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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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Multi-scale simulation of reaction, transport and deactivation in a SBA-16 supported catalyst for the conversion of ethanol to butadiene

Effective design of heterogeneous catalytic systems requires careful coordination of physiochemical phenomena that span orders or magnitude in length and time scales. Multiscale modelling and simulation tools can provide useful insight for understanding and improving the performance of such systems. Mesoporous silica catalyst support materials present a versatile platform wherein support attributes may be tuned to control transport phenomena throughout the system. In this study we develop an integrated multiscale modelling approach for the conversion of ethanol to butadiene over a SBA-16 mesoporous silica supported catalyst. We use molecular dynamics simulations to calculate domain specific diffusivities of reactants and products in the various domains of SBA-16's nanostructure. This is used to calculate a resultant effective diffusivity through its microstructure using finite element method (FEM) models of the tessellated unit cell. The resultant intraparticle effective diffusivity enables the development of a reduced-order reactor level FEM model that is able to implicitly account for the SBA-16's transport effects without the explicit consideration of its detailed geometry. Experimental bench-scale conversion data for the ethanol to butadiene process over SBA-16 is used to extract intrinsic kinetic rate constants for a simplified reaction mechanism using this reduced order bench-scale reactor FEM model. The model is able to reproduce experimental trends in conversion and activity lifetimes. The impact of varying key support attributes such as pore-size and particle size on catalytic activity lifetimes is then explored. We demonstrate the utility of this multi-scale modelling strategy in guiding catalyst design for the development of rational strategies to improve the performance of heterogeneous supported catalytic systems.

09 BIOMASS FUELS↗
DOE OSTI2016

An Affinity-to-Commons Model of Public Support For Environmental Energy Policy

As atmospheric CO 2 continues to rise above 450 PPM, policymakers struggle with uncertainty concerning predictors of citizen support for environmental energy policies (EEPs) and preferences for their design, topics which have received limited attention in empirical literature. Here we present an original model of policy support based on citizens’ affinity-to-commons: pathways by which individuals enjoy natural public goods that in turn shape preferences between alternative policy mechanisms. We evaluate this model using a survey of southern California electricity customers, with results indicating the model's utility in predicting public support of EEP. Stronger community ties are associated with preferences for “pull”-type subsidies, whereas stronger connections to natural commons are linked to support for both “pull” and “push”-type sanctions. Findings have implications for coalition building as advocates may engender support for green energy policy by framing sanctions as protecting natural commons, and framing subsidies either in this same way and/or as producing benefits for communities.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2026

Elucidating the role of surface species in CO oxidation catalyzed by boron nitride nanotube supported transition metal oxides

Boron nitride nanotube (BNNT) is considered a highly promising catalyst support due to its outstanding thermal stability and chemical inertness. These characteristics make BNNT an attractive alternative for high-temperature applications. However, most studies to date have focused on incorporating platinum group metals (PGMs) to achieve high activity. Although BNNT-supported PGM catalysts are highly effective, their scarcity and high cost hinder widespread use in industrial processes. In this study, BNNT-supported transition metal oxides (TMO x /BNNT; TM = Fe, Co, Ni, and Cu) catalysts were investigated, and CO oxidation was applied as a model reaction to evaluate their catalytic performance. Several characterization techniques, including SEM-EDX, TEM, SXRD, H 2 -TPR, and XPS, were employed to examine their physicochemical properties. Notably, the particle size of the metal oxides differed significantly depending on the metal type. This variation is primarily attributed to the inherent metal–support interactions and the thermodynamic stability of each oxide during synthesis. These properties also affected catalytic activity, and various parameters, such as oxygen mobility and redox behavior, played important roles in determining performance. Finally, in situ DRIFTS, CO-TPSR, reaction-order analysis, and 18 O 2 isotope-labeling experiment were used to investigate the reaction mechanism. In conclusion, the findings provide insights into the design of cost-effective BNNT-supported catalysts and highlight their potential applicability in oxidation reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Supported oxorhenate catalysts prepared by thermal spreading of metal Re{sup 0} for methanol conversion to methylal

TiO{sub 2}-anatase and SiO{sub 2} supported oxorhenate catalysts were prepared by an original and simple technique based on the oxidative dispersion of metallic rhenium under dry conditions. The dispersion process of the supported oxorhenate phase as a function of the rhenium coverage and the support properties are discussed on the base of in situ characterization. The structures of the as prepared catalysts were found to be comparable to those of materials prepared using the incipient wetness impregnation technique. The absence of water in the preparation technique has made it possible to highlight the role of the hydration level on the rhenium oxide volatilization. The as-prepared Re/TiO{sub 2} catalysts were found to be effective for the direct conversion of methanol to methylal. - Graphical Abstract: Evolution of the 900-1000 cm{sup -1} region of the Raman spectrum of a mixture of metal rhenium with anatase TiO{sub 2} K03 upon heating in pure O{sub 2}. Highlights: > Supported rhenium catalysts can be easily prepared from metal Re. > This dry process is mainly a CVD immediately followed by rhenium deposition. > Hydration of the oxorhenate phase is dependent on the support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Essential elucidation for preparation of supported nickel phosphide upon nickel phosphate precursor

Preparation of supported nickel phosphide (Ni{sub 2}P) depends on nickel phosphate precursor, generally related to its chemical composition and supports. Study of this dependence is essential and meaningful for the preparation of supported Ni{sub 2}P with excellent catalytic activity. The chemical nature of nickel phosphate precursor is revealed by Raman and UV–vis spectra. It is found that initial P/Ni mole ratio ≥0.8 prohibits the Ni-O-Ni bridge bonding (i.e., nickel oxide). This chemical bonding will not result in Ni{sub 2}P structure, verified by XRD characterization results. The alumina (namely, γ-Al{sub 2}O{sub 3}, θ-Al{sub 2}O{sub 3}, or α-Al{sub 2}O{sub 3}) with distinct physiochemical properties also results in diverse chemical nature of nickel phosphate, and then different nickel phosphides. The influence of alumina support on producing Ni{sub 2}P was explained by the theory of surface energy heterogeneity, calculated by the NLDFT method based on N{sub 2}-sorption isotherm. The uniform surface energy of α-Al{sub 2}O{sub 3} results only in the nickel phosphosate precursor and thus the Ni{sub 2}P phase. - Graphical abstract: Surface energy heterogeneity in alumina (namely α-Al{sub 2}O{sub 3}, θ-Al{sub 2}O{sub 3}, and γ-Al{sub 2}O{sub 3}) supported multi-oxidic precursors with different reducibilities and thus diverse nickel phosphides (i.e., Ni{sub 3}P, Ni{sub 12}P{sub 5}, Ni{sub 2}P). - Highlights: • Preparing pure Ni{sub 2}P. • Elucidating nickel phosphate precursor. • Associating with surface energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Particle size effect of redox reactions for Co species supported on silica

Conversions of chemical states during redox reactions of two silica-supported Co catalysts, which were prepared by the impregnation method, were evaluated by using an in situ XAFS technique. The addition of citric acid into the precursor solution led to the formation on silica of more homogeneous and smaller Co particles, with an average diameter of 4 nm. The supported Co{sub 3}O{sub 4} species were reduced to metallic Co via the divalent CoO species during a temperature-programmed reduction process. The reduced Co species were quantitatively oxidized with a temperature-programmed oxidation process. The higher observed reduction temperature of the smaller CoO particles and the lower observed oxidation temperature of the smaller metallic Co particles were induced by the higher dispersion of the Co oxide species, which apparently led to a stronger interaction with supporting silica. The redox temperature between CoO and Co{sub 3}O{sub 4} was found to be independent of the particle size. - Graphical abstract: Chemical state conversions of SiO{sub 2}-supported Co species and the particle size effect have been analyzed by means of in situ XAFS technique. The small CoO particles have endurance against the reduction and exist in a wide temperature range. Display Omitted - Highlights: • The conversions of the chemical state of supported Co species during redox reaction are evaluated. • In operando XAFS technique were applied to measure redox properties of small Co particles. • A small particle size affects to the redox temperatures of cobalt catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Characterization of 430L porous supports obtained by powder extrusion moulding for their application in solid oxide fuel cells

The characterization of 430L stainless steel planar porous supports obtained by powder extrusion moulding was performed in this work. A thermoplastic multicomponent binder based on high density polyethylene and paraffin wax was selected for the process. Green supports were shaped by extrusion moulding, and subsequently the binder was removed by a thermal cycle previously optimized. Sintering was carried out at different temperatures in low vacuum. Density of sintered parts was measured by Archimedes' method and porosity was also evaluated through a microstructural analysis by optical microscopy. The porosity degree of samples sintered at low temperature was close to 35% which is a very suitable value for their application in SOFCs. Tensile tests were carried out in order to determine mechanical strength as a function of porosity degree. Based on these results, the best feedstock composition and processing parameters were selected. The oxidation behaviour in static air at high temperature was studied, and formed oxides were characterized in a scanning electron microscope equipped with energy dispersive analysis of X-rays. X-ray diffraction experiments were performed in order to identify the formed oxides based on formula Fe{sub 2−x}Cr{sub x}O{sub 3}. The results of these studies showed that this kind of ferritic stainless steel would be more suitable to be used as anodic supports where a rich hydrogen atmosphere is employed. Preliminary deposition tests allowed obtaining a homogeneous Ni–YSZ anode layer with a thickness of 10 μm on the porous metallic substrates. - Highlights: • 430L stainless steel porous supports were obtained by powder extrusion moulding. • Porosity degree was controlled sintering at different temperatures in low vacuum. • Tensile tests allowed determining mechanical strength of porous supports. • A study about its oxidation behaviour in static air at high temperature was realized. • After oxidation, formed oxides were characterized by EDS–SEM and XRD.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Photocatalytic hydrogen production using visible-light-responsive Ta{sub 3}N{sub 5} photocatalyst supported on monodisperse spherical SiO{sub 2} particulates

Graphical abstract: A simple and effective sol–gel process followed by nitridation in an NH{sub 3} flow has been developed to deposit Ta{sub 3}N{sub 5} semiconductor photocatalyst layers onto monodisperse spherical SiO{sub 2} particles. The obtained Ta{sub 3}N{sub 5}/SiO{sub 2} particles maintain an original spherical morphology of SiO{sub 2} and a sub-micrometer size with a narrow size distribution and without aggregation. The presence of SiO{sub 2} support shows at least no detrimental effects on photocatalytic activity, but tunes the secondary particle size to control dispersibility of the photocatalyst in the solution. - Highlights: • Fine nanoparticles of Ta{sub 3}N{sub 5} were immobilized on the surfaces of SiO{sub 2} giving SiO{sub 2}@Ta{sub 3}N{sub 5} core–shell spheres successfully produced H{sub 2} from methanol solution under visible light. • The presence of support (SiO{sub 2}) ensures the dispersion of the particulate in solution maintaining high photocatalytic activity of Ta{sub 3}N{sub 5}. • The obtained supported photocatalyst gives uniform size distribution and control the degree of dispersibility in the solution, which may control nature of light absorption and reflection of the photoreactor. - Abstract: Fine nanoparticles of Ta{sub 3}N{sub 5} (10–20 nm) were synthesized on the surfaces of SiO{sub 2} spheres with a diameter of ∼550 nm. A sol–gel method was used to modify the surface of SiO{sub 2} with Ta{sub 2}O{sub 5} from TaCl{sub 5} dissolved in ethanol in the presence of citric acid and polyethylene glycol. The resulting oxide composites were treated in an NH{sub 3} flow at 1123 K to form core–shell structured Ta{sub 3}N{sub 5}/SiO{sub 2} sub-microspheres. The obtained samples were characterized using powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDX), transmission electron microscopy (TEM), and photocatalytic activity measurements for H{sub 2} evolution from an aqueous methanol solution. The XRD results demonstrate the expected sequential formation of Ta{sub 2}O{sub 5} layers, followed by Ta{sub 3}N{sub 5} after nitridation on the Ta{sub 2}O{sub 5}/SiO{sub 2} composite. SEM and TEM observations indicate that the obtained Ta{sub 3}N{sub 5}/SiO{sub 2} sub-microspheres have a uniform size distribution with high crystallinity and an obvious core–shell structure. The presence of support maintained the intrinsic photocatalytic activity of Ta{sub 3}N{sub 5} nanoparticles, but it did drastically improve the dispersion of the photocatalysts in the solution. This study proposes the use of an inert support in photocatalytic reactors to improve ease of handling the powder photocatalyst for gas-phase photocatalysis and the suspension of the solution, controlling nature of light harvesting and degree of scattering of the photoreactor.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Vector-model-supported approach in prostate plan optimization

Lengthy time consumed in traditional manual plan optimization can limit the use of step-and-shoot intensity-modulated radiotherapy/volumetric-modulated radiotherapy (S&S IMRT/VMAT). A vector model base, retrieving similar radiotherapy cases, was developed with respect to the structural and physiologic features extracted from the Digital Imaging and Communications in Medicine (DICOM) files. Planning parameters were retrieved from the selected similar reference case and applied to the test case to bypass the gradual adjustment of planning parameters. Therefore, the planning time spent on the traditional trial-and-error manual optimization approach in the beginning of optimization could be reduced. Each S&S IMRT/VMAT prostate reference database comprised 100 previously treated cases. Prostate cases were replanned with both traditional optimization and vector-model-supported optimization based on the oncologists' clinical dose prescriptions. A total of 360 plans, which consisted of 30 cases of S&S IMRT, 30 cases of 1-arc VMAT, and 30 cases of 2-arc VMAT plans including first optimization and final optimization with/without vector-model-supported optimization, were compared using the 2-sided t-test and paired Wilcoxon signed rank test, with a significance level of 0.05 and a false discovery rate of less than 0.05. For S&S IMRT, 1-arc VMAT, and 2-arc VMAT prostate plans, there was a significant reduction in the planning time and iteration with vector-model-supported optimization by almost 50%. When the first optimization plans were compared, 2-arc VMAT prostate plans had better plan quality than 1-arc VMAT plans. The volume receiving 35 Gy in the femoral head for 2-arc VMAT plans was reduced with the vector-model-supported optimization compared with the traditional manual optimization approach. Otherwise, the quality of plans from both approaches was comparable. Vector-model-supported optimization was shown to offer much shortened planning time and iteration number without compromising the plan quality.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2014

Multi-wavelength Raman spectroscopy study of supported vanadia catalysts: Structure identification and quantification

Revealing the structure of supported metal oxide catalysts is a prerequisite for establishing the structure - catalysis relationship. Among a variety of characterization techniques, multi-wavelength Raman spectroscopy, combining resonance Raman and non-resonance Raman with different excitation wavelengths, has recently emerged as a particularly powerful tool in not only identifying but also quantifying the structure of supported metal oxide clusters. In our review, we make use of two supported vanadia systems, VO x /SiO 2 and VO x /CeO 2 , as examples to showcase how one can employ this technique to investigate the heterogeneous structure of active oxide clusters and to understand the complex interaction between the oxide clusters and the support. Moreover, the qualitative and quantitative structural information gained from the multi-wavelength Raman spectroscopy can be utilized to provide fundamental insights for designing more efficient supported metal oxide catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Enhancing the Carbon Monoxide Oxidation Performance through Surface Defect Enrichment of Ceria-Based Supports for Platinum Catalyst

Effective synthesis and application of single-atom catalysts on supports lacking enough defects remain a significant challenge in environmental catalysis. Herein, we present a universal defect-enrichment strategy to increase the surface defects of CeO 2 -based supports through H 2 reduction pretreatment. The Pt catalysts supported by defective CeO 2 -based supports, including CeO 2 , CeZrO x , and CeO 2 /Al 2 O 3 (CA), exhibit much higher Pt dispersion and CO oxidation activity upon reduction activation compared to their counterpart catalysts without defect enrichment. Specifically, Pt is present as embedded single atoms on the CA support with enriched surface defects (CA-HD) based on which the highly active catalyst showing embedded Pt clusters (Pt C ) with the bottom layer of Pt atoms substituting the Ce cations in the CeO 2 surface lattice can be obtained through reduction activation. Embedded PtC can better facilitate CO adsorption and promote O 2 activation at Pt C –CeO 2 interfaces, thereby contributing to the superior low-temperature CO oxidation activity of the Pt/CA-HD catalyst after activation.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Composite Carbon Molecular Sieve Hollow Fiber Membranes: Resisting Support Densification via Silica Particle Stabilization

Resisting densification of hollow fiber support layers under high-temperature pyrolysis is vital to form carbon molecular sieve hollow fiber membranes with thin separation layer and attractive productivity. In this paper, a new silica particle stabilization approach is introduced to form thin-skinned composite carbon molecular sieve hollow fiber membranes with excellent resistance to support layer densification. By dispersing small-sized silica particles with low bulk density in the support layer of polymer precursor hollow fibers, composite carbon molecular sieve hollow fiber membranes were formed with highly porous supports. The composite carbon molecular sieve hollow fiber membranes exhibited very attractive selectivities and productivities higher than those of monolithic asymmetric carbon molecular sieve hollow fiber membranes formed by the standard sol–gel support stabilization technique.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO 2 Capture Applications: A Quasielastic Neutron Scattering Study

Composite gas sorbents, formed from an active polymer phase and a porous support, are promising materials for the separation of acid gases from a variety of gas streams. Significant changes in sorption performance (capacity, rate, stability etc.) can be achieved by tuning the properties of the polymer and the nature of interactions between polymer and support. We utilize quasielastic neutron scattering (QENS) and coarse-grained molecular dynamics (MD) simulations to characterize the dynamic behavior of the most commonly reported polymer in such materials, poly(ethylenimine) (PEI), both in bulk form and when supported in a mesoporous silica framework. The polymer chain dynamics (rotational and translational diffusion) are characterized using two neutron backscattering spectrometers that have overlapping time scales, ranging from picoseconds to a few nanoseconds. Two modes of motion are detected for the PEI molecule in QENS. At low energy transfers, a “slow process” on the time scale of ~200 ps is found and attributed to jump-mediated, center-of-mass diffusion. Second, a “fast process” at ~20 ps scale is also found and is attributed to a locally confined, jump-diffusion. Characteristic data (time scale and spectral weight) of these processes are compared to those characterized by MD, and reasonable agreement is found. For the nanopore-confined PEI, we observe a significant reduction in the time scale of polymer motion as compared to the bulk. The impacts of silica surface functionalization and of polymer fill fraction in the silica pores (controlling the portion of polymer molecules in contact with the pore walls), are both studied in detail. Hydrophobic functionalization of the silica leads to an increase of the PEI mobility above that in native silanol-terminated silica, but the dynamics are still slower than those in bulk PEI. Sorbents with faster PEI dynamics are also found to be more efficient for CO 2 capture, possibly because sorption sites are more accessible than those in systems with slower PEI dynamics. Therefore, this work supports the existence of a link between the affinity of the support for PEI and the accessibility of active sorbent functional groups.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Assessing the Activity of Ni Clusters Supported on TiC(001) toward CO 2 and H 2 Dissociation

Small Ni particles supported on TiC(001) were shown to display a very high activity for the catalytic hydrogenation of CO 2 but the underlying chemistry is, to a large extent, unknown. Here, by means of periodic density functional theory (DFT) calculations with the BEEF–vdW functional, we explore the adsorption and subsequent dissociation of CO 2 and H 2 on several Ni n clusters ( n = 4, 9, 13, and 16) supported on TiC(001) and compare the results to those obtained for the bare Ni(111) and TiC(001) surfaces using exactly the same computational approach. The calculations reveal that the Ni n /TiC system exhibits stronger adsorption energies and lower dissociation energy barriers for CO 2 and H 2 than the bare Ni(111) and TiC(001) surfaces. Furthermore, this is in line with the experimental finding evidencing that the Ni/TiC system has a catalytic activity higher than that of the separated Ni and TiC constituents. In addition, the calculated results show that two-dimensional (2D) supported clusters adsorb CO 2 and H 2 stronger than the three-dimensional (3D) supported clusters and also the 2D clusters exhibit lower energy barriers for CO 2 dissociation. Within the 2D supported clusters, larger particles feature slightly stronger adsorption energies and lower CO 2 dissociation energy barriers. Finally, H 2 dissociation proceeds with a very low energy barrier on all of the studied models, which makes these novel systems potential good candidates for hydrogenation reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enhancing CO Oxidation Activity via Tuning a Charge Transfer Between Gold Nanoparticles and Supports

Charge transfer from the supports to nanoparticles at the interface is one of the key factors to determine the catalytic performances of supported nanoparticles. In this work, we revealed that the charge transfer from semiconductor support to Au nanoparticle catalysts enhanced their activity toward CO oxidation. In this work, a novel Au/SiO 2 /Si composite system with precisely controllable SiO 2 layer thickness was fabricated to tune the magnitude of interfacial charge transfer. With the support of X-ray photoelectron spectroscopy and numerical simulations, it was demonstrated that the Schottoky barrier formed across the Au/SiO 2 /Si heterojunction led to negative charge accumulation at the surface of Au nanoparticles, which may be transferred to the antibonding orbitral of adsorbed O 2 molecules to the O-O bonds. This discovery highlights a new perspective in explaining the role of strong metal-support interactions for catalytic reactions and provides a fresh path for designing the next generation of nanocatalysts.

36 MATERIALS SCIENCE↗
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 OSTI2022

Tuning Strong Metal–Support Interaction Kinetics on Pt-Loaded TiO 2 (110) by Choosing the Pressure: A Combined Ultrahigh Vacuum/Near-Ambient Pressure XPS Study

Pt catalyst particles on reducible oxide supports often change their activity significantly at elevated temperatures due to the strong metal–support interaction (SMSI), which induces the formation of an encapsulation layer around the noble metal particles. However, the impact of oxidizing and reducing treatments at elevated pressures on this encapsulation layer remains controversial, partly due to the “pressure gap” between surface science studies and applied catalysis. In the present work, we employ synchrotron-based near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) to study the effect of O 2 and H 2 on the SMSI-state of well-defined Pt/TiO 2 (110) catalysts at pressures of up to 0.1 Torr. Further, by tuning the O 2 pressure, we can either selectively oxidize the TiO 2 support or both the support and the Pt particles. Catalyzed by metallic Pt, the encapsulating oxide overlayer grows rapidly in 1 × 10 –5 Torr O 2 , but orders of magnitude less effectively at higher O 2 pressures, where Pt is in an oxidic state. While the oxidation/reduction of Pt particles is reversible, they remain embedded in the support once encapsulation has occurred.

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

Molecular Design of Supported MoO x Catalysts with Surface TaO x Promotion for Olefin Metathesis

A series of supported 3% MoOx catalysts were synthesized by incipient-wetness impregnation of 5%-15% TaO x surface modified γ-Al 2 O 3 support. The catalysts were characterized by in situ spectroscopies (DRIFTS, Raman, UV-vis, XAS) and multiple chemical probes (C 2 H 4 /C 4 H 8 titration, C 3 H 6 -TPSR, steady state propylene metathesis, NH 3 -IR adsorption). The supported tantalum oxide phase was present as surface TaO x sites on the γ-Al 2 O 3 support that capped that Al 2 O 3 surface hydroxyls. The change in available surface hydroxyls caused the subsequent anchoring of MoOx species to occur at different surface hydroxyls. This shifted the anchoring of MoO x species from basic (Al-OH) to neutral (Al 2 -OH) to more acidic (Al 3 -OH) surface hydroxyls as well as perturbation of the remaining alumina surface hydroxyls by the surface TaO x sites. The TaO x surface modified γ-Al 2 O 3 support increased the number of activated surface MoO x sites (Ns) by ~6x and the TOF by ~10x resulting in an increased activity of ~60x. In conclusion, It was found that the specific anchoring surface hydroxyls rather than the extent of oligomerization of the surface MoO x sites control the number of activated MoO x sites and TOF for propylene metathesis. No relationship between the nature of the surface Lewis/Brønsted acid sites and Ns and TOF were found to be present.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗