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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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Benchmark CO 2 separation achieved by highly fluorinated nanoporous molecular sieve membranes from nonporous precursor via in situ cross-linking

Molecular sieve membranes with rigid micropores and CO 2 -philic functionalities within the architectures are promising candidates in CO 2 separation. However, the development of ctieve approaches for their fabrication still remains a significant challenge. In this study, an in situ cross-linking strategy is developed for the preparation of nanoporous fluorinated moleffecular sieve membranes using commercially available dense and non-porous polystyrene (M PS ) as a precursor template. Based on the dehydrative Friedel-Crafts reactions with highly fluorinated benzylic alcohols, M PS membranes are cross-linked in situ upon exposure to Brønsted acid (CF 3 SO 3 H), affording fluorinated microporous polymeric membranes with surface areas up to 523 m 2 g –1 and the presence of micropores centered at 1.1–1.3 nm as well as ultra-micropores (~0.6 nm). The obtained modified membranes exhibit good ideal CO 2 permeability of 797 barrer and CO 2 /N 2 selectivity of 28.5. In addition, high fluorine content (up to 28.5 wt%) and good thermal stability made the cross-linked membranes promising candidates to produce fluorinated carbon molecular sieve membranes with improved textural properties, exhibiting surface areas up to 1020 m 2 g –1 and ultra-micropores of ~0.4 nm. These membranes achieve superior CO 2 /N 2 separation performances exceeding the Robeson upper bound limit (2008).

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

Grain growth of nanocrystalline aluminum under tensile deformation: A combined in situ TEM and atomistic study

Nanocrystalline Al thin films have been strained in situ in a transmission electron microscope using two separate nanomechanical techniques involving a push-to-pull device and a microelectromechanical system (MEMS) device. Deformation-induced grain growth was observed to occur via stress-assisted grain boundary migration with extensive grain growth occurring in the necked region, indicating that the increase in local stress drives the boundary migration. Under applied tensile stresses close to the ultimate tensile strength of 450 MPa for a nanocrystalline Al specimen, measured boundary migration speeds are 0.2 – 0.7 nm s -1 for grains outside necked region and increases to 2.5 nm s -1 for grains within the necked region where the local estimated tensile stresses are elevated to around 630 MPa. By tracking grain boundary motion over time, molecular dynamics simulations showed qualitative agreement in terms of pronounced grain boundary migration with the experimental observations. The combined in situ observation and molecular dynamics simulation results underscore the important role of stress-driven grain growth in plastically deforming nanocrystalline metals, leading to intergranular fracture through predominant grain boundary sliding in regions with large localized deformation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In situ study of the electronic structure of polar-to-polar SrTiO 3 /($000\bar1$)ZnO heterointerface

The SrTiO 3 (STO)/ZnO heterointerface, which is widely used in the fabrication of novel optoelectronic devices, is a classical system combining functional perovskite oxides and wurtzite-structure semiconductor materials. The electronic structure of the heterointerface often plays a significant role in controlling the functions of novel devices. In this study, the electronic structure was explored using in situ photoemission spectroscopy and X-ray absorption spectroscopy. X-ray diffraction results showed the coexistence of (111) STO and (011) STO orientations for the STO film deposited on the ZnO-($000\bar1$) substrate via pulsed laser deposition. High-resolution transmission electron microscopic results revealed two types of polar interfaces: [$11\bar2$][$10\bar1$](111) STO //[$1\bar210$][$10\bar10$]($000\bar1$) ZnO and [111][$2\bar1\bar1$](011) STO //[$10\bar21$][$10\bar10$]($000\bar1$)ZnO. In situ photoemission spectroscopic results revealed downward band bending and the transformation of the valence states of Ti from 4+ to 3+, with extra electrons transferring to the hybridization states between O 2p and Ti t 2g orbitals at the polar-to-polar STO/ZnO interface. We propose that the polar discontinuity drives the electron transfer to the STO/ZnO interface during the growth process. This study provides insight into the electronic structure of the STO/($000\bar1$)ZnO heterointerface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Stresses within rare-earth doped yttria-stabilized zirconia thermal barrier coatings from in-situ synchrotron X-ray diffraction at high temperatures

There is a growing interest for smart coatings that can be integrated into turbine engines for in-situ temperature measurements or health monitoring. The addition of rare-earth dopants into standard thermal barrier ceramic top coat materials is used to obtain luminescent coatings that enable spectral measurements, for real-time temperature or health monitoring. The thermomechanical performance and durability of such novel coating compositions in extreme environments still remains to be evaluated. Consequently, the ability to manufacture sensor coatings which present suitable thermal properties needs to be demonstrated. For this study, highly luminescent erbium and europium doped yttria-stabilized zirconia and state-of-the-art yttria-stabilized zirconia coatings manufactured by air plasma spray were characterized to determine the effects of the embedded rareearth dopants on coating internal strain and stress and to quantify and compare their high temperature response using synchrotron X-ray diffraction. In-situ depth-resolved strain measurements were performed at 15 μm intervals along the depth of the coatings to evaluate materials response at key locations, specifically at layer interfaces. In-plane stress was calculated for the coatings and a finite element model was implemented to supplement the results and enable further predictions. The results show that the sensor coatings that were manufactured in this work revealed only minor variations in the strain response of sensor coatings under a typical thermal cycle and especially at temperatures closer to that of gas turbine operating conditions, compared to state-of-the-art coatings. This work demonstrates the viability of manufacturing rare-earth doped yttria-stabilized zirconia coatings that provide beneficial spectroscopic monitoring capabilities while having minimal impact on the thermomechanical response of the thermal barrier coatings.

Air plasma spray↗
DOE OSTI2020

Modeling of thermal pressurization in tight claystone using sequential THM coupling: Benchmarking and validation against in-situ heating experiments in COx claystone

We apply thermoporoelasticity and a sequentially coupling technique for modeling thermally-driven coupled Thermo-Hydro-Mechanical (THM) processes in tight claystone. A THM benchmark case with a corresponding analytic solution for thermoporoelasticity under a constant heat loading verifies the model. Thereafter, two in situ heating experiments are simulated for model validation: a smaller-scale heating experiment (TED experiment) and a larger-scale experiment (ALC experiment) in Callovo-Oxfordian (COx) claystone at the Meuse/Haute-Marne underground research laboratory in France. The model exhibits good performance to match the observed temperature and pore pressure evolution for the smaller-scale TED experiment. For the larger-scale ALC experiment, general trends of thermal-pressurization are captured in the modeling, but pressure is underestimated at some monitoring points during cool-down. This indicates that the THM response in the field may be affected by the variability of rock's properties or irreversible or time-dependent mechanical processes that are not included in the current thermoporoelastic model. The main contributions of this work are as follows: (1) we verify and validate the numerical simulator, TOUGH-FLAC, to be a valuable coupled THM modeling tool; (2) prove that the laboratory determined material parameters can be used as reference values for upscaling experiments. However, to better identify and quantify THM processes with modeling of in situ tests, more emphasize should be dedicated to obtaining high-quality mechanical deformation data.

58 GEOSCIENCES↗
DOE OSTI2021

In Situ Wood Delignification toward Sustainable Applications

As one of the most abundant and versatile natural materials on Earth, recently wood has attracted tremendous attention from scientists and engineers due to its outstanding advantages, including hierarchically porous microstructure, high mechanical strength, environmental friendliness, renewability, and biodegradability. Wood’s hierarchically porous structure and chemical components (e.g., cellulose, hemicelluloses, and lignin) enable its mechanical, ionic, optical, and thermal properties to be tuned via physical, chemical, and/or thermal modifications. Among these various approaches, the chemical delignification of bulk wood is the most fascinating, in which the majority of lignin and hemicelluloses is removed while leaving the cellulose intact, maintaining wood’s physical integrity and hierarchical structure. This delignified structure is unique, composed of hollow, aligned channels made up of cellulose microfibrils, and particularly attractive given its origin from a sustainable and renewable resource. As a result, delignified wood has attracted increasing attention for applications that go far beyond traditional wood utilization, such as lightweight yet strong structural materials, energy storage and conversion, environmental remediation, flexible electronics, and bioengineering. Here, we review recent developments in bulk wood delignification strategies toward the achievement of such advanced wood technologies for sustainable applications, with a focus on the research in our group. Similar to chemical pulping and bleaching, wood delignification involves a series of nucleophilic reactions based on alkaline Na 2 SO 3 or Na 2 S systems (i.e., chemical pulping) or electrophilic, radical, and oxidation reactions based on H 2 O 2 , ClO 2 , or NaClO systems (i.e., chemical bleaching) to deconstruct, fragment, and promote the hydrophilicity of lignin macromolecules, which finally make lignin easier to be removed. We discuss the structure and properties of partially and near-completely delignified wood, with a focus on process-structure–property relationships. The resulting delignified wood materials, with tunable structure and properties, demonstrate various advanced functions, in a wide range of advanced applications, such as building and construction, green energy, and electronics. Finally, the potential challenges and appealing perspectives of in situ wood delignification are discussed. In situ wood delignification, as a powerful modification strategy, has speeded up the development of advanced wood technologies and wood-based functional materials and products.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Molecular Examination of Ion-Pair Competition in Alkaline Aluminate Solutions Using In Situ Liquid SIMS

Understanding the structure and composition of aluminate complexes in extremely alkaline systems such as Bayer liquors has received enormous attentions due to its fundamental and industrial importance. However, obtaining direct molecular information of the underlying ion-ion interactions using traditional approaches such as NMR or Raman spectroscopy is challenging due to the weakness of these interactions and/or their complex overlapping spectral signatures. Here, we exploit in situ liquid secondary ion mass spectrometry (SIMS) as a new approach and show how it enables new insights. In contrast with traditional techniques, using SIMS we succeeded in acquiring information on dominant ion clusters in these alkaline systems. In Na + /K + mixed alkaline aluminate solutions we clearly observe preferential formation of Na + -anion clusters over K + -anion clusters. Further, evaluation of these clusters by density functional theory (DFT) calculations shows that these structures are stable and that their relative bond energies are consistent with their observed SIMS signal intensity differences. This demonstrates a key advantage of in situ liquid SIMS for overcoming ambiguities obscuring important information in these systems on constituent molecular clusters defined by relatively weak ion pair competition and ion-solvent interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

In Situ Synchrotron X-ray Scattering Investigation of Cathodic ZIF-8 Deposition on Graphite Using 3D-Printed Cells

Electrochemical approaches provide unique means to fabricate thin films of metal organic frameworks (MOFs). However, the kinetics of electrochemical MOF deposition has not been quantitatively investigated so far. In this study, we report the first in situ measurements of electrochemical MOF growth using transmission synchrotron X-ray scattering. Electrochemical cells based on poly(lactic acid) with two windows were fabricated using fused-deposition modelling. Here, the resulting 3D-printed cells, the surface of which was coated with paraffin wax to prevent solvent percolation through the polymer material, were used to monitor the cathodic growth of zeolitic imidazolate framework-8 (ZIF-8) on graphite in a methanol solution containing ZnCl 2 and 2-methylimidazole (Hmim) at different cathodic potentials. The resulting time-resolved X-ray diffraction data showed a gradual increase in crystal size with negligible changes in crystal orientation during the cathodic ZIF-8 deposition. More importantly, the time-resolved data provided a means to quantitatively assess the kinetics of the cathodic ZIF-8 growth using the Gualtieri model, revealing that the cathodic potential and Hmim concentration affected crystal growth kinetics, but not nucleation kinetics. These ZIF-8 samples exhibited changes in X-ray diffraction pattern after being washed with methanol and dried in air, indicating that in situ measurements are essential to investigate mechanisms behind MOF electrodeposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

In Situ Observations of Barium Sulfate Nucleation in Nanopores

In this work, the nucleation and growth of barium sulfate in nanoporous silica was investigated using in situ small-angle X-ray scattering and X-ray pair distribution function analysis, together with ex situ transmission and scanning transmission electron microscopy (TEM and STEM) imaging. We found that crystalline barite formation in micropores is likely preceded by a nonbulk barite phase in the nanopores, indicating a possible nonclassical nucleation pathway for barium sulfate under confinement. The nucleation of barium sulfate inside the nanopores stopped at ~12% of the pores filled and was seemingly limited by the formation of crystals near the exterior of the silica particles, which likely blocked subsequent solute transport into the interior of the nanopores. The growth rate of barium sulfate was fit using the Johnson–Mehl–Avrami–Kolmogorov equation and constrained using a growth rate of barite of ~1.0 × 10 –7 mol/m 2 /s, obtained from previous studies, but is consistent with TEM and STEM observations made here. The inferred nucleation rate of barium sulfate inside nanopores is estimated to be on the order of 1.0 × 10 9 nuclei/m 2 /s, which is 2 orders of magnitude higher than previous measurements on a planar silica substrate (~1.0 × 10 7 nuclei/m 2 /s). This implies that the ability of silica nanopores to promote barium sulfate nucleation is sufficiently high as to create a potentially self-limiting condition, where the nucleation reaction is shut down prematurely because rapid growth blocks reactant transport.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In Situ Methods for Metal-Flux Synthesis in Inert Environments

Flux growth synthesis is an advantageous synthetic method as it allows for the growth of single crystals of both congruently melting and metastable phases. The determination of synthetic parameters for the flux growth of new crystalline phases is complex as many factors and parameters need to be considered, such as purity and morphology of starting material and heating profile variables including maximum temperature, dwell time, cooling rate and flux removal temperature. In situ monitoring of crystallite growth can lead to elucidation of reaction intermediates and growth mechanisms. The determination of pivotal reaction parameters can revolutionize the way growth parameters are selected. In this work, we report a new sample environment and furnace apparatus for synchrotron in situ synthesis of crystalline materials, including flux grown intermetallics.

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

Thermal Stability of Quasi-1D NbS 3 Nanoribbons and Their Transformation to 2D NbS 2 : Insights from in Situ Electron Microscopy and Spectroscopy

Here in situ electron microscopy imaging and spectroscopy enabled us to study the evolution of quasi-1D NbS 3 -IV nanoribbons with respect to morphology and chemical structure at temperatures between room temperature and 1000 °C. Scanning transmission electron microscopy (STEM) experiments included imaging in the secondary electron, (transmitted) bright field, and high-angle annular dark-field modes while operating in the low kV regime. The results showed that NbS 3 -IV samples transform dramatically from smooth nanoribbons into highly textured configurations featuring polyhedral divots and steps. Similar in situ heating experiments conducted with aberration-corrected STEM revealed that bilayers of NbS 3 -IV chains convert topotactically into aligned 2H-NbS 2 sheets upon loss of sulfur. Atomic resolution imaging, fast Fourier transform analysis, and electron energy loss spectroscopy confirmed these chemical changes, from which we propose an atomistic mechanism for the NbS 3 -IV → 2H-NbS 2 conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Design, Synthesis, and Evaluation of Noble Metal Nanoparticles and In Situ-Decorated Carbon-Supported Nanoparticle Electrocatalysts Using Hypergolic Reactions

Here, we report the first synthesis of metal nanoparticles and supported metal nanoparticles on carbon by using hypergolic reactions. Specifically, we report the synthesis of noble metal nanoparticles (Pt, Ag, and Au) using sodium hydride (NaH) as both an ignition trigger and a reducing agent for the corresponding metal salt precursors. In addition, we report the one-step, in situ synthesis of Pt nanoparticles supported on carbon by adding sucrose as the carbon source. The hypergolically synthesized nanoparticles display elliptical morphology and are more crystalline compared with those conventionally synthesized in solution using sodium borohydride (NaBH 4 ). When tested as electrocatalysts, the hypergolic Pt nanoparticles exhibit more than 2 times higher specific electrochemical active surface area (ECSA) and a higher half-wave potential (E 1/2 ) of 0.94 V vs the reversible hydrogen electrode (RHE) compared to the conventionally synthesized ones. In addition, the electrocatalyst based on the in situ synthesized carbon that was decorated with the Pt nanoparticles synthesized hypergolically outperforms an analogous, state of the art, commercial PtC system. For example, the former shows an attractive E 1/2 (0.94 V) compared with 0.9 V for the commercial PtC. Accelerated durability tests (ADT) in an alkaline environment add another advantage. After 10 000 cycles, the hypergolically synthesized system shows a smaller reduction of E 1/2 and less degradation compared to the commercial PtC (10 mV compared to ∼30 mV). The work described here represents the first reported synthesis using hypergolic reactions of metal nanoparticles as well as supported metal nanoparticles. The properties of the resulting electrocatalysts demonstrate the versatility and promise of the new approach in materials synthesis and open new avenues for further investigation as electrocatalysts.

Chalmpes, Nikolaos↗
DOE OSTI2020

Probing the Core–Shell Organization of Nanoconfined Methane in Cylindrical Silica Pores Using In Situ Small-Angle Neutron Scattering and Molecular Dynamics Simulations

Determining the structure of nanoconfined fluids is essential for predicting the fate of these fluids in subsurface geologic formations with nanoporous features and for engineering novel nanoporous materials for storing compressed gases. In this study, we probe the structure of nanoconfined methane at pressures in the range of 15–100 bar using in situ small-angle neutron scattering (SANS) measurements and molecular dynamics (MD) simulations. The structure of methane is probed in MCM-41 and SBA-15 with cylindrical pores and diameters of 3.3 and 6.8 nm, respectively. In situ SANS measurements and MD simulations showed that the confined methane molecules are organized in a core–shell structure, with the shell arising from the adsorption of methane molecules on the silica surface. The shell thicknesses of the adsorbed deuterated methane (CD4) molecules in MCM-41 obtained by SANS measurements are 1.4 ± 0.5, 2.1 ± 0.1, 3.2 ± 0.8, 4.0 ± 0.3, and 6.0 ± 0.7 Å at equilibrated pressures of 15.6, 35.6, 55.5, 73.3, and 95.7 bar, respectively. The shell thicknesses of the adsorbed CD4 layer in SBA-15 pores are 2.7 ± 0.5, 4.3 ± 0.7, 6.6 ± 0.7, 10.2 ± 0.3, and 14.6 ± 0.8 Å at equilibrated pressures of 15.5, 32.7, 52.4, 70, and 99.5 bar, respectively. These experimental results are in close agreement with the results predicted from MD simulations. Adsorption of methane molecules on the silica surfaces is primarily driven by van der Waals interactions between the methane molecules and the hydroxyl groups on the silica surface, while electrostatic interactions play a minor role. In conclusion, the experimental and simulation approaches described in this study provide fundamental insights into the organization of confined gases using methane as a specific example in the context of compressed fluid storage in natural and engineered materials for adaptive energy use.

03 NATURAL GAS↗
DOE OSTI2022

In Situ Visualization of Local Distortions in the High- T c Molecule-Intercalated Li x (C 5 H 5 N) y Fe 2– z Se 2 Superconductor

A time-resolved synchrotron X-ray total scattering study sheds light on the evolution of the different structural length scales involved during the intercalation of the layered iron–selenide host by organic molecular donors, aiming at the formation of the expanded-lattice Li x (C 5 H 5 N) y Fe 2– z Se 2 hybrid superconductor. The intercalates are found to crystallize in the tetragonal ThCr 2 Si 2 -type structure at the average level, however, with an enhanced interlayer iron–selenide spacing ( d = 16.2 Å) that accommodates the heterocyclic molecular spacers. Quantitative atomic pair distribution function (PDF) analysis at variable times suggests distorted FeSe 4 tetrahedral local environments that appear swollen with respect to those in the parent β-FeSe. Simultaneously acquired in situ synchrotron X-ray powder diffraction data disclose that secondary phases (α-Fe and Li 2 Se) grow significantly when a higher lithium concentration is used in the solvothermal reaction or when the solution is aged. These observations are in line with the strongly reducing character of the intercalation medium’s solvated electrons that mediate the defect chemistry of the expanded-lattice superconductor. In the latter, intralayer correlated local distortions indicate electron-donating aspects that reflect in somewhat enlarged Fe–Se bonds. Additionally, they also reveal a degree of relief of chemical pressure associated with a large distance between Fe and Se sheets (“taller” anion height) and a stretched Fe–Fe square planar topology. The elongation of the latter, derived from the in situ PDF study, speaks for a plausible increase in the Fe-site vacancy concentration. The evolution of the local structural parameters suggests an optimum reaction window where kinetically stabilized phases resemble the distortions of the edge-sharing Fe–Se tetrahedra, required for a high- T c in expanded-lattice iron-chalcogenides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

In Situ Studies of the Formation of MoP Catalysts and Their Structure under Reaction Conditions for Higher Alcohol Synthesis: The Role of Promoters and Mesoporous Supports

Three formulations of a molybdenum phosphide (MoP) catalyst system were characterized for the higher alcohol synthesis (HAS) reaction using in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD), monitoring the chemical phase evolution during activation and under reaction conditions. Here, the in situ study herein provides important insights into the effect of the support and of K that lead to high performance in HAS for K-promoted MoP supported on carbon, as evidenced by previous studies (ethanol selectivity: 29%; conversion: 5%). During the activation process, XAS shows that the carbon-supported samples reduce and reach a highly crystalline state at a lower temperature than the SBA-15-supported sample, indicating a substantial difference in catalyst activation. After activation, the samples are introduced to relevant reaction conditions resulting in spectra fairly similar to one another. XRD results corroborate the difference in the degree of crystallinity of these samples, in alignment with the XAS, and reveal the formation of crystalline potassium pyrophosphate (K 4 P 2 O 7 ) during the activation period of the K-promoted samples. This K 4 P 2 O 7 phase remains present under reaction conditions. Taken together, these results provide insights into the roles played by the carbon support and K promotion, connecting activity to electronic and crystal structure.

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

Etched-And-Regrown GaN P–N Diodes with Low-Defect Interfaces Prepared by In Situ TBCl Etching

The ability to form pristine interfaces after etching and regrowth of GaN is a prerequisite for epitaxial selective area doping, which in turn is needed for the formation of lateral PN junctions and advanced device architectures. In this work, we report the electrical properties of etched-and-regrown GaN PN diodes using an in situ Cl-based precursor, tertiary butylchloride (TBCl). We demonstrated a regrowth diode with I–V characteristics approaching that from a continuously grown reference diode. The sources of unintentional contamination from the silicon (Si) impurity and the mediating effect of Si during the TBCl etching are also investigated in this study. Furthermore, this work points to the potential of in situ TBCl etching toward the realization of GaN lateral PN junctions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

In Situ Tracking of Nonthermal Plasma Etching of ZIF-8 Films

Surface characterization is critical for understanding the processes used for preparing catalysts, sorbents, and membranes. Nonthermal plasma (NTP) is a process that achieves high reactivity at low temperatures and is used to tailor the surface properties of materials. In this work, we combine the capabilities of infrared reflection absorption spectroscopy (IRRAS) with NTP for the in situ interrogation of zeolitic imidazolate framework-8 (ZIF-8) thin films to probe modifications in the material induced by oxygen and nitrogen plasmas. The IRRAS measurements in oxygen plasma reveal etching of organic ligands with sequential removal of the methyl group and imidazole ring and with the formation of carbonyl moieties (C═O). In contrast, nitrogen plasma induces mild etching and grafting of nitrile groups (−C≡N). Scanning electron microscopy imaging shows that oxygen plasma, at prolonged times, significantly degrades the ZIF-8 film at the grain boundaries. Treatment of ZIF-8 membranes using mild plasma conditions yields a fivefold enhancement for H 2 /N 2 and CO 2 /CH 4 ideal selectivities and an eightfold enhancement for CO 2 /N 2 ideal selectivity. Additionally, the new tools described here can be used for spectroscopic in situ tracking of plasma-induced chemistry on thin films in general.

IRRAS↗
DOE OSTI2026

In Situ Studies of Ru-CeO 2 –TiO 2 Catalysts for Selective CO 2 Hydrogenation to Methane: Importance of Metal ↔ Oxide–Oxide Interactions

Here, this work investigates Ru-CeO 2 -TiO 2 catalysts for the CO 2 methanation reaction and compares their performance with previously studied Ru-CeO 2 systems. Despite the lower Ru loading, the TiO 2 -containing catalysts exhibit significantly higher activity. To understand this behavior, in situ X-ray absorption spectroscopy (XAS) was carried out at the Ru K-edge and Ce L 3 -edge. Unlike Ru-CeO 2 , which displays reversible redox behavior of Ru, the Ru-CeO 2 -TiO 2 catalysts show irreversible Ru reduction and a substantially higher fraction of Ce 3+ species under all tested conditions (H 2 , CO 2 , H 2 /CO 2 ). The stabilization of metallic Ru during methanation, together with the enhanced formation of Ce 3+ promoted by TiO 2 through interfacial electronic transfer, accounts for their superior performance. Complementary in situ DRIFTS measurements reveal the formation and rapid consumption of bidentate carbonates and formates. These species act as a key intermediate in methane formation. Overall, these findings highlight the crucial role of the mixed CeO 2 -TiO 2 oxide in tuning the surface chemistry of the catalysts by stabilizing metallic Ru, enhancing ceria reducibility, and promoting efficient reaction pathways for CO 2 methanation. The manipulation of metal↔oxide-oxide interactions can be a very useful tool when dealing with the valorization of CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗