Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction
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Eilert, André↗
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Results for “COPPER”
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A Purple Cupredoxin from Nitrosopumilus maritimus Containing a Mononuclear Type 1 Copper Center with an Open Binding Site
Mononuclear cupredoxin proteins usually contain a coordinately saturated type 1 copper (T1Cu) center and function exclusively as electron carriers. Here we report a cupredoxin isolated from the nitrifying archaeon Nitrosopumilus maritimus SCM1, called Nmar1307, that contains a T1Cu center with an open binding site containing water. It displays a deep purple color due to strong absorptions around 413 nm (1880 M –1 cm –1 ) and 558 nm (2290 M –1 cm –1 ) in the UV–vis electronic spectrum. EPR studies suggest the protein contains two Cu(II) species of nearly equal population, one nearly axial, with hyperfine constant A∥ = 98 × 10 –4 cm –1 , and another more rhombic, with a smaller A∥ value of 69 × 10 –4 cm –1 . The X-ray crystal structure at 1.6 Å resolution confirms that it contains a Cu atom coordinated by two His and one Cys in a trigonal plane, with an axial H2O at 2.25 Å. Both UV–vis absorption and EPR spectroscopic studies suggest that the Nmar1307 can oxidize NO to nitrite, an activity that is attributable to the high reduction potential (354 mV vs SHE) of the copper site. These results suggest that mononuclear cupredoxins can have a wide range of structural features, including an open binding site containing water, making this class of proteins even more versatile.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A competition between 2D and 3D magnetic orderings in novel mixed valent copper frameworks
Low-dimensional hybrid inorganic–organic frameworks exhibit high structural flexibility and allow for the inclusion of various magnetic and optically-active species into their host structures. The emergence of copper-based hybrid structures for various optical applications provides a promising foundation for exploring the integration of magnetic sublattices, paving the way for advancements in magneto-optical coupling and multifunctional materials. Herein, we introduce a novel class of hybrid copper frameworks with covalently-connected alternating magnetic 2D copper(II) formate and non-magnetic copper(I) bromide layers. The anionic framework is stabilized by A + cations to form ACu 5 Br 4 (COOH) 4 (A + = Na + , K + , Rb + , NH 4 + ) semiconductors (bandgaps 2.1–2.2 eV) with optical transitions suitable for optoelectronic applications. Comprehensive magnetometry studies show that ACu 5 Br 4 (COOH) 4 compounds exhibit low-dimensional 2D short-range antiferromagnetic order within the formate layers, characterized by strong exchange coupling (J/k B ∼ −100 K). Upon further temperature reduction, interactions between Cu(II) layers give rise to 3D long-range magnetic order at ∼40 K, despite the large (8.6–8.8 Å) spatial separation of the magnetic Cu(II) formate layers by nonmagnetic Cu(I)–Br bridging layers. This transition is further supported by electron paramagnetic resonance (EPR) spectroscopy. In conclusion, this study expands our understanding of low-dimensional hybrid frameworks and opens new avenues for the design of 2D multifunctional materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The bacterial copper resistance protein CopG contains a cysteine-bridged tetranuclear copper cluster
CopG is an uncharacterized protein ubiquitous in Gram-negative bacteria whose gene frequently occurs in clusters of copper resistance genes and can be recognized by the presence of a conserved CxCC motif. To investigate its contribution to copper resistance, here we undertook a structural and biochemical characterization of the CopG protein from Pseudomonas aeruginosa . Results from biochemical analyses of CopG purified under aerobic conditions indicate that it is a green copper-binding protein that displays absorbance maxima near 411, 581, and 721 nm and is monomeric in solution. Determination of the three-dimensional structure by X-ray crystallography revealed that CopG consists of a thioredoxin domain with a C-terminal extension that contributes to metal binding. We noted that adjacent to the CxCC motif is a cluster of four copper ions bridged by cysteine sulfur atoms. Structures of CopG in two oxidation states support the assignment of this protein as an oxidoreductase. On the basis of these structural and spectroscopic findings and also genetic evidence, we propose that CopG has a role in interconverting Cu(I) and Cu(II) to minimize toxic effects and facilitate export by the Cus RND transporter efflux system.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Transformation of shock-compressed copper to the body-centered-cubic structure at 180 GPa
Abstract not provided
Sharma, Surinder M.↗
Annual Copper Mountain Conferences on Multigrid and Iterative Methods, Copper Mountain, Colorado
This project supported the Copper Mountain Conference on Multigrid and Iterative Methods, held from 2007 to 2015, at Copper Mountain, Colorado. The subject of the Copper Mountain Conference Series alternated between Multigrid Methods in odd-numbered years and Iterative Methods in even-numbered years. Begun in 1983, the Series represents an important forum for the exchange of ideas in these two closely related fields. This report describes the Copper Mountain Conference on Multigrid and Iterative Methods, 2007-2015. Information on the conference series is available at http://grandmaster.colorado.edu/~copper/.
22 GENERAL STUDIES OF NUCLEAR REACTORS↗
From Copper to Basic Copper Carbonate: A Reversible Conversion Cathode in Aqueous Anion Batteries
Dual-ion batteries that use anions and cations as charge carriers represent a promising energy-storage technology. However, an uncharted area is to explore transition metals as electrodes to host carbonate in conversion reactions. Here we report the reversible conversion reaction from copper to Cu 2 CO 3 (OH) 2 , where the copper electrode comprising K 2 CO 3 and KOH solid is self-sufficient with anion-charge carriers. This electrode dissociates and associates K + ions during battery charge and discharge. The copper active mass and the anion-bearing cathode exhibit a reversible capacity of 664 mAh g –1 and 299 mAh g –1 , respectively, and relatively stable cycling in a saturated mixture electrolyte of K 2 CO 3 and KOH. Finally, the results open an avenue to use carbonate as a charge carrier for batteries to serve for the consumption and storage of CO 2 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Isolation and Structural Elucidation of 15–Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two–Electron Copper Superatom
Highly reactive copper-dihydride clusters, [Cu 15 (H) 2 (S 2 CNR 2 ) 6 (C 2 Ph) 6 ](PF 6 ) {R = n Bu (1 H ), n Pr (2 H ), i Bu (3 H )}, are isolated during the reaction of [Cu 28 H 15 {S 2 CN n Bu 2 } 12 ](PF 6 ) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu 13 (S 2 CNR 2 ) 6 (C 2 Ph) 4 ] + . Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH 3 CN) 4 ](PF 6 ), BH 4 – and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu 15 (D) 2 (S 2 CNR 2 ) 6 (C 2 Ph) 6 ] + , and a single-crystal neutron structure of 2 H . Structural characterization of 1 H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH 2 ) – unit. In conclusion, reaction of 3 H with Au(I) salts yields a highly luminescent [AuCu 12 (S 2 CNiBu 2 ) 6 (C 2 Ph) 4 ] + cluster.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Brazing of Martensitic Stainless Steel to Copper Using Electroplated Copper and Silver Coatings
Brazing of 3 mm thick sheets of low-carbon martensitic stainless steel and Cu-Cr-Zr-Ti alloy was attempted using electroplated coatings of Cu and Ag. Ni coating of 5 µm thick was provided on the MSS base metal to enhance the wettability. Brazing experiments were carried out at 985 °C for a holding of 15 min. Detailed microstructural studies, hardness, lap-shear, tensile, and pressure tests were carried out on the brazed joints. The reaction between the Cu and Ag coatings lead to the formation of in situ braze metal. The microstructure of the braze metal was found to consist of Cu-rich primary alpha (α{sub P}) and Ag-rich eutectic mixture (β + α{sub E}). In lap-shear tests, the brazed joints produced with an overlap of 9 and 6 mm were found to fail in copper base metal, while the joints produced with an overlap of 3 mm failed in the braze metal exhibiting a lap-shear strength of 147 MPa. In tensile tests, the butt brazed joints were found to fail in copper base metal as well with an average tensile strength of 213 MPa. The braze metal hardness was found to be higher than the hardness of the copper base metal. In pressure tests, the brazed panels were found to survive a pressure of 750 bar without undergoing any damage. These results show that electroplated coatings of Cu and Ag can be advantageously utilized for brazing of large, complex-shaped parts such as thrust chambers in space industry.
36 MATERIALS SCIENCE↗
Ultra-low thermal resistance and pressure drop copper and copper-tungsten diamond-shaped pin fin cold plates for liquid cooling of electronics
Modern and future data centers face increasing cooling challenges due to increasing chip thermal design power and die size, along with the need to reduce energy consumption used for cooling. High performance cooling solutions that maintain a low chip junction temperature are needed to ensure electronics reliability. This work develops an ultra-low thermal resistance and low pressure drop 75 mm × 75 mm cold plate, intended for next-generation electronics cooling. The cold plate features an array of diamond-shaped pin fins and integrated copper tungsten heat spreader, selected for its low coefficient of thermal expansion which reduces thermomechanical deformation and allows for closer integration of the cold plate with silicon dies. Starting with 300 candidate designs, three-dimensional computational fluid dynamics simulations predict the thermal-hydraulic performance of cold plate subsections. The highest performing geometries are evaluated with high fidelity simulations. Four cold plates are manufactured for experiments: three with diamond-shaped pin fins and one with straights fins for comparison purposes. The cold plates are fabricated from copper-tungsten (CuW), copper (Cu), or aluminum-silicon-magnesium alloy (AlSi10Mg). The diamond-shaped pin fins achieve a roughly 15 % lower thermal resistance compared to the conventional straight fin microchannel. The highest performing design achieves a chip-to-coolant (including thermal interface material) thermal resistance of 9.0 K/kW in CuW and 6.9 K/kW in Cu under a 1 kW heat load with an inlet-to-outlet pressure drop of 9.0 kPa and water as the working fluid. This work demonstrates ultra-low thermal resistance and pressure drop cold plates for large die, high heat load applications, and shows that CuW is an attractive cold plate material for improved reliability in next generation data center cooling.
Coefficient of thermal expansion↗
Replacement of the axial copper ligand methionine with lysine in amicyanin converts it to a zinc-binding protein that no longer binds copper
The mutation of the axial ligand of the type I copper protein amicyanin from Met to Lys results in a protein that is spectroscopically invisible and redox inactive. M98K amicyanin acts as a competitive inhibitor in the reaction of native amicyanin with methylamine dehydrogenase indicating that the M98K mutation has not affected the affinity for its natural electron donor. The crystal structure of M98K amicyanin reveals that its overall structure is very similar to native amicyanin but that the type I binding site is occupied by zinc. Anomalous difference Fourier maps calculated using the data collected around the absorption edges of copper and zinc confirm the presence of Zn{sup 2+} at the type I site. The Lys98 NZ donates a hydrogen bond to a well-ordered water molecule at the type I site which enhances the ability of Lys98 to provide a ligand for Zn{sup 2+}. Attempts to reconstitute M98K apoamicyanin with copper resulted in precipitation of the protein. The fact that the M98K mutation generated such a selective zinc-binding protein was surprising as ligation of zinc by Lys is rare and this ligand set is unique for zinc.
08 HYDROGEN↗
Understanding Mass Transport in Copper Electrolyte-Based Dye-Sensitized Solar Cells
Copper redox shuttles, particularly [Cu(tmby) 2 ] 2+/1+ (tmby = bis(4,4',6,6'-tetramethyl-2,2'-bipyridine)), proved to be among the best electrolytes for dye-sensitized solar cells (DSCs), realizing higher power conversion efficiencies both under full sun and indoor illumination than conventional iodide/triiodide and cobalt electrolytes. Even though [Cu(tmby) 2 ] 2+/1+ renders a relatively higher performance, this metal complex is bulky and is limited by mass transport. Since the regeneration of the dye ground state by Cu I and the reaction of Cu II at the counter electrode are comparatively faster processes, the efficiency of DSC involving Cu I /Cu II electrolytes under relatively high light intensities is largely governed by the diffusion of Cu I /Cu II species. Understanding mass transport in these solar cells will enable further improvements in the performance of such copper-based DSCs. Here in the present study, the role of illumination intensity on the photogenerated current and its relationship to mass transport is evaluated using the best cosensitized dye (D35:XY1) and copper electrolyte ([Cu(tmby) 2 ] 2+/1+ ) combination.
14 SOLAR ENERGY↗
Understanding and control of bipolar self-doping in copper nitride
Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu{sub 3}N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu{sub 3}N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu{sub 3}N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu{sub 3}N with 10{sup 17} electrons/cm{sup 3} for low growth temperature (≈35 °C) and p-type with 10{sup 15} holes/cm{sup 3}–10{sup 16} holes/cm{sup 3} for elevated growth temperatures (50 °C–120 °C). Mobility for both types of Cu{sub 3}N was ≈0.1 cm{sup 2}/Vs–1 cm{sup 2}/Vs. Additionally, temperature-dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that V{sub Cu} defects form preferentially in p-type Cu{sub 3}N, while Cu{sub i} defects form preferentially in n-type Cu{sub 3}N, suggesting that Cu{sub 3}N is a compensated semiconductor with conductivity type resulting from a balance between donor and acceptor defects. Based on these theoretical and experimental results, we propose a kinetic defect formation mechanism for bipolar doping in Cu{sub 3}N that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials and provide a framework that can be applied when considering the properties of such materials in general.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
From Copper to Basic Copper Carbonate: A Reversible Conversion Cathode in Aqueous Anion Batteries
Abstract Dual‐ion batteries that use anions and cations as charge carriers represent a promising energy‐storage technology. However, an uncharted area is to explore transition metals as electrodes to host carbonate in conversion reactions. Here we report the reversible conversion reaction from copper to Cu 2 CO 3 (OH) 2 , where the copper electrode comprising K 2 CO 3 and KOH solid is self‐sufficient with anion‐charge carriers. This electrode dissociates and associates K + ions during battery charge and discharge. The copper active mass and the anion‐bearing cathode exhibit a reversible capacity of 664 mAh g −1 and 299 mAh g −1 , respectively, and relatively stable cycling in a saturated mixture electrolyte of K 2 CO 3 and KOH. The results open an avenue to use carbonate as a charge carrier for batteries to serve for the consumption and storage of CO 2 .
Gallagher, Trenton C.↗
Interfacial corrosion of copper in concentrated chloride solution and the formation of copper hydroxychloride
This work aims to investigate the waterline corrosion of pure copper in 4 M NaC1 solution. Three distinct regions are identified. Corrosion products formed at the waterline are characterized by micro-Raman spectroscopy, complemented by SEM/EDS, as a function of immersion time. The co-existence of four copper species is explained by thermodynamic equilibrium consideration. The composition of spreading region is determined and compared with the oxide film formation in different pH NaOH solutions. The anodic dissolution of copper exposed to the bulk electrolyte is investigated by electrochemical methods. The pH and potential profiles across three regions are proposed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Heterogeneous microstructural evolution during hydrodynamic penetration of a high-velocity copper microparticle impacting copper
Microparticle hydrodynamic penetration (HDP) may be associated with the erosion regime in cold spray processing and other high-velocity impact events. Here, in an experimental approach where we can individually launch particles and study the impact sites, we explore copper microparticles impacted on copper substrates at velocities above 900 m/s where HDP begins. We lift cross-sectional lamellae from the impact sites with a focused-ion beam for further microstructural characterization using electron backscatter diffraction and scanning transmission electron microscopy. Due to the gradients of strain, strain rate, and temperature associated with HDP, heterogeneous microstructures result. The structural evolution processes observed include deformation twinning and multiple dislocation-mediated grain recrystallization mechanisms—geometric dynamic recrystallization (gDRX), discontinuous DRX (dDRX), and meta DRX (mDRX). The higher strains at the interface lead to the most significant structural changes and complex mechanisms. In contrast, there is a gradient to more conventional dislocation plasticity away from the interface (on either the particle or substrate side). Here, these microstructural observations are consistent with the deformation map for copper and extend the observations of impact-induced recrystallization across new regimes of behavior.
Cold spray process↗
Copper/TEMPO Redox Redux: Analysis of PCET Oxidation of TEMPOH by Copper(II) and the Reaction of TEMPO with Copper(I)
Copper salts and organic aminoxyls, such as TEMPO (2,2,6,6- tetramethylpiperidine N -oxyl), are versatile catalysts for aerobic alcohol oxidation. Previous reports in the literature contain conflicting proposals concerning the redox interactions that take place between copper(I) and copper(II) salts with the aminoxyl and hydroxylamine species, TEMPO and TEMPOH, respectively. In this work, we reinvestigate these reactions in an effort to resolve the conflicting claims in the literature. Under anaerobic conditions, CuIIX2 salts [X= acetate (OAc), trifluoroacetate (TFA), triflate (OTf)] are shown to promote rapid proton-coupled oxidation of TEMPOH to TEMPO: Cu II X 2 + TEMPOH → Cu I X + TEMPO + HX. In the reaction with acetate, yet, slow reoxidation of Cu I OAc occurs. This process requires both TEMPO and HOAc and coincides with reduction of TEMPO to 2,2,6,6-tetramethylpiperidine. Analogous reactivity is not observed with trifluoroacetate and triflate species. As a whole, the facility of proton-coupled oxidation of TEMPOH by Cu II salts suggests that this process could contribute to catalyst regeneration under aerobic oxidation conditions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗