Engineering topics

Vajda, Stefan

Publications and source records attributed to Vajda, Stefan.

8 records

DOE OSTI2021

Probing Active Sites in Cu x Pd y Cluster Catalysts by Machine-Learning-Assisted X-ray Absorption Spectroscopy

Size-selected clusters are important model catalysts because of their narrow size and compositional distributions, as well as enhanced activity and selectivity in many reactions. Still, their structure-activity relationships are, in general, elusive. The main reason is the difficulty in identifying and quantitatively characterizing the catalytic active site in the clusters when it is confined within subnanometric dimensions and under the continuous structural changes the clusters can undergo in reaction conditions. Using machine learning approaches for analysis of the operando X-ray absorption near-edge structure spectra, we obtained accurate speciation of the Cu x Pd y cluster types during the propane oxidation reaction and the structural information about each type. As a result, we elucidated the information about active species and relative roles of Cu and Pd in the clusters.

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DOE OSTI2021

Subnanometer catalytic clusters for water splitting, method for splitting water using subnanometer catalyst clusters

The invention provides a catalytic electrode for converting molecules, the electrode comprising a predetermined number of single catalytic sites supported on a substrate. Also provided is a method for oxidizing water comprising contacting the water with size selected catalyst clusters. The invention also provides a method for reducing an oxidized moiety, the method comprising contacting the moiety with size selected catalyst clusters at a predetermined voltage potential.

Vajda, Stefan↗

DOE OSTI2021

CO 2 Methanation on Cu-Cluster Decorated Zirconia Supports with Different Morphology: A Combined Experimental In Situ GIXANES/GISAXS, Ex Situ XPS and Theoretical DFT Study

We report that subnanometer copper tetramer-zirconia catalysts turn out to be highly efficient for CO 2 hydrogenation and its conversion to methane. The cluster size and substrate morphology are controlled to optimize the catalytic performance. The two types of zirconia supports investigated are prepared by atomic layer deposition (~ 3 nm thick film) and supersonic cluster beam deposition (nanostructured film, ~ 100 nm thick). The substrate plays a crucial role in determining the activity of the catalyst as well as its cyclability over repeated thermal ramps. A temperature-programmed reaction combined with in situ X-ray characterization reveals the correlation between the evolution in the oxidation state and catalytic activity. Ex situ photoelectron spectroscopy indicates Cu clusters with stronger interactions with the nanostructured film, which can be the cause for the higher activity of this catalyst. Density functional theory calculations based on the Cu 4 O 2 cluster supported on a ZrOx subunit reveal low activation barriers and provide mechanism for CO 2 hydrogenation and its conversion to methane. Altogether, the results show a new way to tune the catalytic activity of CO 2 hydrogenation catalysts through controlling the morphology of the support at the nanoscale.

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DOE OSTI2020

Selective oxidative dehydrogenation of propane to propylene

The invention provides a method for generating alkenes, the method having the steps of contacting an alkane with catalyst clusters no greater than 10 nm for a time sufficient to convert the alkane to alkene.

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DOE OSTI2020

Interpreting the Operando XANES of Surface-Supported Subnanometer Clusters: When Fluxionality, Oxidation State, and Size Effect Fight.

X-ray absorption near edge structure (XANES) spectroscopy is widely used for operando catalyst characterization. We show that, for highly fluxional supported nanoclusters, the customary extraction of the oxidation state of the metal from the XANES data by fitting to the bulk standards is highly questionable. The XANES signatures as well as the apparent oxidation state for such clusters arise from a complex combination of many factors, and not only from the chemical composition in reaction conditions (e.g., oxygen content in oxidizing atmosphere). The thermally accessible isomerization and population of several structurally distinct cluster forms, cluster-support interaction, and intrinsic size effects all impact the metal oxidation state and XANES signal. We demonstrate this on copper oxide clusters with different compositions, Cu4Ox(x = 2-5) and Cu5Oy (y = 3, 5), deposited on amorphous alumina and ultrananocrystalline diamond, for which we computed the XANES spectra and compare the results to the experiment. We show in addition that fitting the experimental spectrum to calculated spectra of supported clusters can, in contrast, provide good agreement and insight into the spectrum-composition-structure relation. Experimental XANES interpreted using the proposed fitting scheme shows the partial reduction of Cu oxide clusters at rising temperatures, and pinpoints the specific stoichiometries that dominate in the ensemble of cluster states as the temperature changes.

Zandkarimi, Borna↗

DOE OSTI2020

Catalytic properties of model supported nanoparticles

Nanoparticles of late transition metals are used as catalysts and electrocatalysts for industrial chemical reactions that produce fuels, convert chemical energy to electricity and clean up pollution associated with the generation and use of these fuels. For such applications, metals are usually bonded onto the surfaces of oxide or carbon support materials. To provide the energy needed for sustained economic development, we must develop new and improved solid catalysts and electrocatalysts for a variety of reactions that take better advantage of traditional and alternate energy sources (solar, wind, biomass, etc.) and avoid serious environmental problems. Additionally, since these metals are often expensive and in limited supply (e.g., Pt), we also need to develop catalysts that do not require precious metals. As a consequence, recent years have seen a dramatic increase in research aimed at providing the basic understanding needed to develop new and improved catalysts and electrocatalysts for a variety of reactions that involve nanoparticles of late transition metals supported on oxide or carbon materials. It is therefore timely to present a special issue that focusses on Catalytic Properties of Model Supported Nanoparticles. The collection highlights some of the most exciting new directions for research in this area, and provides in depth examples of some of the most cutting-edge methods, both experimental and theoretical, for studying this class of catalysts, which provide insights into structure, mechanisms, kinetics and energetics with unprecedented accuracy and detail. Finally, as Guest Editors, we present below a few of the many excellent papers published in the collection.

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DOE OSTI2020

Structural reversibility of Cu doped NU-1000 MOFs under hydrogenation conditions

The metal-organic framework (MOF), NU-1000, and its metalated counterparts have found proof-of-concept application in heterogeneous catalysis and hydrogen storage amongst others. A vapor-phase technique, akin to atomic layer deposition (ALD), is used to selectively deposit divalent Cu ions on oxo, hydroxo-bridged hexa-zirconium(IV) nodes capped with terminal –OH and -OH 2 ligands. Subsequent reaction with steam yields node-anchored, CuII-oxo,hydroxo clusters. We find that cluster installation via AIM (= ALD In MOFs) is accompanied by an expansion of MOF mesopore (channel) diameter . We investigated the behavior of the cluster-modified material, termed Cu-AIM-NU-1000, to heat treatment up to 325 °C, at atmospheric pressure with a low flow of H2 into the reaction cell. The response under these conditions revealed two important results: (1) Above 200 °C, the initially installed few-metal-ion clusters reduce to neutral Cu atoms. The neutral atoms migrate from the nodes and aggregate into Cu nanoparticles. While the size of particles formed in the MOF interior is constrained by the width of mesopores (ca. 3 nm), those formed on the exterior surface of the MOF can grow as large as ca. 8 nm. (2) Reduction and release of Cu atoms from the MOFs nodes is accompanied NU-1000 undergoes dynamic structural transformation as it reverts back to its original dimension following the release. These results show while the MOF framework itself remains intact at 325 °C in an H 2 atmosphere, the small, AIM-installed Cu II -oxo,hydroxo clusters are stable with respect to reduction and conversion to metallic nanoparticles only up to ~200 °C.

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NASA NTRS1998

NEAR Gamma Ray Spectrometer Characterization and Repair

This report covers the work completed in the third year of the contract. The principle activities during this period were (1) the characterization of the NEAR 2 Gamma Ray Spectrometer using a neutron generator to generate complex gamma ray spectra and a large Ge Detecter to identify all the major peaks in the spectra; (2) the evaluation and repair of the Engineering Model Unit of the Gamma Ray Spectrometer for the NEAR mission; (3) the investigation of polycapillary x-ray optics for x-ray detection; and (4) technology transfer from NASA to forensic science.

Groves, Joel Lee↗