Results for “copper complexes” — Page 15

DOE OSTI2017

Paramagnetic Cu{sup II} complexes with 1-(hetarylmethyl)silatranes

The structures of paramagnetic complexes CuCl{sub 2}•L with L = HetCH{sub 2}Si(OCH{sub 2}CH{sub 2}){sub 3}N [Het = pyrrol-1-yl (1), indol-1-yl (2), carbazol-9-yl (3), imidazole-1-yl (4), 3,5-dimethylpyrazol-1-yl (5), 1,2,4-triazol-1-yl (6), benzimidazol-1-yl (7), and 1,2,3-benzotriazol-1-yl (8)] were studied by the ESR and quantum chemical methods in terms of the density functional theory (DFT) approximation. The difference in structures of complexes CuCl{sub 2}•1—CuCl{sub 2}•8 is mainly determined by the nature of the five-membered heterocycle. The ESR spectra at room temperature are typical of the mononuclear complexes of Cu{sup II} of axial symmetry with various types of distortions. In complexes CuCl{sub 2}•1—CuCl{sub 2}•3, narrow symmetric signals of zero-valent copper are recorded. These signals remain in the spectra for at least six months, which can characterize them as efficient stabilizing matrices of nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2026

An Activity-Based Sensing Approach to Monitor Nanomaterial-Promoted Changes in Labile Metal Pools in Living Systems

Metal-based nanoparticles are a promising class of materials for diagnosis and treatment of cancer and other diseases. However, mechanisms of action of these nanomedicines remain insufficiently understood due in large part to our limited understanding of the dynamic equilibria between solid metal nanoparticles and labile metal ions generated from these nanoparticles within complex biological milieus. Here, we apply activitybased sensing to directly identify and investigate the fate of labile copper pools with metal and oxidation state-specificity generated by anticancer copper nanomedicines. We found that treatment of cells with copper-releasing nanoparticles alter labile Cu(I)/Cu(II) ratios through an increase in labile Cu(II), while overall labile copper levels decrease. Labile copper release triggers compensatory responses in two major antioxidant pathways, glutathione (GSH) and nuclear factor erythroid 2-related factor 2 (NRF2), as well as in metal homeostasis to limit copper availability via regulation of copper export (ATP7B) and copper import (CTR1) proteins. These findings establish the value of activity-based sensing as a generalizable approach for labile metal imaging to help decipher molecular mechanisms of bioactive metal nanoparticles and guide the development of more effective nanomedicine diagnostics and therapies to target metal-dependent disease vulnerabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

Trans-Bis(acetato-o)bis(4-methylpyridine-N)copper(II)

The structure of trans-bis(acetato-O)bis(4-methyl- pyridine-N)copper(II), (Cu(C2H302)(sub 2)(C6H7N)(sub 2)), re- ported herein, represents a monomeric parent acetate complex with a distorted square-planar arrangement of acetate and 4-methylpyridine ligands around the Cu atom with the following distances and angles: Cu-N = 2.027 (4) and Cu-O1 = 1.950 (3) A; O1-Cu-N = 89.1 (2) and O1 -Cu-N' = 90.9 (2)deg. The Cu atom resides on a center of inversion. The most important dihedral angles are the angle between the 4-methylpyridine plane and the acetate plane (O1, O2, C21 and C22), 78.2 deg and the angle between the 4-methylpyridine ring and the coordination plane (Cu, N, O1), 31.6 deg.

Jedrzejas, Marek J.↗

DOE OSTI2022

Copper migration and surface oxidation of CuxBi2Se3 in ambient pressure environments

Abstract Chemical modifications such as intercalation can be used to modify surface properties or to further functionalize the surface states of topological insulators (TIs). Using ambient pressure x-ray photoelectron spectroscopy, we report copper migration in C u x B i 2 S e 3 , which occurs on a timescale of hours to days after initial surface cleaving. The increase in near-surface copper proceeds along with the oxidation of the sample surface and large changes in the selenium content. These complex changes are further modeled with core-level spectroscopy simulations, which suggest a composition gradient near the surface which develops with oxygen exposure. Our results shed light on a new phenomenon that must be considered for intercalated TIs—and intercalated materials in general—that surface chemical composition can change when specimens are exposed to ambient conditions.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Chromatographic and Spectroscopic Study of the Interaction between Polysulfides and Copper Sulfides

To mitigate the “polysulfide shuttle” in lithium–sulfur batteries, different hosting materials that can interact with the polysulfide species physically or chemically have been widely investigated. Copper sulfides as one type of material are believed to have strong chemical interactions with the polysulfide species to consequently influence the performances of Li–S batteries. In this work, high-performance liquid chromatography (HPLC), electrospray ionization mass spectrometry (ESI/MS), scanning electron microscopy with energy-dispersive X-ray spectrometry (SEM-EDS), and inductively coupled plasma optical emission spectroscopy (ICP-OES) were used to systematically investigate the interactions between ether-based polysulfide solutions and copper sulfides (as well as silver sulfide). Furthermore, based on chromatographic and spectroscopic results, the interactions between polysulfides and Cu 2 S can be classified into two types of reactions: one is the redox reaction with the formation of CuS, while another is the complexation reaction with the formation of soluble LiCuS n (n ≥ 4). Contrarily, Ag 2 S (and CuS) shows no interactions with polysulfides. Accordingly, the cycling behaviors of Li–S batteries with copper sulfides as hosting materials or with copper as additives were explained reasonably.

25 ENERGY STORAGE↗

DOE OSTI2024

Intercalative Redox Tuning for Cu/Li x Mn 2 O 4 -Catalyzed Oxidative Alkyne Coupling

Modulation of heterogeneous catalyst structure is ubiquitous within efforts to improve catalytic activity and selectivity at the molecular level. Herein, manganese oxide (MnO 2 ) is employed as a continuously tunable catalyst support through increasing extent of lithium intercalation and reduced surface potential. Oxidative grafting of an organocopper complex onto various lithium manganese oxides (Li x Mn 2 O 4 , x = 0-2.1) produced divalent and monovalent copper species on the partially reduced (0 ≤ x ≤ 1.2) and fully reduced (x = 2.1) surfaces, respectively, as determined by X-ray absorption fine structure (XAFS) analysis. In this study, the resultant materials are catalytically active for the oxidative coupling of terminal alkynes, with steady-state reaction rate data of oxidative propyne dimerization (200 °C, 0.6-2.4 kPa propyne, 2.4-9.9 kPa O 2 ) indicating that complete support lithiation (Li 2.1 Mn 2 O 4 ) provides increased catalytic performance and renders reoxidation steps less kinetically demanding compared to the unreduced parent material. Enacting a dual site (Cu and MnO x ) kinetic model can account for dimerization rates measured over Cu/Li 2.1 Mn 2 O 4 under various reactant concentrations, copper loadings, and surface coverages, providing supporting evidence for the synergistic role of the metal and support in facilitating the coupling reaction. Overall, results presented here provide an extension for general strategies of systematically controlling catalytic structure and function through lithium reduction of bulk oxides and subsequent electronic modulation of the metals supported thereon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction

Single crystals and shape-controlled nanocrystals are well known to exhibit facet-dependent catalytic properties. However, few studies have investigated how those nanocrystals evolve and (de)activate during reactions, calling for the development of nanoscale time-resolved operando methods. In this context, we have designed Cu nanocubes as a model system to elucidate the underlying driving force of dynamic nanocatalyst reconstruction during the CO2 reduction reaction (CO2RR). Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and synchrotron-based X-ray spectroscopy reveal the size- and potential-dependent complete transformation from (100)-oriented Cu@Cu2O nanocubes to polycrystalline metallic Cu nanograins under CO2RR conditions. In addition, machine learning-assisted operando four-dimensional STEM reveals that large Cu nanograins derived from nanocubes form mainly crystalline domains, while their smaller counterparts are more amorphous due to faster evolution kinetics. In situ Raman spectroscopy and density functional theory calculations suggest that CO drives the ejection of single Cu atoms, resulting in few-nanometre Cu clusters and the surface migration of highly mobile copper carbonyl (Cu–CO) species. Combined, these multimodal operando methods and theoretical approaches pave the way for understanding the complex structural evolution of energy-related nanocatalysts under electrochemical conditions.

Yang, Yao↗

DOE OSTI2018

Trapping intermediates in metal transfer reactions of the CusCBAF export pump of Escherichia coli

Escherichia coli CusCBAF represents an important class of bacterial efflux pump exhibiting selectivity towards Cu(I) and Ag(I). The complex is comprised of three proteins: the CusA transmembrane pump, the CusB soluble adaptor protein, and the CusC outer-membrane pore, and additionally requires the periplasmic metallochaperone CusF. Here we used spectroscopic and kinetic tools to probe the mechanism of copper transfer between CusF and CusB using selenomethionine labeling of the metal-binding Met residues coupled to RFQ-XAS at the Se and Cu edges. The results indicate fast formation of a protein–protein complex followed by slower intra-complex metal transfer. An intermediate coordinated by ligands from each protein forms in 100 ms. Stopped-flow fluorescence of the capping CusF-W44 tryptophan that is quenched by metal transfer also supports this mechanism. The rate constants validate a process in which shared-ligand complex formation assists protein association, providing a driving force that raises the rate into the diffusion-limited regime.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1994

Large-displacement structural durability analyses of simple bend specimen emulating rocket nozzle liners

Large-displacement elastic and elastic-plastic, finite-element stress-strain analyses of an oxygen-tree high-conductivity (OFHC) copper plate specimen were performed using an updated Lagrangian formulation. The plate specimen is intended for low-cost experiments that emulate the most important thermomechanical loading and failure modes of a more complex rocket nozzle. The plate, which is loaded in bending at 593 C, contains a centrally located and internally pressurized channel. The cyclic crack initiation lives were estimated using the results from the analyses and isothermal strain-controlled low-cycle fatigue data for OFHC copper. A comparison of the predicted and experimental cyclic lives showed that an elastic analysis predicts a longer cyclic life than that observed in experiments by a factor greater than 4. The results from elastic-plastic analysis for the plate bend specimen, however, predicted a cyclic life in close agreement with experiment, thus justifying the need for the more rigorous stress-strain analysis.

Arya, Vinod K.↗

DOE OSTI2025

Best Practices for Grid Communications

As the grid evolves, the communications architecture will need to evolve with it. That architecture affords a structured means by which the evolving complexities of the modern electric grid can be managed. This document provides best practices that can be implemented in the grid of today and evolve towards the grid and grid architecture of the future. The evolving grid and its control communications increasingly rely on commercial communications providers and a variety of technologies, from wireless (e.g., 5G, microwave, Wi-Fi) to wireline (fiber, copper) to radio communications (P25, other repeater-based systems), and all these communications systems rely on electric power. A reliable and resilient grid must account for this complex set of interdependencies in its planning activities, especially those involving restoration and recovery. The participation of all relevant parties in both planning and exercising of plans can prevent unexpected conditions that impede the reliable operation and recovery of the grid. Best practices for grid communications include using a Network Management System to document the operational state, define and monitor baselines, detect changes, and accelerate response to abnormalities. If transitioning from SONET to IP/packet-based systems, translating grid requirements into communications requirements for latency, bandwidth and throughput, IP packet delay variation, packet loss, and availability should inform and drive technology planning and selection as well as that communication system’s Quality of Service (QoS) policies and Service Level Agreements (SLAs). Secure and reliable timing is another key component of a reliable and resilient grid that can operate through adverse events. A trusted internal NTP configuration, an integrated and diverse timing delivery system, optimizing the timing architecture based on the transport technologies of the communications system, and using established standards can deliver the level of timing accuracy required by a range of time-sensitive power system applications.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2020

In Situ Studies of Methanol Decomposition Over Cu(111) and Cu2O/Cu(111): Effects of Reactant Pressure, Surface Morphology, and Hot Spots of Active Sites

The dissociative adsorption of methanol was investigated on Cu(111) and ultrathin Cu 2 O films. We employed synchrotron-based Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Scanning Tunneling Microscopy (STM) to study the dynamics of gas–solid interactions, and calculations based on Density Functional Theory (DFT) were used to examine the reaction path. C 1s XPS spectra revealed that methanol underwent dissociative adsorption on plain Cu(111) to form methoxy (CH 3 O), formaldehyde (H 2 CO), and formate (HCOO) at a pressure range of 0.5–10 mTorr, with these species remaining on the surface after evacuation. This was accompanied by the appearance of a low coverage (~0.05 ML) of O ads in the O 1s which can be considered a highly active site for methanol activation. The high activity is apparent by a coverage of 0.8 ML of methoxy at room temperature. STM was unable to image these species at room temperature as they were highly mobile on metallic copper. In contrast, for CH 3 OH on Cu 2 O/Cu(111), STM showed clear hot spots for reaction and a complex array of adsorption structures. On the oxide substrate, there was decomposition of methanol to H 2 CO, CH 3 O, HCOO, and hydrocarbon species (CH x ) due to the subsequent interactions of methanol with lattice oxygen. Cu(111) remained entirely saturated with decomposition products under 10 mTorr of methanol (θ ≈ 0.97 ML), whereas the Cu 2 O overlayer was saturated at a much lower coverage (θ ≈ 0.30 ML). STM revealed rows and step edges of Cu 2 O decorated with decomposition products and metallic Cu islands ~5 nm in size. The difference in activity between Cu(111) and Cu 2 O/Cu(111) is attributed to the significant amount of O present on the oxide surface. Additionally, Density Functional theory (DFT) calculations described the XPS measurements well, showing a likely methanol dissociation to *CH 3 O and therefore a surface reduction. More importantly, the DFT results revealed that it was the chemisorbed oxygen on Cu 2 O/Cu(111) which oxidized the dissociated *CH 3 O to *HCOO and eventually CO 2 , while the reaction only involving upper oxygen on the Cu 2 O hexagonal ring led to the formation of H 2 CO.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Carrier providers or killers: The case of Cu defects in CdTe

Defects play important roles in semiconductors for optoelectronic applications. Common intuition is that defects with shallow levels act as carrier providers and defects with deep levels are carrier killers. Here, taking the Cu defects in CdTe as an example, we show that relatively shallow defects can play both roles. Using first-principles calculation methods combined with thermodynamic simulations, we study the dialectic effects of Cu-related defects on hole density and lifetime in bulk CdTe. Because CuCd can form a relatively shallow acceptor, we find that increased Cu incorporation into CdTe indeed can help achieve high hole density; however, too much Cu can cause significant non-radiative recombination. We discuss strategies to balance the contradictory effects of Cu defects based on the calculated impact of Cd chemical potential, copper defect concentrations, and annealing temperature on lifetime and hole density. Lastly, these findings advance the understanding of the potential complex defect behaviors of relatively shallow defect states in semiconductors.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2019

Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu 2+ + e ↔ Cu 1+ Redox Reaction in Ethaline Deep Eutectic Solvent

Deep eutectic solvent (DES) based electrolytes are gaining attention for electrochemical applications. As such, knowledge of the charge transfer kinetics in DES and its dependence on electrolyte composition and temperature is important. Using Cu 2+ + e ↔ Cu 1+ as a model system, we demonstrate that metal redox reactions in chloride-containing DES media suffer from sluggish charge transfer kinetics. The exchange current density, i 0 , displayed a peculiar inverse relationship with the bulk chloride concentration, [Cl – ] b . The i 0 decreased from 7.9 to 3.0 mA/cm 2 when [Cl – ] b increased from 2.8 to 4.6 M at 30°C. Such dependence is shown to originate from Cl – complexation with reactant and product species. Furthermore, i 0 increased with an increase in Cu n + bulk concentration in the 50–200 mM range. Also, increase in temperature elevated i 0 . The charge transfer coefficient α c , however, remained constant (~0.5) and was unaffected by Cu n + or Cl – concentrations or by temperature. To explain how charge transfer kinetics depend on the various system parameters, a model incorporating complexation phenomena was developed and its predictions were compared to experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Ultrafast infrared nano-spectroscopy and nano-imaging of unconventional superconductivity in cuprate and pnictide high- T c systems

High- T c superconductivity is surpassed by few, if any, other unsolved problems in contemporary physics in terms of its richness, complexity, impact on other fields, and potential technological importance. Before 2008, the term “high- T c superconductivity” was reserved for copper oxides or cuprates (maximum T c ~160 K). The discovery of superconductivity in Fe-based pnictides compounds with Tc almost as high as 60 K has prompted a renewed surge of research activity. Systematic studies have revealed both common and contrasting trends in the cuprate and pnictide superconductors. In both classes of materials, superconductivity occurs in close proximity with other electronic phases: an antiferomagnetic (AF) Mott insulator state in the case of the (hole-doped) cuprates and metallic spin density wave (SDW) phase in the case of the pnictides. One common aspect of Fe- and Cu-based systems is a propensity towards electronic and magnetic self-organization, leading to dynamic inhomogeneities at nano-to-mesoscopic length scales. The inhomogeneities have so far been documented with quasi-static probes such as nuclear magnetic resonance, neutron and x-ray scattering along with scanning tunneling microscopies. In contrast, ultrafast infrared/optical studies enable characterization of dynamics and fluctuations in superconductors. However, such experiments have been carried out using diffraction-limited optics and therefore probe length scales that inform us of a “mixed” response involving contributions from the multiple electronic, chemical and structural phases occurring in real materials while averaging over nanoscale heterogeneities. As a result, the interpretation of area-averaged ultrafast optics data has often remained both complicated and ambiguous.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS1990

Advanced tube-bundle rocket thrust chamber

An advanced rocket thrust chamber for future space application is described along with an improved method of fabrication. Potential benefits of the concept are improved cyclic life, reusability, and performance. Performance improvements are anticipated because of the enhanced heat transfer into the coolant which will enable higher chamber pressure in expander cycle engines. Cyclic life, reusability and reliability improvements are anticipated because of the enhanced structural compliance inherent in the construction. The method of construction involves the forming of the combustion chamber with a tube-bundle of high conductivity copper or copper alloy tubes, and the bonding of these tubes by an electroforming operation. Further, the method of fabrication reduces chamber complexity by incorporating manifolds, jackets, and structural stiffeners while having the potential for thrust chamber cost and weight reduction.

Kazaroff, John M.↗

NASA NTRS1990

Advanced tube-bundle rocket thrust chamber

An advanced rocket thrust chamber for future space application is described along with an improved method of fabrication. Potential benefits of the concept are improved cyclic life, reusability, and performance. Performance improvements are anticipated because of the enhanced heat transfer into the coolant which will enable higher chamber pressure in expander cycle engines. Cyclic life, reusability and reliability improvements are anticipated because of the enhanced structural compliance inherent in the construction. The method of construction involves the forming of the combustion chamber with a tube-bundle of high conductivity copper or copper alloy tubes, and the bonding of these tubes by an electroforming operation. Further, the method of fabrication reduces chamber complexity by incorporating manifolds, jackets, and structural stiffeners while having the potential for thrust chamber cost and weight reduction.

Kazaroff, John M.↗

NASA NTRS2019

Additive Manufacturing and Hot-Fire Testing of Bimetallic GRCop-84 and C-18150 Channel-Cooled Combustion Chambers Using Powder Bed Fusion and Inconel 625 Hybrid Directed Energy Deposition

Additive manufacturing (AM) is an advanced fabrication technique that is demonstrating tremendous potential to reduce fabrication lead times and costs for liquid rocket engine components. The additive manufacturing technology lends itself to fabricate components with complex features such as internal coolant channels in combustion chambers that would otherwise require complex manufacturing operations. A requirement for high performance engines is to use high conductivity, high strength materials such as copper-alloys for combustion chamber liners to provide adequate wall temperatures and meet subsequent structural margins. A further requirement of this configuration is to minimize weight by defining and fabricating material in discrete locations as required. NASA and Industry partner, Virgin Orbit, have been working to advance these technologies through development of bimetallic additive manufacturing techniques under a public-private partnership through NASA’s Announcement of Collaborative Opportunity (ACO). This partnership is advancing a bimetallic hybrid additively manufactured combustion chamber that integrates Powder Bed Fusion (PBF), specifically Selective Laser Melting (SLM), and Directed Energy Deposition (DED) blown powder techniques to optimize the chamber materials and subsequent assembly. The SLM process is being developed for the combustion chamber liner to use copper-alloys GRCop-84 (Copper-Chrome-Niobium) or C-18150 (Copper-Chrome-Zirconium). The hybrid DED blown powder technology is used to apply an integrated structural jacket and manifolds using an Inconel 625 superalloy on the outer surface of the SLM copper liner. The hybrid DED technology being used on this program is a DMG Mori Seiki AM machining center which integrates the DED blown powder with an integral subtractive (traditional) machining to minimize overall setups. A series of chambers were fabricated using these techniques with GRCop-84/Inconel 625 and C-18150/Inconel and hot-fire tested at NASA Marshall Space Flight Center (MSFC) in LOX/Kerosene (RP-1). This paper describes the process development to integrate these AM technologies into an integrated bimetallic assembly, the design of the chamber, results from hot-fire testing, and further development.

Gradl, Paul R.↗

NASA NTRS2019

Additive Manufacturing and Hot-fire Testing of Bimetallic GRCop-84 and C-18150 Channel-Cooled Combustion Chambers using Powder Bed Fusion and Inconel 625 Hybrid Directed Energy Deposition

Additive manufacturing (AM) is an advanced fabrication technique that is demonstrating tremendous potential to reduce fabrication lead times and costs for liquid rocket engine components. The additive manufacturing technology lends itself to fabricate components with complex features such as internal coolant channels in combustion chambers that would otherwise require complex manufacturing operations. A requirement for high performance engines is to use high conductivity, high strength materials such as copper-alloys for combustion chamber liners to provide adequate wall temperatures and meet subsequent structural margins. A further requirement of this configuration is to minimize weight by defining and fabricating material in discrete locations as required. NASA and Industry partner, Virgin Orbit, have been working to advance these technologies through development of bimetallic additive manufacturing techniques under a public-private partnership through NASA’s Announcement of Collaborative Opportunity (ACO). This partnership is advancing a bimetallic hybrid additively manufactured combustion chamber that integrates Powder Bed Fusion (PBF), specifically Selective Laser Melting (SLM), and Directed Energy Deposition (DED) blown powder techniques to optimize the chamber materials and subsequent assembly. The SLM process is being developed for the combustion chamber liner to use copper-alloys GRCop-84 (Copper-Chrome-Niobium) or C-18150 (Copper-Chrome-Zirconium). The hybrid DED blown powder technology is used to apply an integrated structural jacket and manifolds using an Inconel 625 superalloy on the outer surface of the SLM copper liner. The hybrid DED technology being used on this program is a DMG Mori Seiki AM machining center which integrates the DED blown powder with an integral subtractive (traditional) machining to minimize overall setups. A series of chambers were fabricated using these techniques with GRCop-84/Inconel 625 and C-18150/Inconel and hot-fire tested at NASA Marshall Space Flight Center (MSFC) in LOX/Kerosene (RP-1). This paper describes the process development to integrate these AM technologies into an integrated bimetallic assembly, the design of the chamber, results from hot-fire testing, and further development.

Gradl, Paul↗