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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Shapeshifting Nanocatalyst for CO2 Conversion

The conversion of CO2 into high-value chemicals through a photoreduction reaction in water is a promising route to reduce the dependence on fossil fuels. Enhancing selectivity toward hydrocarbons or alcohols can be achieved by Ag-Cu alloys. However, the stabilized surface state created by Ag-Cu interactions is still poorly understood. In this work, multi-modal in situ X-ray experiments reveals underlying mechanisms and the evolution of Ag-Cu nanoparticles under CO2 reduction reaction (CO2RR) conditions. Both morphological and chemical changes of Ag and Cu species induced by diffusion mechanics are tracked during nanocatalyst operation. The initial spheroid Ag-Cu nanoparticles are composed of a Cu-rich shell and Ag-rich core. The reduction treatment promotes Ag migration toward the surface. During photocatalytic CO2 reduction reaction, Cu atoms migrate back to the surface, forming Ag-Cu-O species. The study observes the surface oxidation of Cu(0) to Cu+ and the presence of Ag at the sub-surface region. Furthermore, nanoparticles change their shape, decreasing their specific surface area, driven by Cu diffusion during the CO2 photoreduction reaction. The results provide invaluable insights into the dynamic restructuring of the catalyst under reaction conditions and into the active species responsible for CO2 conversion.

CO2 reduction reaction↗
DOE OSTI2022

Shape-Controlled Synthesis of Copper Nanocrystals for Plasmonic, Biomedical, and Electrocatalytic Applications

As a metal that can occur in nature in the elemental form, copper (Cu) has been used by humans since ca. 8000 BC. With most properties matching those of Ag and Au, Cu has played a more significant role in commercial applications owing to its much higher (the 25th among all elements) abundance in Earth’s crust and thus more affordable price. In addition to its common use as a conductor of heat and electricity, it is a constituent of various metal alloys for hardware, coins, strain gauges, and thermocouples. Bulk Cu is also widely utilized as a building material. When downsized to the nanoscale, Cu and Cu-based structures have found widespread use in applications ranging from electronics to optoelectronics, plasmonics, catalysis, sensing, and biomedicine. Besides Ag and Au, for example, Cu is another metal known for its localized surface plasmon resonance (LSPR) in the visible and near-infrared regions when prepared as nanocrystals. As a potential replacement for indium–tin oxide (ITO) films, polymer coatings containing Cu nanowires are strong candidates for the fabrication of transparent and flexible electrodes key to touchscreen display and related applications. The commercial catalysts for water–gas shift and gas detoxification reactions are also based on Cu nanoparticles. Most recently, Cu nanocrystals have attracted considerable interest for their superior selectivity toward hydrocarbons and multicarbon species during the electrochemical reduction of CO 2 . The success of all these applications critically depends on our ability to control the shape and surface structure of the nanocrystals. Relative to Ag and Au, it is more challenging to generate Cu-based nanocrystals using colloidal methods due to its lower reduction potential and greater vulnerability to oxidation. Here, in this account, we discuss recent progress in the colloidal synthesis of Cu nanocrystals with controlled shapes for plasmonic, biomedical, and catalytic applications. With glucose serving as a reducing agent, Cu nanocrystals bearing a twinned or single-crystal structure can be synthesized using an aqueous system with the assistance of hexadecylamine (HDA). In this synthetic protocol, HDA not only passivates the surface to protect the nanocrystals from oxidation but also manipulates the reduction kinetics of Cu(II) precursor through coordination and an increase of solution pH. Typical products include nanocubes and penta-twinned nanowires whose surfaces are dominated by {100} facets. When seeds produced either in situ or ex situ are introduced, Cu-based nanocrystals featuring a singly twinned, core–shell, or Janus structure can be readily synthesized. Aside from segmented structures, Cu-based alloys with various noble metals can be synthesized through coreduction or a galvanic replacement reaction with preformed Cu nanocrystals. By controlling the size and/or shape of Cu nanocrystals, their LSPR peaks can be tuned into the near-infrared region, making them promising candidates for optical imaging contrast enhancement and photothermal treatment. The inclusion of the 64 Cu isotope makes them immediately useful in positron emission tomography and thus image-guided therapy. The surface structure, elemental distribution, and valence state of Cu-based nanocrystals can all be tailored to augment their electrocatalytic performance. It is hoped that this Account will inspire more studies into the development of rational methods capable of producing Cu-based nanocrystals with diverse and well-controlled shapes, internal structures, and compositions for a broader range of applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys

Ethanol dehydrogenation presents a promising pathway towards the production of acetaldehyde, a valuable building block in chemicals production. Under non-oxidative conditions, the reaction is facilitated by supported Cu nanoparticles which afford reasonable activity and high selectivity. The stability issues associated with Cu nanoparticle sintering can be addressed by the addition of small amounts of Ni, which further boost reactivity while retaining selectivity. Despite the promise of NiCu single-atom alloys for non-oxidative ethanol dehydrogenation, little is known about the role of each component and the pathway of this mechanistically complex process. Herein, kinetic investigations from reactor tests identify C-H bond scission as the rate limiting step, while 1-hydroxyethyl is detected as the intermediate via IR spectroscopy. Temperature program desorption studies are employed to examine the effect of Ni coverage and to demonstrate that Ni atoms activate ethanol selectively at lower temperatures, resulting in higher acetaldehyde yield than pure Cu. Temperature program desorption experiments also reveal the spillover of intermediates from the Ni atom to neighboring Cu sites as a relevant step in the reaction pathway. Density functional theory calculations are used to investigate the 2 reaction energetics and to confirm that C-H bond scission is the initial reaction step, while a clear effect of H 2 partial pressure on the reaction pathway is realized. Further, counter to the expected behavior that all reaction steps take place on the Ni atoms, our degree of rate control analysis reveals that a mechanism involving spillover of the 1-hydroxyethyl intermediate from the Ni atom to the Cu surface, where it will dehydrogenate further, is more likely. Furthermore, our combined kinetic, spectroscopic, and theoretical approach sheds light on this complex reaction mechanism and represents a promising method for the understanding and designing of highly active, selective, and stable single-atom alloys for other multistep catalytic processes.

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

Dry Printing Pure Copper with High Conductivity and Adhesion for Flexible Electronics

Additive manufacturing of functional devices on various rigid and flexible substrates is rising rapidly due to their design flexibility, rapid manufacturing, and lower cost. Current printing technologies are ink-based and focused on printing silver (Ag) as conductive lines due to its matured ink formulation process, low sintering temperature, ease of printing, and low oxidation rate. However, Ag is the 68th most abundant element on Earth, while copper (Cu) is the 25th, making it much cheaper (>100×) while having a comparable conductivity to Ag. Therefore, printing Cu has become technologically and economically more attractive than Ag. Nevertheless, Cu printing is still a significant challenge in ink-based printing methods due to the higher sintering temperature relative to the glass-transition temperature of most flexible substrates, the higher oxidation rate, the challenging ink formulation process, and ink stability concerns. Here, we demonstrate printing highly conductive Cu on flexible polyimide substrates using a dry printing technique. Cu nanoparticles (~3–30 nm) are generated by on-demand laser ablation of a solid Cu target inside the printer head and under argon background gas. These Cu nanoparticles are then transported through a nozzle and onto the substrate, where they are laser-sintered in real time. The argon gas plays three critical roles in laser plume condensation for nanoparticle generation, transport, and sheath gas to avoid oxidation during sintering. The sintered nanoparticles thus show high electrical conductivity and mechanical stability under static and cyclic tests. Our dry printing technique can potentially revolutionize how electronic devices and sensors are additively manufactured for earth and space applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Biomineralization of Cu 2 S Nanoparticles by Geobacter sulfurreducens

Biomineralization of Cu has been shown to control contaminant dynamics and transport in soils. However, very little is known about the role that subsurface microorganisms may play in the biogeochemical cycling of Cu. In this study, we investigate the bioreduction of Cu(II) by the subsurface metal-reducing bacterium Geobacter sulfurreducens. Rapid removal of Cu from solution was observed in cell suspensions of G. sulfurreducens when Cu(II) was supplied, while transmission electron microscopy (TEM) analyses showed the formation of electron-dense nanoparticles associated with the cell surface. Energy-dispersive X-ray spectroscopy (EDX) point analysis and EDX spectrum image maps revealed that the nanoparticles are rich in both Cu and S. This finding was confirmed by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses, which identified the nanoparticles as Cu 2 S. Biomineralization of Cu x S nanoparticles in soils has been reported to enhance the colloidal transport of a number of contaminants, including Pb, Cd, and Hg. However, formation of these Cu x S nanoparticles has only been observed under sulfate-reducing conditions and could not be repeated using isolates of implicated organisms. As G. sulfurreducens is unable to respire sulfate, and no reducible sulfur was supplied to the cells, these data suggest a novel mechanism for the biomineralization of Cu 2 S under anoxic conditions. The implications of these findings for the biogeochemical cycling of Cu and other metals as well as the green production of Cu catalysts are discussed.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Liquid–Solid Mixtures of Ga Metal Infused with Cu Microparticles and Nanoparticles for Microscale and Nanoscale Patterning of Solid Metals at Room Temperature

This paper demonstrates and characterizes a simple ink for nanopatterning of solid metallic structures under ambient conditions by taking advantage of the low melting point of gallium and its affinity to form intermetallics with other metals. Bare copper micro- and nanoparticles readily mix with liquid gallium near room temperature to form a paste that ultimately amalgamates into a dense solid when mixed at the appropriate concentration ratios. The paste has sufficient shelf life that can be extruded from a nozzle at modest temperatures to form solid three-dimensional (3D) shapes. Additionally, the paste can be molded at room temperature to replicate feature sizes ranging from a few millimeters down to hundreds of nanometers. In situ X-ray diffraction (XRD) and thermo-mechanical analysis (TMA) data show gallium and copper readily interdiffuse to form the thermodynamically expected intermetallic phase. We describe the capabilities and limitations of a simple way to pattern solid metals in an additive fashion (syringe-based extrusion) and with high resolution (molding) at or near room temperature. Here, the use of a paste that solidifies provides a novel route for 3D printing of solid metals at ambient temperatures as well as the creation of micro- and nanostructured metallic surfaces that may be useful for optics, non-wetting surfaces, or electronic microcomponents.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Photoreversible Color-Switching Cu-Doped TiO2 Nanoparticles for High-Contrast Rewritable Printing

Light-printable rewritable paper that can be used multiple times has attracted extensive attention because of its potential benefits in reducing environmental pollution and energy consumption. Developing rewritable paper with high black-to-colorless contrast, lasting legibility, and a fast response is fascinating but challenging. Here, we integrate the redox chemistry of Cu2+ ions into photoreductive TiO2 nanoparticles to produce Cu-doped TiO2 nanoparticles capable of highly photoreversible switching between colorless and black with excellent contrast and color stability. Incorporating such nanoparticles into hydroxyethyl cellulose produces a rewritable paper with the same appearance as that of conventional paper. More importantly, it demonstrates great features promising for practical applications, including high black-to-colorless contrast, fast light-printing (<20 s), long legible time (>3 days), high reversibility (>50 cycles), high resolution (90 μm), and large scale (A4 size) applicability.

Wang, Wenshou↗
DOE OSTI2023

Cascade electrocatalysis via AgCu single-atom alloy and Ag nanoparticles in CO 2 electroreduction toward multicarbon products

Electrocatalytic CO 2 reduction into value-added multicarbon products offers a means to close the anthropogenic carbon cycle using renewable electricity. However, the unsatisfactory catalytic selectivity for multicarbon products severely hinders the practical application of this technology. In this paper, we report a cascade AgCu single-atom and nanoparticle electrocatalyst, in which Ag nanoparticles produce CO and AgCu single-atom alloys promote C-C coupling kinetics. As a result, a Faradaic efficiency (FE) of 94 ± 4% toward multicarbon products is achieved with the as-prepared AgCu single-atom and nanoparticle catalyst under ~720 mA cm -2 working current density at -0.65 V in a flow cell with alkaline electrolyte. Density functional theory calculations further demonstrate that the high multicarbon product selectivity results from cooperation between AgCu single-atom alloys and Ag nanoparticles, wherein the Ag single-atom doping of Cu nanoparticles increases the adsorption energy of *CO on Cu sites due to the asymmetric bonding of the Cu atom to the adjacent Ag atom with a compressive strain.

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

Energetics of Cu Adsorption on and Adhesion to Rutile-TiO 2 (100) Studied by Cu Vapor Adsorption Calorimetry

The heat of adsorption of Cu vapor versus coverage was measured on rutile-TiO 2 (100) at 300 and 100 K using single-crystal adsorption calorimetry. At these conditions, Cu nanoparticles nucleate and then grow larger. The average Cu particle size versus Cu coverage was measured using He + low-energy ion scattering spectroscopy. These data were analyzed with the recently introduced spherical cap model (SCM) to provide the heat of Cu adsorption and Cu chemical potential versus Cu particle size, as well as the contact angle (67°) and adhesion energy (2.50 J/m 2 ) at the Cu particle/rutile-TiO 2 (100) interface. The hemispherical cap model (HCM) was used to model the data first, and then those HCM results were converted to the more accurate SCM results using a recently published mathematical approximation whose high accuracy was validated here. Furthermore, the adhesion energy of Cu on rutile-TiO 2 (100) measured here is compared to prior values for Ag and Au on rutile-TiO 2 (100), showing a nearly proportional increase in adhesion energy with metal oxophilicity (per unit area).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The intrinsic electrochemical behavior of layered Cu 2 WSe 4 nanoparticles

Nanoplates of Cu 2 WSe 4 (~50 nm) were synthesized via a hot-injection method by one-pot selenation of WCl 6 and Cu(acac) 2 . This synthetic route provided another perspective towards the intrinsic electrochemical properties of Cu 2 MSe 4 (M = Mo or W), where their nanoparticles were previously synthesized via a metathesis route. In conclusion, cations-dependent cathodic events and surface activation anodic events were identified by cyclic voltammetry in acetonitrile.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2026

Controlling Exsolution Dynamics in High‐Entropy Oxides for Highly Active and Selective Acetylene Semi‐Hydrogenation

Exsolution-derived catalysts feature robust metal–support interactions that enhance catalytic performance; yet achieving precise control over exsolution dynamics in multicomponent oxides remains challenging. In this study, we demonstrate that exsolution behavior in high-entropy oxides (HEOs) can be rationally tuned through coupled lattice- and valence-engineering to create a highly active and selective catalyst for acetylene semi-hydrogenation. Incorporation of Li + into a rock salt-structured HEO (LiNiMgCuZnCoO x and LiHEO) induces local lattice distortion, generates oxygen vacancies, and partially oxidizes Co sites from Co 2+ to Co 3+ , collectively modulating local charge redistribution. This strategy enables facilitated Cu nanoparticle exsolution and alters the exsolution sequence from Cu 0 > Ni 0 > Co 0 in pristine HEO to Cu 0 > Co 0 > Ni 0 in the LiHEO. The resulting catalyst via controlled exsolution exhibits superior activity and ethylene selectivity, outperforming state-of-the-art transition metal systems. This work establishes entropy-enabled lattice and valence engineering as a facile route to programmable exsolution for enhanced catalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effect of the magnetic field on the size of nanoparticles obtained by ablation of a cobalt – copper target in a liquid

Co – Cu nanoparticles were obtained by pulsed laser ablation in a liquid medium in a constant magnetic field. The organic solvent, hexane, served as a liquid medium. The influence of the magnetic field on the formation of nanoparticles was studied. It is shown that the magnetic field leads to a decrease in the size distribution width of the resulting nanoparticles. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Heterogeneous photo-Fenton-like degradation of emerging pharmaceutical contaminants in wastewater using Cu-doped MgO nanoparticles

In this study, a facile thermal decomposition method was utilized to synthesize Cu-doped MgO nanoparticles possessing mesoporosity. These mesoporous Cu doped MgO nanoparticles were shown to be efficient photo-Fenton-like catalysts for the degradation of emerging pharmaceutical contaminants in wastewater and were able to completely oxidize salicylic acid within 1 hour under optimized conditions. Tetracycline was shown to be converted to other intermediates with a large portion of it undergoing full mineralization. Batch experiments were conducted to demonstrate the effects of Cu loading on MgO, overall catalyst loading, and H 2 O 2 concentration on the salicylic acid and tetracycline conversion and rate constants. Quenching experiments revealed that both •OH radicals or HO 2 •/•O 2 - radicals were involved in the reaction, with the latter showing a higher contribution. The surface dissolution of MgO was shown to facilitate a high pH environment which completely prevented Cu from leaching out of the catalyst while retaining high activity. The catalyst reusability was shown to be satisfactory with high activity and conversion being preserved over five cycles.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2022

Dynamical Change of Valence States and Structure in NiCu 3 Nanoparticles during Redox Cycling

Alloyed materials are promising candidates to improve catalytic processes. Ni–Cu nanoparticles are used for various reactions, including processes with biomass-derived components. However, dynamical restructuring effects alter the catalytic properties and can deactivate the sample. To understand these structural modifications, a multimodal investigation of NiCu 3 /C was performed to determine compositional and morphological changes during a redox cycle to simulate reduction and oxidation of the catalyst during reaction. We exploit a novel correlative, multimodal approach that combines in situ X-ray absorption spectroscopy (XAS) and in situ scanning transmission electron microscopy and electron energy-loss spectroscopy (STEM-EELS) to describe changes that occur in the sample in realistic conditions. In the fresh sample, there are two morphologies present: core–shell and hollow. Segregation of Cu was observed in both types of particles after synthesis, with Cu being more oxidized in the hollow structures. Upon reduction for 2 h under H 2 at 400 °C, the Cu was reduced, although segregation of Cu and Ni was still observed. Subsequent exposure to O 2 at 400 °C led to a strong reoxidation of Cu with the formation of hollow particles with compositional heterogeneities. The oxidation of metals and segregation phenomena can be related to known catalytic properties of NiCu 3 /C particles, especially regarding the hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗