Atomic level fluxional behavior and activity of CeO2-supported Pt catalysts for CO oxidation

Reducible oxides are widely used catalyst supports that can increase oxidation reaction rates by transferring lattice oxygen at the metal-support interface. There are many outstanding questions regarding the atomic-scale dynamic meta-stability (i.e., fluxional behavior) of the interface during catalysis. Here, we employ aberration-corrected operando electron microscopy to visualize the structural dynamics occurring at and near Pt/CeO2 interfaces during CO oxidation. We show that the catalytic turnover frequency correlates with fluxional behavior that (a) destabilizes the supported Pt particle, (b) marks an enhanced rate of oxygen vacancy creation and annihilation, and (c) leads to increased strain and reduction in the CeO2 support surface. Overall, the results implicate the interfacial Pt-O-Ce bonds anchoring the Pt to the support as being involved also in the catalytically-driven oxygen transfer process, and they suggest that oxygen reduction takes place on the highly reduced CeO2 surface before migrating to the interfacial perimeter for reaction with CO.

Reducing the irreducible: Dispersed metal atoms facilitate reduction of irreducible oxides.

Oxide reducibility is a central concept quantifying the role of the support in catalysis. While reducible oxides are often considered catalytically active, irreducible oxides are seen as inert supports. Enhancing the reducibility of irreducible oxides has, however, emerged as an effective way to increase their catalytic activity while retaining their inherent thermal stability. In this work, we focus on the prospect of using single metal atoms to increase the reducibility of a prototypical irreducible oxide, zirconia. Based on extensive self-consistent DFT+U calculations, we demonstrate that single metal atoms significantly improve and tune the surface reducibility of zirconia. Detailed analysis of the observed single atom induced reducibility allows us to attribute the enhanced reducibility to strong interactions between the metal atom and the electrons trapped in the vacancy, and d-p orbital interactions between the metal atom and oxygen. This analysis enables transferring the obtained theoretical understanding to other irreducible oxides as well. The detailed understanding of how oxide reducibility can be tuned offers precise control over the catalytic properties of metal--oxides.

Sequential geochemical extractions and mineralogy of Fe-bearing minerals in carbonatized mantle rocks in the Samail Ophiolite, Oman

<p>Within the Samail Ophiolite, Oman, there are intervals of listvenite outcrops between layers of serpentinite zones above the basal thrust zone, atop the metamorphic sole. Near the base of the ophiolite mantle section, some peridotites underwent 100% carbonation from metasomatic introduction of CO<sub>2</sub>-bearing fluids <200°C to form listvenites during the time of emplacement (97 ± 29 Ma, Falk and Kelemen, 2015). The carbonate rocks comprise mostly magnesite and/or dolomite, quartz, Cr-spinel, and Fe-(hydr)oxides; with carbonates as the sole Mg-minerals and quartz as the only silicate phase. The aim of this study is to chemically and petrographically investigate the Fe-bearing minerals within the fluid-altered mantle rocks in drill core samples from hole BT1B of the ICDP Oman Drilling Project. Sequential chemical extractions are useful for recognizing iron pools based on the minerology. We investigated the quantities of Fe-oxide/hydroxide phases through a series of chemical extractions (Poulton and Canfield, 2005) via atomic absorption spectroscopy in addition to optical microscope, SEM/EDS, EPMA/WDS and ICP analysis. Extractions performed at room temperature and one at 50°C included: carbonate-associated Fe (sodium acetate) targeting siderite, HCl-extractable Fe(II), reducible oxides (citrate-dithionite) targeting hematite and possible goethite, and magnetite (oxalate). Carbonate-based Fe in the listvenites from a sodium acetate extraction ranges from 12-28 mg/g, while the same extraction performed at 50°C for twice as long resulted in higher proportions of carbonate-associated Fe (15-35 mg/g). Easily reducible iron quantities from the diluted HCl solution extraction display the lowest overall Fe fractions (0.75-5.5 mg/g) following the room temperature acetate and 0.63-1.7 mg/g after the 50°C acetate extraction. Fe in reducible oxides extracted by dithionite ranged from 1.4-15 mg/g with similar result after both a room-temperature acetate and a 50°C acetate step. Oxalate extraction succeeding the room-temperature acetate yielded magnetite concentrations of 1.9-8.0 mg/g, while the increased temperature and time in the first step (acetate extraction) were followed by significantly lower amounts of Fe extracted by oxalate (0.47- 3.6 mg/g). Additionally, the same extractions were performed on a pure siderite sample from Greenland. For siderite samples crushed a week prior to analysis, the carbonate-associated Fe in sodium acetate extract was 165±17 mg/g; the sidenote yielded 42 wt% of overall extracted Fe (392±33 mg/g). This is only slightly lower than the expected 48.2 wt% of Fe for a pure siderite sample. Dilute HCl extractions display results of 126±5.4 mg/g, dithionite solution extracted 25±0.5 mg/g and oxalate proportions were 76±9 mg/g. Due to possible oxidation of siderite to magnetite occurring during the time between powdering the samples and analysis, the full dissolution of siderite may not be fully represented in only the acetate. Microprobe data shows a total amount of FeO in carbonates as 1.3-10.8 wt%. This is more than or similar to the acetate and HCl proportions of Fe which represent carbonate associated minerals in the listvenites. Data obtained from EMPA and ICP will additionally be discussed in relation to the Fe-oxide phases with relation to the listvenites minerology.</p>

Machine Learning in Computational Surface Science and Catalysis: Case Studies on Water and Metal–Oxide Interfaces

The goal of many computational physicists and chemists is the ability to bridge the gap between atomistic length scales of about a few multiples of an Ångström (Å), i. e., 10−10 m, and meso- or macroscopic length scales by virtue of simulations. The same applies to timescales. Machine learning techniques appear to bring this goal into reach. This work applies the recently published on-the-fly machine-learned force field techniques using a variant of the Gaussian approximation potentials combined with Bayesian regression and molecular dynamics as efficiently implemented in the Vienna ab initio simulation package, VASP. The generation of these force fields follows active-learning schemes. We apply these force fields to simple oxides such as MgO and more complex reducible oxides such as iron oxide, examine their generalizability, and further increase complexity by studying water adsorption on these metal oxide surfaces. We successfully examined surface properties of pristine and reconstructed MgO and Fe3O4 surfaces. However, the accurate description of water–oxide interfaces by machine-learned force fields, especially for iron oxides, remains a field offering plenty of research opportunities.

Sequential geochemical extractions and mineralogy of Fe-bearing minerals of mantle rocks in the Samail Ophiolite, Oman

<p>Within the Samail Ophiolite, Oman, there are intervals of listvenite outcrops between layers of serpentinite zones above the basal thrust zone, atop the metamorphic sole. Near the base of the ophiolite mantle section, some peridotites underwent 100% carbonation from metasomatic introduction of CO<sub>2</sub>-bearing fluids (~100°C) to form listvenites during the time of emplacement (97 ± 29 Ma, Falk and Kelemen, 2015). The carbonate rocks comprise mostly magnesite and/or dolomite, quartz, spinel, and Fe-(hydr)oxides; with carbonates as the sole Mg-minerals and quartz as the only silicate phase. The aim of this study is to chemically and petrographically investigate the Fe-bearing minerals within the fluid-altered mantle rocks in drill core samples from hole BT1B of the ICDP Oman Drilling Project. We investigated the quantities of Fe-oxide/hydroxide phases through a series of chemical extractions (Poulton and Canfield, 2005) via atomic absorption spectroscopy in addition to optical microscope/ SEM/EDS analysis. Sequential chemical extractions are useful for recognizing iron pools based on the minerology. Extractions preformed at room temperature show varying proportions of carbonate-associated Fe (sodium acetate), reducible oxides (citrate-dithionite), magnetite (oxalate), and HCl-extractable Fe(II). The amount of Fe in carbonates based on sodium acetate extraction ranges from 17-54% of the overall extracted iron (12-28 ‰) in the samples. The same extraction performed at 50°C for twice as long resulted in higher proportions of carbonate-associated Fe extracted with a range of 44-85% of the total extracted iron (15-35 ‰). Easily reducible iron quantities from a diluted HCl solution extraction display the lowest overall Fe fractions at 6.2-25% following the room temperature acetate and 2.6-6.2% after the 50°C acetate extraction. Reducible oxides extracted by dithionite were wide ranging (8.3-49%) as a proportion of the overall extracted iron, with similar results following the 50°C acetate step (5.3-48%). Oxalate extraction succeeding the room temperature acetate revealed magnetite proportions of 13-28%, while the increased temperature and time in the first step (acetate extraction) resulted in significantly lower proportions of Fe extracted by oxalate (3.1-10%). Falk and Kelemen (2015) suggest significant amounts of poorly crystalline Fe-phases or amorphous oxides within the listvenites not detected by X-ray diffraction, but we do not see evidence of this based on the relatively small HCl fractions. Further examination of the total elemental compositions of the individual solutions and electron microprobe analyses will reveal more details about the Fe-minerals dissolved in each extract and weather they represent separate Fe-oxide/hydroxide phases.    </p><p> </p><p>Falk, E. S., & Kelemen, P. B. (2015). Geochemistry and petrology of listvenite in the Samail ophiolite, Sultanate of Oman: Complete carbonation of peridotite during ophiolite emplacement.<em> Geochimica et Cosmochimica Acta</em>, 160, 70-90.</p><p>Poulton, S. W., & Canfield, D. E. (2005). Development of a sequential extraction procedure for iron: implications for iron partitioning in continentally derived particulates. <em>Chemical Geology</em>, 214(3-4), 209-221.</p><p> </p>

What Changes on the Inverse Catalyst? Insight From CO Oxidation on Au-Supported Ceria Nanoparticles Using Ab Initio Molecular Dynamics

Oxidation reactions catalyzed by Au nanoparticles supported on reducible oxides have been widely studied both experimentally and theoretically, whereas <i>inverse catalysts</i>, in which oxide nanoparticles are supported on metal surfaces, received considerably less attention. In both systems catalytic activity at metal – oxide interfaces can arise not only from each material contributing its functionality, but also from their interactions creating properties beyond the sum of individual components. Inverse catalysts may retain the synergy between the metal and oxide functionalities, while offering further specific advantages, e.g. a possibility to have better control over interfacial sites or to yield improved stability, activity, and selectivity. Our work provides the mechanism of O atom/vacancy diffusion-assisted Mars-van-Krevelen CO oxidation on gold-supported ceria nanoparticle through state-of-the-art ab initio molecular dynamic simulation studies.

What Changes on the Inverse Catalyst? Insight From CO Oxidation on Au-Supported Ceria Nanoparticles Using Ab Initio Molecular Dynamics

Oxidation reactions catalyzed by Au nanoparticles supported on reducible oxides have been widely studied both experimentally and theoretically, whereas <i>inverse catalysts</i>, in which oxide nanoparticles are supported on metal surfaces, received considerably less attention. In both systems catalytic activity at metal – oxide interfaces can arise not only from each material contributing its functionality, but also from their interactions creating properties beyond the sum of individual components. Inverse catalysts may retain the synergy between the metal and oxide functionalities, while offering further specific advantages, e.g. a possibility to have better control over interfacial sites or to yield improved stability, activity, and selectivity. Our work provides the mechanism of O atom/vacancy diffusion-assisted Mars-van-Krevelen CO oxidation on gold-supported ceria nanoparticle through state-of-the-art ab initio molecular dynamic simulation studies.