the Mn 2+ terrace site in a tilted geometry, which is also observed experimentally and computationally on the similarly-structured NiO(100) transition metal oxide surface. TPD results for large doses show a plateauing of the coverage at about 0.4 monolayers of CO at 85 K, with a defect coverage equivalent to 0.08 monolayers. Adsorption associated with defect sites is indicated by a high-temperature desorption tail which is not satisfactorily explained by DFT simulations of simple step or oxygen vacancy defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗