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At least 325 records · Page 18

Extraordinary Thermal Stability and Sinter Resistance of Sub-2 nm Platinum Nanoparticles Anchored to a Carbon Support by Selenium

Nanoparticle sintering has long been a major challenge in developing catalytic systems for use at elevated temperatures. Here we report an in situ electron microscopy study of the extraordinary sinter resistance of a catalytic system comprised of sub-2 nm Pt nanoparticles on a Se-decorated carbon support. When heated to 700 °C, the average size of the Pt nanoparticles only increased from 1.6 to 2.2 nm, while the crystal structure, together with the {111} and {100} facets, of the Pt nanoparticles was well retained. Our electron microscopy analyses suggested that the superior resistance against sintering originated from the Pt–Se interaction. Confirmed by energy-dispersive X-ray elemental mapping and electron energy loss spectra, the Se atoms surrounding the Pt nanoparticles could survive the heating. This work not only offers an understanding of the physics behind the thermal behavior of this catalytic material but also sheds light on the future development of sinter-resistant catalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomically Precise Single-Site Catalysts via Exsolution in a Polyoxometalate–Metal–Organic-Framework Architecture

Single-site catalysts (SSCs) achieve a high catalytic performance through atomically dispersed active sites. A challenge facing the development of SSCs is aggregation of active catalytic species. Reducing the loading of these sites to very low levels is a common strategy to mitigate aggregation and sintering; however, this limits the tools that can be used to characterize the SSCs. Here we report a sintering-resistant SSC with high loading that is achieved by incorporating Anderson–Evans polyoxometalate clusters (POMs, MMo 6 O 24 , M = Rh/Pt) within NU-1000, a Zr-based metal–organic framework (MOF). The dual confinement provided by isolating the active site within the POM, then isolating the POMs within the MOF, facilitates the formation of isolated noble metal sites with low coordination numbers via exsolution from the POM during activation. The high loading (up to 3.2 wt %) that can be achieved without sintering allowed the local structure transformation in the POM cluster and the surrounding MOF to be evaluated using in situ X-ray scattering with pair distribution function (PDF) analysis. Notably, the Rh/Pt···Mo distance in the active catalyst is shorter than the M···M bond lengths in the respective bulk metals. Furthermore, models of the active cluster structure were identified based on the PDF data with complementary computation and X-ray absorption spectroscopy analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rinse-Free, Sodium-Efficient Synthesis of O3-Type Layered Oxide Materials Enabled by Acetate Precursors

Sodium-ion batteries (SIBs) are a sustainable alternative to lithium-ion systems for global electrification, with O3-type layered oxide cathodes offering high specific capacity and feasibility of scalable synthesis. Industrial co-precipitation synthesis of these cathodes typically uses transition metal sulfates, requiring extensive water rinsing to remove Na 2 SO 4 impurities, a process that consumes significant water and risks residual inactive phases if incomplete. Here, this work introduces a rinse-free, resource-efficient approach using metal acetate precursors. Residual sodium acetate in non-rinsed precursors decomposes during sintering to generate Na 2 CO 3 in situ, partially substituting an external sodium resource (e.g., NaOH and Na 2 CO 3 ) and reducing its consumption by ∼18–20%. Phase-pure O3-Na 1.0 Ni 1/3 Fe 1/3 Mn 1/3 O 2 (NFM111) cathodes synthesized via this method exhibit microstructure and electrochemical performance comparable to rinsed sulfate-derived counterparts, with initial capacities of 141 mAh g −1 at C/20 (7.5 mA g −1 ). By eliminating rinsing and minimizing sodium reagent use, this acetate-based route enhances sustainability and scalability of layered oxide production for SIBs.

acetate vs. sulfate↗

Electrochemistry-Induced Restructuring of Tin-Doped Indium Oxide Nanocrystal Films of Relevance to CO 2 Reduction

The electrochemical reduction of CO 2 into fuels using renewable electricity presents an opportunity to utilize captured CO 2 . Electrocatalyst development has been a primary focus of research in this area. This is especially true at the nanoscale, where researchers have focused on understanding nanostructure-property relationships. However, electrocatalyst structure may evolve during operation. Indium- and tin-based oxides have been widely studied as electrocatalysts for CO 2 reduction to formate, but evolution of these catalysts during operation is not well-characterized. Here, we report the evolution of nanoscale structure of precise tin-doped indium oxide nanocrystals under CO 2 reduction conditions. We show that sparse monolayer nanocrystal films desorb from the electrode upon charging, but thicker nanocrystal films remain, likely due to an increased number of physical contacts. Upon applying a cathodic voltage of –1.0 V vs RHE or greater, the original 10-nm diameter nanocrystals are no longer visible, and instead form a larger microstructural network. Elemental analysis suggests the network is an oxygen-deficient indium-tin metal alloy. We hypothesize that this morphological evolution is the result of nanocrystal sintering due to oxide reduction. Furthermore, these data provide insights into the morphological evolution of tin-doped indium oxide nanocrystal electrocatalysts under reducing conditions and highlight the importance of post-electrochemical structural characterization of electrocatalysts.

25 ENERGY STORAGE↗

Transition Metal Taggants in UO 2 from First Principles

The incorporation of transition metals into nuclear fuel has gained attention both to improve fuel properties and as a possible nuclear forensics tool. Recent experimental studies by Ulrich et al. and Adorno Lopes et al. have investigated Ni and Fe as candidate transition metal dopants for potential nuclear forensics purposes and found that there is minimal alteration to key UO 2 fuel properties. In the present work, we performed density functional theory (DFT) investigations into possible defect structures for Ni and Fe incorporation. The dynamic stability of these defect structures was validated by calculating the phonon density of states. We found that transition metal incorporation likely occurs via substitution at U sites in the fluorite crystal structure with a nearby O vacancy for charge-balancing, which agrees with experimentally proposed structures. Additionally, this defect structure does not cause long-range alterations to the crystal parameters—an important consideration for use as a nuclear fuel taggant. Future needed work involves computational investigation of additional defect concentrations using larger supercells, additional transition metal charge states, and thermal effects. Such investigations can be carried forward into sintering models for a more complete understanding of the suitability of Ni and Fe as fuel taggants.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Metal structures with parallel pores

Four methods of fabricating metal plates having uniformly sized parallel pores are studied: elongate bundle, wind and sinter, extrude and sinter, and corrugate stack. Such plates are suitable for electrodes for electrochemical and fuel cells.

Sherfey, J. M.↗

Multi-100 kW: Planar low cost solar array development

The applicability of selected low cost options to solar array blanket design was studied by fabricating representative modules and submitting them to thermal cycle environment. Large area (5.9 x 5.9 cm) solar cells of 3 varieties were purchased: (1) Standard wraparound, (2) Copper contacts substituted for the conventional Titanium-Palladium-Silver, and (3) Standard wraparound except with gridded back contact instead of continuous metallization. The baseline cell was purchased to compare fabrication cost and to serve as a control cell during test evaluation of the other two cells. All cells were assembled into either substrate modules where the cell is individually filtered and welded to an integrated Kapton-copper circuit or into a superstrate configuration with 4 cells jointly adhered to a single sheet of microsheet and then welded to the integrated Kapton-copper circuit. Cell quality, particularly in the metallization of contacts, was less than desired. Problems were encountered with copper metallization in laying down a barrier metal which would ohmically bond to the silicon. The cells received were shunted (sintered) or with low contact pull strength (non-sintered), thus leading to the decision to solder rather than weld the copper cells to the Kapton substrate.

Source record↗

Lithological Variation with Depth and Decoupling of Maturity Parameters in Apollo 16 Regolith Core 68001/2

Using FerroMagnetic Resonance (FMR) and Instrumental Neutron Activation Analysis (INAA), we have determined the maturity (surface exposure) parameter I(sub s)/FeO and concentrations of twenty- five chemical elements on samples taken every half centimeter down the 61-cm length of the 68001/2 regolith core (double drive tube) collected at station 8 on the Apollo 16 mission to the Moon. Contrary to premission expectations, no ejecta or other influence from South Ray crater is evident in the core, although a small inflection in the I(sub s)/FeO profile at 3 cm depth may be related the South Ray crater impact. Regolith maturity generally decreases with depth, as in several previously studied cores. We recognize five compositionally distinct units in the core, which we designate A through E, although all are similar in composition to each other and to other soils from the Cayley plains at the Apollo 16 site. Unit A (0-33 cm) is mature to submature throughout (I(sub s)/FeO: 89-34 units) and is indistinguishable in composition from surface soils collected at station 8. Unit B (33-37 cm) is enriched slightly in a component of anorthositic norite composition. Unit D (42-53 cm) is compositionally equivalent to 80 wt% Unit-A soil plus 20 wt% Apollo-16-type dimict breccia consisting of subequal parts anorthosite and impact-melt breccia. Compared to Unit A, Unit E (53-61 cm) contains a small proportion (up to 4%) of some component compositionally similar to Apollo 14 sample 14321. Unit C (37-42 cm) is unusual. For lithophile and siderophile elements, it is similar to Units A and D. However, I(sub s)/FeO is low throughout the unit (less than 30 units) and in a bluish-gray zone at 41 cm depth I(sub s)/FeO drops to 1.6 units, the lowest value that we have observed in several hundred Apollo 16 soil samples. Samples from the bluish-gray zone also have low Zn concentrations, less than 10 micro g/g, compared to 20-30 micro g/g for the rest of the core. Although both values are consistent with fragmented rock material that has received virtually no surface exposure, the abundance of agglutinates in the bluish-gray soil of Unit C is moderately high, typical of a submature soil that would ordinarily have I(sub s)/FeO - 30. We believe that the anomalously low values of I(sub s)/FeO and Zn concentration result because the soil was heated to -800-1000 'C, probably during an impact. This temperature range is sufficient to volatize the surface-correlated Zn and agglomerate the nanophase metal giving rise to the FMR signal but is not great enough to sinter the soil. Alternatively, the unusual soil interval may represent a disaggregated or incipient regolith breccia, although there is no significant difference in the texture or clast-matrix relationships between Unit C and adjacent units.

Korotev, Randy L.↗

Scalable preparation of oxygen carriers for chemical looping

Wet impregnation of active metal precursors into porous substrates, together with selective adsorption of the precursors on the pore surfaces, enables transition metal oxides derived from the precursors to disperse throughout the substrate, even at the nanoscale, without increased sintering or agglomeration, thereby forming oxygen carriers suitable for chemical looping. The porous substrate can be an oxide, for example SiO 2 . The oxygen carriers can comprise relatively large oxide loadings of over about 20 wt % and exhibit high reactivity over many regeneration cycles with substantially no loss in oxygen transport capacity or decrease in kinetics. The use of multiple transition metal oxides, for example NiO in addition to CuO, can greatly enhance chemical looping performance.

O′Malley, Kyle↗

Advances in materials and current collecting networks for AMTEC electrodes

Electrode materials for the Alkali Metal Thermal to Electric Converter (AMTEC) play a significant role in the efficiency of the device. RhW and PtW alloys have been studied to determine the best performing material. While RhW electrodes typically have power densities somewhat lower than PtW electrodes, PtW performance is strongly influenced by the Pt/W ratio. The best performing Pt/W ratio is about 3.4. RhW electrodes sinter more slowly than PtW and are predicted to have operating lifetimes up to 40 years; PtW electrodes are predicted to have lifetimes up to 7 years. Interaction with the current collection network can significantly decrease lifetime by inducing metal migration and segregation and by accelerating the sintering rate.

Ryan, M. A.↗

Recent advances in single-atom catalysts and single-atom alloys: opportunities for exploring the uncharted phase space in-between

Single-atom catalysts (SACs) have gained significant world-wide attention for exhibiting distinct reactivity and selectivity for important reactions, while utilizing precious metals at the ultimate limit of efficiency. SACs involving reducible oxide supports are good catalysts for oxidation reactions, and metal-acid site pairs enable Csingle bondC bond formation, but SACs can deactivate by sintering under reducing conditions. On the other hand, single-atom alloys (SAAs) are robust towards sintering and exhibit exceptional catalytic performance for a wide range of reactions under reducing conditions but can deactivate under oxidizing environments. Therefore, there is tremendous opportunity to explore and exploit catalytic reactivity between the SAC and SAA extremes. Furthermore, this paper focuses on recent advances in both fields and highlights prospects for future research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Method of forming dynamic membrane on stainless steel support

A suitable member formed from sintered, powdered, stainless steel is contacted with a nitrate solution of a soluble alkali metal nitrate and a metal such as zirconium in a pH range and for a time sufficient to effect the formation of a membrane of zirconium oxide preferably including an organic polymeric material such as polyacrylic acid.

Gaddis, Joseph L.↗

JSC Mars-1 Martian Soil Simulant: Melting Experiments and Electron Microprobe Studies

JSC Mars-1 has been developed as a Martian regolith simulant, and is the <1 mm size fraction of a palagonitic tephra (a glassy volcanic ash altered at low temperatures) from Pu'u Nene cinder cone on the Island of Hawaii. The Mars-1 simulant forms the basis for numerous terrestrial studies which aim to evaluate the suitability of Martian soil for materials processing. Martian soil may be sintered to form building materials for construction, and also melted or reacted to extract metals for various uses, as well as oxygen for life support.

Carpenter, P.↗

Microwave-assisted ammonia synthesis over Ru/MgO catalysts at ambient pressure

Here, in this work, a fixed frequency (2.45 GHz) microwave (MW) was used to synthesis ammonia over Ru/MgO catalysts under ambient atmospheric pressure at 320 °C. The loading of Ru catalyst over MgO was varied at 4% and 10 wt %. The metal support interaction was found to play an important role not only catalytically but also altering the microwave-catalyst interaction affecting the ammonia formation rate. The higher metal loading (10 wt%) produced the most activity, stability, and energy efficiency. It was found the Ru was better dispersed at higher loading which decreased the sintering of the catalyst due to lower microwave energy needed to maintain the reaction temperature. Additional effects from the microwave can include enhanced electron movement and/or electric fields formed between the metal sites of the catalyst. The microwave reactor offers a quick on/off catalyst recovery, within 11 min, compared to thermal convectional Haber Bosch (HB) technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Influence of Interstitial Ga and Interfacial Au (sub 2)P (sub 3) on the Electrical and Metallurgical Behavior of Au-Contacted III-V Semiconductors

The introduction of a very small amount of Ga into Au contact metallization on InP is shown to have a significant effect on both the metallurgical and electrical behavior of that contact system. Ga atoms in the interstices of the Au lattice are shown to be effective in preventing the solid state reactions that normally take place between Au and InP during contact sintering. In addition to suppressing the metallurgical interaction, the presence of small amounts of Ga is shown to cause an order of magnitude reduction in the specific contact resistivity. Evidence is presented that the reactions of GaP and GaAs with Au contacts are also drastically affected by the presence of Ga. The sintering behavior of the Au-GaP and the Au-GaAs systems (as contrasted with that of the Au-InP system) is explained as due to the presence of interstitial Ga in the contact metallization. Finally the large, two-to-three order of magnitude drop in the contact resistance that occurs in the Au-InP system upon sintering at 400 degrees Centigrade is shown to be a result of the formation of an Au (sub 2) P (sub 3) layer at the metal-semiconductor interface. Contact resistivities in the 10 (sup -6) ohm square centimeter range are obtained for as-deposited Au on InP when a thin (20 Angstrom) layer of Au (sub 2) P (sub 3) is introduced between the InP and the Au contacts.

Weizer, Victor G.↗

Effect of Surface Temperature on the Distribution and Reactivity of Rh Active Sites for CO Oxidation

Single–atom catalysts are a fast–emerging area in which late–transition metal atoms are supported on oxides, metals, and carbonaceous supports. They show great promise for selective chemical reactions due to their well–defined active sites, and significantly reduce precious metal loading. However, oxide–supported single–atom catalysts have drawbacks such as deactivation due to sintering, and there are on–going debates about the exact nature of the active sites. Herein we report a model system where the surface temperature during Rh deposition on a copper oxide support dictates the Rh size distribution. Here our temperature–programmed desorption experiments reveal that Rh clusters perform CO oxidation at lower temperature than single atoms, and isotopic labelling demonstrates differences in the mechanism in that the C–O bond is broken and reformed on clusters, as opposed to a pure Mars van Krevelen mechanism for CO oxidation at the single–atom Rh sites. We further examine the cluster size distributions with scanning tunneling microscopy and X–ray photoelectron spectroscopy which confirm the presence of both clusters and single atoms for the lower temperature deposition and only single atoms for the higher temperature deposition. Together, these results provide a fundamental understanding of the differences in the CO oxidation mechanism on Rh atoms and clusters.

36 MATERIALS SCIENCE↗

Hydrogen-based ore-to-part manufacturing of near-net-shape stainless steel

Decarbonizing iron and steelmaking, combined with global disruptions to raw material supply chains, necessitates novel approaches to iron and steel production. In this work, we demonstrate a direct ore-to-part manufacturing route using a mixture of ore-derived oxide powders of Fe 2 O 3 , Cr 2 O 3 , NiO, and MoO 3 as feedstock for additive manufacturing, combined with sintering under H 2 to produce a near-net-shape austenitic stainless-steel. Complete reduction of all constituent oxides, including MoO 3 and Cr 2 O 3 , is achieved in-situ at 1300 °C, resulting in dense, crack-free bulk alloy. The fabricated part retains geometric fidelity while undergoing substantial volumetric shrinkage inherent to redox and sintering. Thermodynamic calculations elucidate the co-reduction mechanisms and alloying pathways that enable complete metallization. This work is the first demonstration of net-shaping metal parts directly from ore derived oxides, and this ore-to-part approach can minimize the emissions and lead time for manufacturing associated with downstream processing such as rolling, forging, and machining.

Yang, Mingzhang [Univ. of Waterloo, ON (Canada); F↗

Sandblasting nozzle

A nozzle for use with abrasive and/or corrosive materials is formed of sintered ceramic compositions having high temperature oxidation resistance, high hardness and high abrasion and corrosion resistance. The ceramic may be a binary solid solution of a ceramic oxide and silicon nitride, and preferably a ternary solid solution of a ceramic oxide, silicon nitride and aluminum nitride. The ceramic oxide is selected from a group consisting of Al2O3, Y2O3 and Cr2O3, or mixtures of those compounds. Titanium carbide particles are dispersed in the ceramic mixture before sintering. The nozzles are encased for protection from external forces while in use by a metal or plastic casing.

Perkins, G. S.↗