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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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23 records · Page 2

Electronic interactions and stability issues at the copper-graphene interface in air and in alkaline solution under electrochemical control

A micro-electrochemical cell is sealed with a polymer-free single-layer graphene (SLG) membrane to monitor the stability of Cu nanoparticles (NPs) attached to SLG, as well as the interfacial electronic interactions between Cu NPs and SLG both in air and in a mildly alkaline aqueous solution under electrochemical control. A combination of techniques, including in-situ Kelvin probe force microscopy (KPFM) and ex-situ electron microscopy, are applied. When Cu NPs are metallic at cathodic potentials, there is a relatively bias-independent offset in the SLG work function due to charge transfer at the Cu-SLG contact. When Cu NPs are oxidized at anodic potentials, on the other hand, the work function of SLG also depends on the applied bias in a quasi-linear fashion due to electrochemical gating, in addition to charge transfer at the CuOx-SLG contact. Furthermore, Cu NPs were found to oxidize and detach from SLG when kept under anodic potentials for a few hours, whereas they remain adhered to SLG at cathodic potentials. This is attributed to water intercalation at the CuO-SLG interface associated with the enhanced hydrophilicity of positively polarized graphene, as supported by the absence of Cu detachment following oxidation by galvanic corrosion in air.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Oxidation Studies of High-Entropy Alloy Nanoparticles

Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe 0.28 Co 0.21 Ni 0.20 Cu 0.08 Pt 0.23 HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner's theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe 2 O 3 , CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.

36 MATERIALS SCIENCE↗

MgO Nanostructures on Cu(111): Understanding Size- and Morphology-Dependent CO 2 Binding and Hydrogenation

To design and optimize cost-effective technologies for the capture, utilization, and storage of carbon dioxide (CO 2 ), we need a fundamental knowledge and control of chemical interactions associated with the capture and conversion of the molecule into high-value chemicals, minerals, and all kinds of materials. Bulk magnesium oxide (MgO) is frequently used for the trapping and storage of CO 2 by generation of magnesium carbonates. In this study, the growth and reactivity of MgO nanostructures on a Cu 2 O/Cu(111) substrate were investigated using scanning tunneling microscopy (STM) and synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). For extremely small concentrations of Mg (~ 0.01 monolayer (ML)), a well-ordered film of copper oxide with small clusters (0.2-0.5 nm in width, 0.4-0.6 Å in height) of embedded MgO was seen. At a coverage of 0.1 ML, MgO nanoparticles with a width of 0.4 to 1 nm and a height of ~ 1.5 Å were randomly distributed on the copper oxide. Further, random distribution was also observed when the MgO coverage was raised to 0.25 ML, with the width of the MgO particles increasing to 2-2.5 nm and the height reaching 2 Å. These oxide nanostructures displayed a high reactivity towards CO 2 and H 2 that is not seen for bulk MgO. Dissociation of H 2 was observed at room temperature with reaction of the H adatoms with CuO x and C-containing groups. On the small MgO nanostructures (< 1 nm in width), instead of plain carbonate formation, there was dissociation of CO 2 into CO and C species, opening reaction channels for the conversion of this harmful molecule into oxygenates and light alkanes.

03 NATURAL GAS↗

Energetic decomposition yields efficient bimetallic Cu MOF-derived catalysts

Metal–organic frameworks (MOFs) have recently emerged as efficient self-sacrificial templates to fabricate porous carbon-supported metal nanoparticles (NPs). Due to observed increased activity, catalysts containing bimetallic NPs represent an active frontier for heterogeneous catalyst development. A strategy to synthesize active catalysts with highly dispersed bimetallic metal/metal oxides within a porous carbon matrix via rapid MOF decomposition using dopants is presented in this paper. A 2,4,6-trinitrotoluene (TNT) additive enhances the rapid thermolysis of the metal-doped Cu-based MOFs to minimize particle aggregation. Catalyst characterization reveals that a secondary metal increases dispersion of both metals over the carbon composite support. The catalyst preparation method influences both the metal particle size and oxidation state. Catalytic performance shows increased rates for 4-nitrophenol reduction even with <1 wt% of added secondary metal. Among the synthesized catalysts, the Ni–CuO@C bimetallic catalyst exhibits outstanding activity. This synthetic strategy is useful for creating highly efficient, robust, non-noble metal catalysts for development of sustainable chemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave-Assisted Synthesis of Cu@IrO 2 Core-Shell Nanowires for Low-Temperature Methane Conversion

A facile microwave-assisted synthesis was developed for the tunable fabrication of a novel Cu@IrO 2 core@shell nanowire motif. Experimental parameters, such as (i) reaction time, (ii) the method of addition of the Ir precursor, (iii) capping agent, (iv) reducing agent, as well as (v) the capping agent-to-reducing agent ratio, were subsequently optimized. The viability of other methods based on previously reported literature, such as refluxing, stirring, and physical sonication, was studied and compared with our optimized microwave-assisted protocol in creating our as-prepared materials. It should be noted that the magnitude of the IrO 2 shell could be tailored based on varying the Cu: Ir ratio coupled with judicious variations in the amounts of capping agent and reducing agent. Structural characterization techniques, such as XRD, XPS, and HRTEM (including HRTEM-EDS), were used to analyze our Cu@IrO 2 motifs. Specifically, the shell could be reliably tailored from sizes of 10 nm, 8 nm, 6 nm, and 3.5 nm with corresponding Cu: Ir ratios of 10:1, 15:1, 20:1, and 25:1, respectively. Moreover, the structural integrity of the motifs was probed and found to have been maintained after not only heat treatment but also the post-methane conversion process, indicative of an intrinsically high stability. Both components within the CuO-IrO 2 interface were able to activate methane at temperatures between 400 to 500 K with a reduction of the associated metal cations (Cu 2+ → Cu 1+ ; Ir 4+ → Ir 3+ ) and the deposition of CH x fragments on the surface, as clearly observed in the ambient-pressure XPS results. Thus, on the basis of their stability and chemical activity, these core-shell materials could be very useful for the catalytic conversion of methane into 'higher value" chemicals.

36 MATERIALS SCIENCE↗