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At least 1,495 records · Page 83
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onset potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.

Liu, Xiang↗
DOE OSTI2017

Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance

Copper nanoparticles exhibit intense and sharp localized surface plasmon resonance (LSPR) in the visible region; however, the LSPR peaks become weak and broad when exposed to air due to the oxidation of Cu. In this work, the Cu nanoparticles are successfully encapsulated in SiO 2 by employing trioctyl-n-phosphine (TOP)-capped Cu nanoparticles for the sol–gel reaction, yielding an aqueous Cu–SiO 2 core–shell suspension with stable and well-preserved LSPR properties of the Cu cores. With the TOP capping, the oxidation of the Cu cores in the microemulsion was significantly reduced, thus allowing the Cu cores to sustain the sol–gel process used for coating the SiO 2 protection layer. It was found that the self-assembled TOP-capped Cu nanoparticles were spontaneously disassembled during the sol–gel reaction, thus recovering the LSPR of individual particles. During the disassembling progress, the extinction spectrum of the nanocube agglomerates evolved from a broad extinction profile to a narrow and sharp peak. For a mixture of nanocubes and nanorods, the spectra evolved to two distinct peaks during the dissembling process. The observed spectra match well with the numerical simulations. In conclusion, these Cu–SiO 2 core–shell nanoparticles with sharp and stable LSPR may greatly expand the utilization of Cu nanoparticles in aqueous environments.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Tuning the Deoxygenation of Bulk-Dissolved Oxygen in Copper

Using synchrotron-based ambient-pressure X-ray photoelectron spectroscopy, we report the tuning of the deoxygenation process of bulk dissolved oxygen in copper via a combination of H 2 gas flow and elevated temperature. Here, we show that a critical temperature of ~580 °C exists for driving segregation of bulk dissolved oxygen to form chemisorbed oxygen on the Cu surface, which subsequently reacts with hydrogen to form OH species and then H 2 O molecules that desorb from the surface. This deoxygenation process is tunable by a progressive stepwise increase of temperature that results in surface segregation of oxygen from deeper regions of bulk Cu. Using atomistic simulations, we show that the bulk-dissolved oxygen occupies octahedral sites of the Cu lattice and the deoxygenation process involves oxygen migration between octahedral and tetrahedral sites with a diffusion barrier of ~0.5 eV.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Resolution of Selectivity Steps of CO Reduction Reaction on Copper by Quantum Monte Carlo

Electrochemical reduction of carbon monoxide to valuable fuels and chemicals on copper surfaces remains a challenging area in catalysis due to a limited understanding of adsorption mechanisms and reaction pathways. Although density functional theory (DFT)-based studies have investigated these processes, their accuracy varies across different functionals. Here, in this study, we present the application of fixed-node diffusion Monte Carlo (FNDMC) to benchmark the adsorption energies of CO*, H*, and key CO reduction reaction (CORR) intermediates, COH* and CHO* on the Cu(111) surface. Our results for CO* and H* adsorption energies closely align with experimentally measured chemisorption reactions, highlighting the limitations of DFT and providing site-specific energy comparisons that are often not available experimentally. Additionally, we explore the effect of explicit solvation, demonstrating how water stabilizes the COH* over CHO*, thus suggesting a critical role of COH* in CORR. Finally, we release our high-accuracy FNDMC benchmarks for testing and developing new DFT functionals for electrocatalysis. Overall, this study underscores the potential of FNDMC for detailed surface chemistry studies and offers new insights into catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Electrochemical Growth of Copper Hydroxy Double Salt Films and Their Conversion to Nanostructured p-Type CuO Photocathodes

New electrochemical synthesis methods were developed to produce copper hydroxy double salts (Cu-HDS) films with four different intercalated anions (NO 3 - , SO 4 2- , Cl - , and dodecyl sulfate (DS)) as pure crystalline films as-deposited (Cu 2 NO 3 (OH) 3 , Cu 4 SO 4 (OH) 6 , Cu 2 Cl(OH) 2 , and Cu 2 DS(OH) 3 ). These methods are based on p-benzoquinone reduction, which increases the local pH at the working electrode and triggers the precipitation of Cu 2+ and appropriate anions as Cu-HDS films on the working electrode. The resulting Cu-HDS films could be converted to crystalline Cu(OH) 2 and CuO films by immersing them in basic solutions. Since Cu-HDS films were composed of 2D crystals due to the atomic level layered structure of HDS, the CuO films prepared from Cu-HDS films have unique low dimensional nanostructures, creating high surface areas, which cannot be obtained by direct deposition of CuO that has a 3D atomic level crystal structure. Here, the resulting nanostructures allowed the CuO films to facilitate electron-hole separation and demonstrate great promise for photocurrent generation when investigated as a photocathode for a water splitting photoelectrochemical cell. Electrochemical synthesis of Cu-HDS films and their facile conversion to CuO films will provide new routes to tune morphologies and properties of the CuO electrodes that may not be possible by other synthesis means.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Decoding Active Sites for Highly Efficient Semihydrogenation of Acetylene in Palladium–Copper Nanoalloys

Accurately decoding the three-dimensional atomic structure of surface active sites is essential yet challenging for a rational catalyst design. Here, we used comprehensive techniques combining the pair distribution function and reverse Monte Carlo simulation to reveal the surficial distribution of Pd active sites and adjacent coordination environment in palladium-copper nanoalloys. After the fine-tuning of the atomic arrangement, excellent catalytic performance with 98% ethylene selectivity at complete acetylene conversion was obtained in the Pd 34 Cu 66 nanocatalysts, outperforming most of the reported advanced catalysts. Further, t he quantitative deciphering shows a large number of active sites with a Pd-Pd coordination number of 3 distributed on the surface of Pd 34 Cu 66 nanoalloys, which play a decisive role in highly efficient semihydrogenation. This finding not only opens the way for guiding the precise design of bimetal nanocatalysts from atomic-level insight but also provides a method to resolve the spatial structure of active sites.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Silicon-Copper Helical Arrays for New Generation Lithium Ion Batteries

The helical array (with 10 atom % Cu) exhibits 3130 mAh g–1 with 83% columbic efficiency and retains 83% of its initial discharge capacity after 100th cycle. Homogeneously distributed interspaces between the helical arrays accommodate high volumetric changes upon cycling and copper atoms form a conductive network to buffer the mechanical stress generated in the electrode while minimizing electrochemical agglomeration of Si. Also, ion assistance is believed to enhance the density of the helices at the bottom thus increasing the adhesion

anode↗
DOE OSTI2018

Ultracompliant Heterogeneous Copper–Tin Nanowire Arrays Making a Supersolder

Due to the substantial increase in power density, thermal interface resistance that can constitute more than 50% of the total thermal resistance has generally become a bottleneck for thermal management in electronics. However, conventional thermal interface materials (TIMs) such as solder, epoxy, gel, and grease cannot fulfill the requirements of electronics for high-power and long-term operation. Here, we demonstrate a high-performance TIM consisting of a heterogeneous copper-tin nanowire array, which we term 'supersolder' to emulate the role of conventional solders in bonding various surfaces. The supersolder is ultracompliant with a shear modulus 2-3 orders of magnitude lower than traditional solders and can reduce the thermal resistance by two times as compared with the state-of-the-art TIMs. This supersolder also exhibits excellent long-term reliability with >1200 thermal cycles over a wide temperature range. By resolving this critical thermal bottleneck, the supersolder enables electronic systems, ranging from microelectronics and portable electronics to massive data centers, to operate at lower temperatures with higher power density and reliability.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Unraveling the Formation Mechanism of a Hybrid Zr-Based Chemical Conversion Coating with Organic and Copper Compounds for Corrosion Inhibition

Environmental-friendly chromate-free, zirconium (Zr)-based conversion coating is a promising green technology for corrosion protection. Additives in the surface treatment provides critical functionalities and performance improvements; however, mechanistic understanding as of how the additives influence the coatings remains unclear. In this study, a new organic-inorganic hybrid Zrbased conversion coating which combines copper (Cu) compounds and polyamidoamine (PAMAM), taking advantages of a complementary nature of organic and inorganic additives. Here, a multimodal approach combining electron and X-ray characterization is applied to study the interaction of Cu 2+ and PAMAM and the resulting impacts on the coating formation. Adding PAMAM changed the surface morphology, thickness, distribution of Cu in the cluster and void formation of the coatings. High PAMAM (100-200 pm) leads to little conversion coating formation, and low PAMAM (0-25 ppm) shows voids formation under the coatings. Moreover, PAMAM incorporates in the coating in a form of PAMAM-Cu complex with a higher concentration towards the surface, provides an organic layer at the surface of the coating. X-ray absorption near-edge structure (XANES) spectroscopy shows a difference between the conventional and hybrid coating treatments in an alkaline solution to simulate the E-coat process, suggesting the contribution of PAMAM in the enhanced chemical stability in an alkaline environment. Therefore, an intermediate range of addition of PAMAM (50 ppm) is optimal to 1) avoid excessive voids formation, 2) promote some Cu cluster formation and thus enhancing the Zr-based coating formation and 3) incorporate organic components into the coating to improve the adhesion of the subsequent coatings. Overall, this work furthers our knowledge on the formation mechanism of an effective and environmentally friendly hybrid conversion coating for corrosion inhibition, demonstrating a critical processing-structureproperty relationship. This study will benefit future development of green and effective surface treatment technology.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Channel Scaling Dependent Photoresponse of Copper-Based Flexible Photodetectors Fabricated Using Laser-Induced Oxidation

Copper (Cu) oxide compounds (Cu x O), which include cupric (CuO) and cuprous (Cu 2 O) oxide, have been recognized as a promising p-channel material with useful photovoltaic properties and superior thermal conductivity. Typically, deposition methods or thermal oxidation can be used to obtain Cu x O. However, these processes are difficult to apply to flexible substrates because plastics have a comparatively low glass transition temperature. Also, additional patterning steps are needed to fabricate applications. In this work, we fabricated a metal–semiconductor–metal photodetector using laser-induced oxidation of thin Cu films under ambient conditions. Raman spectroscopy, scanning electron microscopy–energy-dispersive X-ray spectroscopy, and atomic force microscopy were used to study the composition and morphology of our devices. Moreover, the photoresponse of this device is reported herein. We performed an in-depth analysis of the relationship between the channel size and number of carriers using scanning photocurrent microscopy. The carrier transport behaviors were identified; the photocurrent decreased as the length and width of the channel increased. Furthermore, we verified the suitability of the device as a flexible photodetector using a variety of bending tests. Our in-depth analysis of this Cu-based flexible photodetector could play an important role in understanding the mechanisms of other flexible photovoltaic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

3D Morphology of Bimodal Porous Copper with Nano-Sized and Micron-Sized Pores to Enhance Transport Properties for Functional Applications

Multiscale porous metals with multiscale porosity from nanometer to micrometer have a high specific surface area and high effective diffusivity for ion transport, thereby enhancing functionalities and extending the applications of porous metals. Herein, the Cu–Fe–Al ternary system was selected as the precursor alloy to construct multiscale, bimodal porous copper by the chemical dealloying method. The effect of the phase composition and initial microstructure of precursor alloys (Al x Fe 75– x Cu 25 , x = 10–60) on the three-dimensional (3D) morphology of multiscale porous metals was systematically investigated, with a goal to precisely control the multiscale porous structure. The four crystal structure phases (body-centered cubic (BCC), face-centered cubic (FCC), CsCl type (B2), and monoclinic) in precursor alloys were analyzed by synchrotron X-ray diffraction refinement. The 3D morphology, feature size distribution, and tortuosity of four representative porous Cu after dealloying Al x Fe 75– x Cu 25 ( x = 10, 30, 50, and 60) precursor alloys were directly visualized and quantified via advanced synchrotron X-ray nanotomography. The relationship between the phases/crystal structures of precursor alloys and their corresponding porous morphology was established: the micron-sized pores in bimodal porous Cu are formed by dissolving the CuFeAl phase with BCC and monoclinic crystal structures, and the nano-sized pores are formed by dealloying the CuFeAl phase with FCC and B2 crystal structures. The size of the nanoporous structure depends on the ratio between the more noble and more active components in the precursor alloy, while the size of the microporous structure depends on the corresponding phase size in the precursor alloy. The tortuosity results showed that the multiscale porous structure with both nanoporosity and microporosity exhibits lower tortuosity, which will enhance transport properties for functional applications.

25 ENERGY STORAGE↗
DOE OSTI2020

Copper–Carbon Nanotube Composites Enabled by Electrospinning for Advanced Conductors

The power losses associated with the electrical resistance of copper (Cu) have generated considerable interest in the development of advanced conductors that incorporate carbon nanotubes (CNTs) into the Cu matrix—ultraconductive Cu (UCC) composites—to increase energy efficiency in various industrial and residential applications, ranging from electric power transmission and rotating machinery to electronic devices. To meet this demand, we describe an electrospinning-based polymer nanofiber templating strategy for the fabrication of UCC composites with electrical and mechanical performance exceeding that of Cu. Our approach involves electrospinning of polyvinylpyrrolidone (PVP)-based solutions containing CNTs into aligned PVP/CNT nanofibers onto Cu foil substrates, followed by vacuum-assisted thermal removal of organic solvent/polymer from the CNT matrix to achieve a uniformly distributed CNT layer on the Cu surface. Following additional Cu deposition, the Cu–CNT–Cu composites demonstrated similar electrical conductivity, higher current carrying capacity, and improved mechanical properties compared with those obtained from reference Cu. Importantly, after the heat treatment, Raman analysis of the CNT network displayed an increased metallic character that supports the enhanced electrical properties of the UCC composites. Thus, we believe that these performance characteristics together with the commercial viability of the present approach could open new possibilities in designing advanced conductors for a broad range of electrical systems and industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

High-Performance Core–Shell Catalyst with Nitride Nanoparticles as a Core: Well-Defined Titanium Copper Nitride Coated with an Atomic Pt Layer for the Oxygen Reduction Reaction

A class of core–shell structured low-platinum catalysts with well-dispersed inexpensive titanium copper nitride nanoparticles as cores and atomic platinum layers as shells exhibiting high activity and stability for the oxygen reduction reaction is successfully developed. In using nitrided carbon nanotubes (NCNTs) as the support greatly improved the morphology and dispersion of the nitride nanoparticles, resulting in significant enhancement of the performance of the catalyst. The optimized catalyst, Ti 0.9 Cu 0.1 N@Pt/NCNTs, has a Pt mass activity 5 times higher than that of commercial Pt/C, comparable to that of core–shell catalysts with precious metal nanoparticles as the core, and much higher than that the latter if we take into account the mass activity of all platinum group metals. Furthermore, only a minimal loss of activity can be observed after 10000 potential cycles, demonstrating the catalyst’s high stability. After durability testing, atomic-scale elemental mapping confirmed that the core–shell structure of the catalyst remained intact. This approach may open a pathway for the design and preparation of high-performance inexpensive core–shell catalysts for a wide range of applications in energy conversion processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Copper Single Atoms Anchored in Porous Nitrogen-Doped Carbon as Efficient pH-Universal Catalysts for the Nitrogen Reduction Reaction

Artificial nitrogen fixation through the nitrogen reduction reaction (NRR) under ambient conditions is a potentially promising alternative to the traditional energy-intensive Haber–Bosch process. For this purpose, efficient catalysts are urgently required to activate and reduce nitrogen into ammonia. Herein, by the combination of experiments and first-principles calculations, we demonstrate that copper single atoms, attached in a porous nitrogen-doped carbon network, provide highly efficient NRR electrocatalysis, which compares favorably with those previously reported. Benefiting from the high density of exposed active sites and the high level of porosity, the Cu SAC exhibits high NH 3 yield rate and Faradaic efficiency (FE), specifically ~53.3 μg$_{NH_3}$ h –1 mg cat –1 and 13.8% under 0.1 M KOH, ~49.3 μg$_{NH_3}$ h –1 mg cat –1 and 11.7% under 0.1 M HCl, making them truly pH-universal. They also show good stability with little current attenuation over 12 h of continuous operation. Cu–N 2 coordination is identified as the efficient active sites for the NRR catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Sodium-Ion Battery Cathode with Dominating Copper and Oxygen Redox Chemistry

Sodium-ion batteries offer low-cost energy storage solutions for the grid and electric vehicles, leveraging the established "rocking-chair" Li-ion design and the natural abundance of sodium. However, SIBs face challenges such as relatively lower voltage and capacity than lithium-ion batteries, as well as dependence on nickel resources. Here, in this work, a new nickel-free cathode material, Na 0.75 Li 0.08 Cu 0.25 Mn 0.66 O 2 , was designed and synthesized. This material has a capacity of ~125 mAh/g and an average discharge voltage of 3.5 V. Notably, more than one-third of the capacity arises from lithium substitution of Cu (~8 mol.%) and high voltage activation to 4.6 V. Multimodal synchrotron x-ray characterization combining spectroscopy, microscopy, and scattering reveal the capacity is primarily from the redox of copper and oxygen, with a minor contribution from the manganese redox. Lithium substitution alters the phase transition mechanism from a two-phase transition in P3-Na 2/3 Cu 1/3 Mn 2/3 O 2 to a solid-solution in Na 0.75 Li 0.08 Cu 0.25 Mn 0.66 O 2 , enhancing the reversibility of this material.

25 ENERGY STORAGE↗
DOE OSTI2017

Copper Nanoparticles Installed in Metal–Organic Framework Thin Films are Electrocatalytically Competent for CO 2 Reduction

Copper nanoparticles are embedded into a solvothermally grown thin film of a zirconium metal-organic framework (MOF), NU-1000, by installing single-site Cu(II) into the NU-1000 thin film via solvothermal deposition in MOFs (SIM) followed by electrochemical reduction of Cu(II) to metallic Cu. The obtained Cu nanoparticles are electrochemically addressable and exhibit promising electrocatalytic activity for CO2 reduction in an aqueous electrolyte.

Kung, Chung-Wei↗
DOE OSTI2020

Thermal Activation of a Copper-Loaded Covalent Organic Framework for Near-Ambient Temperature Hydrogen Storage and Delivery

Copper(II) formate is efficiently incorporated into the pores of a 2D imine-based covalent organic framework (COF) via coordination with the phenol and imine groups. The coordinated metal ion is then reduced to Cu(I) with a thermal treatment that evolves CO 2 . After loading with hydrogen gas, the majority of H 2 desorbs from the coordinatively saturated Cu(II) COF at temperatures < -100 degrees C. However, the activated Cu(I) COF retains adsorbed H 2 above room temperature. Adsorption/desorption of H 2 was highly reversible. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) strongly supports a molecular hydrogen interaction with Cu(I). A Kissinger analysis of variable ramp rate desorption experiments estimates the enthalpy of H 2 desorption from Cu(I) at 15 kJ mol -1 . The results represent an advance toward practical H 2 storage and delivery in a lightweight, stable, and highly versatile material.

08 HYDROGEN↗
DOE OSTI2024

Unraveling Interdiffusion Phenomena and the Role of Nanoscale Diffusion Barriers in the Copper–Gold System

Diffusion is one of the most fundamental concepts in materials science, playing a pivotal role in materials synthesis, forming, and degradation. Of particular importance is solid state interdiffusion of metals which defines the usable parameter space for material combinations in the form of alloys. This parameter space can be explored on the macroscopic scale by using diffusion couples. However, this method reaches its limit when going to low temperatures, small scales, and when testing ultrathin diffusion barriers. Therefore, this work transfers the principle of the diffusion couples to small scales by using core–shell nanowires and in situ heating. This allows us to delve into the interdiffusion dynamics of copper and gold, revealing the interplay between diffusion and the disorder–order phase transition. Our in situ TEM experiments in combination with chemical mapping reveal the interdiffusion coefficients of Cu and Au at low temperatures and highlight the impact of ordering processes on the diffusion behavior. The formation of ordered domains within the solid-solution is examined using high-resolution imaging and nanodiffraction including strain mapping. In addition, we examine the effectiveness of ultrathin Al 2 O 3 barrier layers to control interdiffusion of the diffusion couple. Our findings indicate that a 5 nm thick layer serves as an efficient diffusion barrier. Furthermore, this research provides valuable insights into the interdiffusion behavior of Cu and Au on the nanoscale, offering potential applications in the development of miniaturized integrated circuits and nanodevices.

alloys↗