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At least 199 records · Page 11

Highly selective electrocatalytic CO 2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper

Direct electrochemical conversion of CO 2 to ethanol offers a promising strategy of lowering CO 2 emission while storing energy from renewable electricity. However, current electrocatalysts offer only limited selectivity toward ethanol. Here we report a copper catalyst synthesized by a unique Cu-Li amalgm method over a commercial carbon support that achieved Faradaic efficiency (FE) higher than 91% at -0.7 V (RHE) and the active potential as low as -0.4 V (RHE) during direct electrocatalytic CO 2 -to-ethanol conversion. The catalyst also demonstrated stability over an extended period of operation. A strong correlation between the catalytic selectivity and the initial Cu atoms dispersion was found and Operando X-ray absorption spectroscopy identified a dynamic and reversible transformation from atomically dispersed copper atoms to Cu n (n = 3 and 4) under the electrochemical reaction. Frist-principles calculations further elucidate the possible catalytic mechanism of CO 2 reduction over Cu n .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanobodies against the metal binding domains of ATP7B as tools to study copper transport in the cell

Abstract Nanobodies are genetically engineered single domain antibodies derived from the unusual heavy-chain only antibodies found in llamas and camels. The small size of the nanobodies and flexible selection schemes make them uniquely versatile tools for protein biochemistry and cell biology. We have developed a panel of nanobodies against the metal binding domains of the human copper transporter ATP7B, a multidomain membrane protein with a complex regulation of enzymatic activity and intracellular localization. To enable the use of the nanobodies as tools to investigate copper transport in the cell, we characterized their binding sites and affinity by isothermal titration calorimetry and NMR. We have identified nanobodies against each of the first four metal binding domains of ATP7B, with a wide affinity range, as evidenced by dissociation constants from below 10−9 to 10−6 M. We found both the inhibitory and activating nanobodies among those tested. The diverse properties of the nanobodies make the panel useful for the structural studies of ATP7B, immunoaffinity purification of the protein, modulation of its activity in the cell, protein dynamics studies, and as mimics of copper chaperone ATOX1, the natural interaction partner of ATP7B.

Uhlemann, Eva-Maria E.↗

Soil Interim Measures Implementation Report Q6 Radar Station – Solid Waste Management Unit 112 Locations of Concern 3 and 10 Kennedy Space Center, Florida

This report presents a summary of the soil interim measures (IM) implementation activities that occurred from January 23 through June 6, 2023, at the Q6 Radar Station (Q6RS) Solid Waste Management Unit (SWMU) 112, located at the John F. Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act Corrective Action Program, which also meets the requirements of Chapter 62-780, Florida Administrative Code. Assessment activities have previously been performed at 10 Q6RS Locations of Concern (LOCs), identified during a SWMU assessment in 2013 (NASA 2013). Since the SWMU assessment, further confirmatory sampling and assessment was conducted for each LOC, and based on the data collected during these assessments, it was determined that Resource Conservation and Recovery Act Facility Investigation to further evaluate soil and groundwater was to be conducted at two LOCs: LOC 1 – Former Underground Storage Tanks (groundwater) and LOC 3 – Radar Antenna Refurbishment Area (soil). The LOC 1 groundwater assessment is ongoing, and the results will be presented under a separate cover. It was also determined that soil IM would be completed at two of the LOCs, LOC 3 and LOC 10 – Compressor Building Condensate Discharge. A Soil IM Work Plan was prepared and submitted in October 2021 (NASA 2021). The plan proposed excavation and disposal of barium and copper impacted soil in the LOC 3 and 10 areas. This report presents a summary and results of the soil IM implementation activities conducted at LOCs 3 and 10. The site contaminates of concern for this soil IM are barium and copper. The activities presented in this report includes soil IM implementation and groundwater sampling. From January 23 through March 24, 2023, AECOM Technical Services, Inc. (AECOM) field personnel conducted IM implementation activities in the LOC 3 and 10 areas. As presented in the IM Work Plan, shallow soils, impacted with metals, were excavated to a depth of 2 feet below land surface in the central area of the site around the radar antenna and associated equipment. AECOM personnel excavated 77.43 tons of soil using hand tools and, when able, heavy equipment. The soils were placed into lined roll-off containers, which were covered and transported under manifest to the Cedar Trail Landfill in Bartow, Florida. The site was restored to original condition using certified clean backfill material (sand), with filter fabric, and gravel. Areas outside of the excavation were restored with grass seed. On June 6, 2023, AECOM field personnel conducted groundwater sampling activities within the soil IM excavation area. AECOM personnel collected one groundwater sample from monitoring well Q6RS-MW0003. The sample was submitted to a fixed-based laboratory for analysis by United States Environmental Protection Agency Method 6020B for metals (barium and copper). Barium and copper were detected at 18 micrograms per liter (µg/L) and 14 µg/L, respectively, and were below the State of Florida Groundwater Cleanup Target Levels (GCTLs) for barium at 2,000 µg/L and copper at 1,000 µg/L.

Chadwick Sloan Lee↗

Flow Boiling Heat Transfer Characteristics of Water for Metal-foam-filled Horizontal Tubes

The goal of this paper is to enhance the in-tube flow boiling heat transfer of water while accounting for potential increase in pressure drop. Metal foams are a class of cellular structure with large surface-area-to-volume ratio and tortuous structure which has shown promising results for various energy conversion and storage applications. The higher heat transfer area and higher nucleation sites density due to the porous media can effectively enhance the heat transfer of water in both single-phase and two-phase operations. This paper presents the local heat transfer and pressure drop measurements of water in a partially metal-foam-filled horizontal copper tube. The ranges of parameters in the experiments are: mass flux from 80 to 200 kg/s-m2, heat flux from 3.5 to 105 kW/m2, and vapor quality from subcooled to 0.3. The results in the metal-foam-filled tube are compared with that of the bare copper tube. The effect of metal foam on the thermal hydraulic characteristics is discussed and analyzed. In addition, the two-phase flow behavior in a transparent tube filled with the same metal foam was visualized and investigated by high-speed imaging system. The experiments were also conducted in the tube without the metal foam for comparison.

Nawaz, Kashif↗

Solving A Corrosion Problem

The corrosion problem, it turned out, stemmed from the process called electrolysis. When two different metals are in contact, an electrical potential is set up between them; when the metals are surrounded by an electrolyte, or a conducting medium, the resulting reaction causes corrosion, often very rapid corrosion. In this case the different metals were the copper grounding system and the ferry's aluminum hull; the dockside salt water in which the hull was resting served as the electrolyte. After identifying the source of the trouble, the Ames engineer provided a solution: a new wire-and-rod grounding system made of aluminum like the ferry's hull so there would no longer be dissimilar metals in contact. Ames research on the matter disclosed that the problem was not unique to the Golden Gate ferries. It is being experienced by many pleasure boat operators who are probably as puzzled about it as was the Golden Gate Transit Authority.

Source record↗

Consistent Controls on Trace Metal Micronutrient Speciation in Wetland Soils and Stream Sediments

Trace metal are essential for microbially-mediated biogeochemical processes occurring in anoxic wetland soils and stream bed sediments, but low availability of these elements may inhibit anaerobic element cycling and transformations. Solid-phase speciation is likely a critical control on trace metal availability but has seen limited study in anoxic systems having concentrations similar to geological background levels, where metal limitations may be most prevalent. We have investigated trace metal concentrations and solid-phase speciation in three freshwater subsurface aquatic systems: marsh wetland soils, riparian wetland soils, and the sediments of a streambed. These systems displayed low solid-phase trace metal concentrations, generally at or below geological background levels, which generally followed the trend Zn > Cu ≈ Ni > Co and showed no correlation with major element compositions. All soils and sediments were dominated by quartz but varied in clay mineralogy as well as the organic matter, total sulfur, and total iron contents. X-ray absorption near-edge structure (XANES) spectroscopy shows that sulfur speciation in both wetlands is dominated by organic sulfur. Elemental sulfur and iron sulfides together made up <25% of the sulfur in the wetland soils, but the distribution between inorganic and organic forms was reversed in the stream sediments. Ferrous and ferric iron in clay minerals were common species identified by both XANES and extended X-ray absorption fine structure (EXAFS) spectroscopies at all sites. Iron(III) oxides were substantial components in all but the marsh wetland soils. Quantitative analysis of copper, nickel, and zinc XANES spectra revealed similar metal speciation across all sites. Copper speciation was dominated by sulfides, adsorbed species, and minor amounts of copper bound to organic matter; no metallic copper was detected. Nickel speciation also varied little and was dominated by nickel in clay mineral octahedral sheets and nickel sulfide, with adsorbed species also present. Zinc speciation was slightly more varied, with the marsh wetland soils and stream bed sediments containing adsorbed species, zinc associated with clay mineral structures, and zinc bound to reduced sulfur groups on organic matter, whereas the riparian wetland soils lacked clay-associated zinc but contained zinc sulfide. Trace metals bound to reduced sulfur occurred at every site, with a greater sulfur-bound fraction for copper. The fractional abundance of sulfur-bound species showed no relationship with soil or sediment total sulfur content, which varied by two orders of magnitude. More broadly, the observations in this study suggest that trace metal speciation in freshwater wetland soils and stream sediments is consistently dominated by a small set of recurring components which are distinct for each metal. Furthermore, this may represent a general geochemical phenomenon in anoxic soils and sediments containing trace metals at background concentrations (as low as 3 µg g -1 ) that was not predicted from systems that are contaminated with or naturally-enriched in copper, nickel, or zinc.

54 ENVIRONMENTAL SCIENCES↗

Morphology and chemical behavior of model CsO x /Cu 2 O/Cu(111) nanocatalysts for methanol synthesis: Reaction with CO 2 and H 2

Cs is a promoter of Cu-based catalysts for the synthesis of alcohols from CO 2 hydrogenation. Scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy were used to study the morphology and chemical properties of surfaces generated by the deposition of cesium on Cu 2 O/Cu(111) and Cu(111) substrates. CsO x nanostructures were formed after Cs metal was deposited on Cu 2 O/Cu(111) at 300 K. The formed CsO x protrude over the surface of copper oxide by 2–4 Å, with the dimension at the base of the nanostructures being in the range of 1–3 nm. Heating to elevated temperature induced significant changes in the size and dispersion of the CsO x nanostructures, and there was a clear reconstruction of the copper oxide substrate, which then exhibited long range order with a hexagonally packed structure. The as-deposited and annealed surfaces of CsO x /Cu 2 O/Cu(111) were more reactive toward CO 2 than plain Cu 2 O/Cu(111) or clean Cu(111). Yet, none of them were stable in the presence of H 2 , which fully reduced the copper oxide at 400–450 K. In CsO x /Cu(111), the CsO x nanoclusters were dispersed all over the metallic copper in no particular order. The CsO x species had an average width of 2 nm and ~1 Å height. The CsO x /Cu(111) systems exhibited the highest activity for the binding and dissociation of CO 2 , indicating that the CsO x -copper interface plays a key role in alcohol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tutorial on forming through-silicon vias

Through-silicon vias (TSVs) are a critical technology for three-dimensional integrated circuit technology. These through-substrate interconnects allow electronic devices to be stacked vertically for a broad range of applications and performance improvements such as increased bandwidth, reduced signal delay, improved power management, and smaller form-factors. There are many interdependent processing steps involved in the successful integration of TSVs. This article provides a tutorial style review of the following semiconductor fabrication process steps that are commonly used in forming TSVs: deep etching of silicon to form the via, thin film deposition to provide insulation, barrier, and seed layers, electroplating of copper for the conductive metal, and wafer thinning to reveal the TSVs. Recent work in copper electrochemical deposition is highlighted, analyzing the effect of accelerator and suppressor additives in the electrolyte to enable void-free bottom-up filling from a conformally lined seed metal.

42 ENGINEERING↗

Assessment of Additive Manufacturing of Particle Accelerator [Slides]

Metal additive manufacturing of copper components has been commercialized on multiple printing modalities; including Bound Metal Deposition (BMD), Laser Powder Bed Fusion (LPBF), and Electron Beam Melting (EBM). BMD was selected at the primary printing modality for this TED because of the availability of the Markforged Metal X machine within the LANL E-2 AM research lab. Linear accelerator (LINAC) structures are similarly demonstrated technology. Accelerator structures are typically made of high purity oxygen-free electronic copper owing to the material’s high electrical and thermal conductivity. Conventionally machined and brazed, welded, or bolted designs are difficult to manufacture and require long lead times.

36 MATERIALS SCIENCE↗

Progress in demonstrating the performance of Engineered Barriers for the disposal of HLW and SNF: lab studies and demonstration experiments - 20293

Disposal of high-level radioactive waste (HLW) and spent nuclear fuels (SNF) in a geological disposal facility requires a fundamental understanding of the degradation processes of materials used in its engineered barrier system (EBS) over very long timescales. Beyond the wasteform itself (i.e. the borosilicate glass for HLW or the fuel matrix and cladding for SNF), materials often employed in a disposal concept include metallic containers (typically copper and/or carbon steel) and clay-based buffer materials (typically bentonite). In this paper we explore key developments on the long-term evolution of materials employed for the immobilisation, isolation and containment of HLW and SNF in a geological disposal facility, including nuclear glasses, candidate container materials and clay buffers. Our discussion is based on the latest findings from both experimental studies and in-situ demonstration experiments. We present relevant findings from the long-term evolution of HLW glasses (UK composition), metallic materials for the containment system (envisaged in Switzerland, Sweden, Canada and other countries), and bentonite clays (envisaged in many national disposal programmes). (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Methane Activation by a Mononuclear Copper Active Site in the Zeolite Mordenite: Effect of Metal Nuclearity on Reactivity

The direct conversion of methane to methanol would have a wide reaching environmental and industrial impact. Copper-containing zeolites can perform this reaction at low temperatures and pressures at a previously defined O 2 -activated [Cu 2 O] 2+ site. However, after autoreduction of the copper-containing zeolite mordenite and removal of the [Cu 2 O] 2+ active site, the zeolite is still methane reactive. In this study, we use diffuse reflectance UV–vis spectroscopy, magnetic circular dichroism, resonance Raman spectroscopy, electron paramagnetic resonance, and X-ray absorption spectroscopy to unambiguously define a mononuclear [CuOH] + as the CH 4 reactive active site of the autoreduced zeolite. The rigorous identification of a mononuclear active site allows a reactivity comparison to the previously defined [Cu 2 O] 2+ active site. We perform kinetic experiments to compare the reactivity of the [CuOH] + and [Cu 2 O] 2+ sites and find that the binuclear site is significantly more reactive. From the analysis of density functional theory calculations, we elucidate that this increased reactivity is a direct result of stabilization of the [Cu 2 OH] 2+ H-atom abstraction product by electron delocalization over the two Cu cations via the bridging ligand. This significant increase in reactivity from electron delocalization over a binuclear active site provides new insights for the design of highly reactive oxidative catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Film and interstitial formation of metals in plasma-sprayed ceramics

A method is described to electrodeposit noble metals such as platinum and ordinary metals such as copper on and within plasma-sprayed ceramic materials and ceramic fiber materials. Low-density ceramic fiber bodies were vacuum impregnated with plating solution and attached to an electrode. Light micrographs illustrating the density and location of deposited materials are presented and discussed. Voids in the plasma-sprayed ceramic were filled with deposits that vary from spherical to lens-shaped circular and have particle size corresponding to the full range of void size. Multiple coatings of ceramic and metal can be sequenced.

Hendricks, R. C.↗

Film and interstitial formation of metals in plasma-sprayed ceramics

A method is described to electrodeposit noble metals such as platinum and ordinary metals such as copper on and within plasma-sprayed ceramic materials and ceramic fiber materials. Low-density ceramic fiber bodies were vacuum impregnated with plating solution and attached to an electrode. Light micrographs illustrating the density and location of deposited materials are presented and discussed. Voids in the plasma-sprayed ceramic were filled with deposits that vary from spherical to lens-shaped circular and have particle size corresponding to the full range of void size. Multiple coatings of ceramic and metal can be sequenced.

Hendricks, R. C.↗

Copper alloys for interconnectors and methods for making the same

Metallic alloy interconnects (which can comprise copper) with low electrical resistivity and methods for making the same are disclosed. The electrical resistivity of thin film copper alloys was reduced by 36% with niobium solute and by 51% with iron solute compared to pure copper counterpart in dilute solute regimes (0-1.5 atomic %). The fabrication method is operated at room temperature, and does not require a high temperature annealing step.

Gianola, Daniel S.↗

The friction behavior of semiconductors Si and GaAs in contact with pure metals

The friction behavior of the semiconductors silicon and gallium arsenide in contact with pure metals was studied. Five transition and two nontransition metals, titanium, tantalum, nickel, palladium, platinum, copper, and silver, slid on a single crystal silicon (111) surface. Four metals, indium, nickel, copper and silver, slid on a single crystal gallium arsenide (100) surface. Experiments were conducted in room air and in a vacuum of 10 to the minus 7th power N/sq cm (10 to the minus 9th power torr). The results indicate that the sliding of silicon on the transition metals exhibits relatively higher friction than for the nontransition metals in contact with silicon. There is a clear correlation between friction and Schottky barrier height formed at the metal silicon interface for the transition metals. Transition metals with a higher barrier height on silicon had a lower friction. The same effect of barrier height was found for the friction of gallium arsenide in contact with metals.

Mishina, H.↗

Life-cycle analysis of battery metal recycling with lithium recovery from a spent lithium-ion battery

Demand for critical materials (nickel, cobalt, manganese [NCM], and lithium) for use in batteries is increasing rapidly due to the expansion of the battery-electric vehicles market. Battery metal recycling (BMR) is an important technology that can potentially realize environmental and economic benefits in cathode active material (LiNi x Mn y Co z O 2 ) production using recycled materials. While current major battery recycling technologies recover cathode materials (NCM) and other metals (steel, aluminum, copper, etc.) from the spent battery, the lithium (Li) recovery rate is less than 1% in the world. In this study, we analyze the environmental benefits of a BMR process that recovers lithium in the form of lithium hydroxide monohydrate (LiOH∙H 2 O) along with other cathode materials. Using life-cycle analysis (LCA), we evaluate the life-cycle greenhouse gas (GHG) emissions, criteria air pollutant emissions, and water consumption of the new BMR technology in terms of lithium hydroxide production and cathode active material production. The LCA results show that the life-cycle GHG emissions recycled LiOH are 37–72% lower than those of virgin LiOH production from Chilean brine and Australian ore, respectively. In addition, the life-cycle GHG emissions of NCM811 produced using the recycled materials are 40–48% lower compared to virgin cathode active material production. Furthermore, recovering lithium from the spent batteries reduces associated air pollutant emissions and water consumption relative to using the virgin materials or materials from other recycling technologies without LiOH recovery.

25 ENERGY STORAGE↗