Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Cu”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Self-Assembled Bolaamphiphile-Based Organic Nanotubes as Efficient Cu(II) Ion Adsorbents

Self-assembled organic nanotubes (ONTs) have been actively examined for various applications such as chemical separations and catalysis owing to their well-defined tubular nanostructures with distinct chemical environments at the wall and internal/external surfaces. Adsorption of heavy metal ions onto ONTs plays an essential role in many of these applications, but it has rarely been assessed quantitatively. Herein, we investigated interactions between Cu 2+ and single-/quadruple-wall bolaamphiphile-based ONTs having inner carboxyl groups with different inner diameters, COOH-ONT 10nm and COOH-ONT 20nm . We first examined the effects of Cu 2+ on their nanotubular structures using SAXS, STEM, and AFM. COOH-ONT 10nm was stable in aqueous Cu 2+ solution in contrast to COOH-ONT 20nm owing to the presence of polyglycine-II-type hydrogen bonding networks within its wall. Subsequently, we studied the Cu 2+ adsorption behavior of COOH-ONT 10nm by monitoring the concentration of unbound Cu 2+ using linear sweep anodic stripping voltammetry. The Cu 2+ adsorption was quick, attributable to efficient Cu 2+ partitioning through the open ends of the ONT, followed by fast Cu 2+ diffusion in the uniform, relatively large nanochannel. More importantly, the Cu 2+ adsorption capacity and affinity of COOH-ONT 10nm were measured at different pH using the Langmuir adsorption model. The adsorption capacity was similar at the pH range examined, showing the participation of approximately 25% of the inner carboxyl groups in the adsorption. The adsorption affinity increased with pH, indicating the essential role of the deprotonated carboxyl groups in the Cu 2+ adsorption. Most interestingly, the Langmuir adsorption constant was significantly higher than those of previously reported synthetic adsorbents and planar monolayer based on carboxyl binding sites. The high Cu 2+ affinity of the ONT was attributable to the highly dense binding sites on the well-defined nanoscale concave structure of the inner channel. Furthermore, these results provide a valuable guideline to designing self-assembled nanomaterials for efficient chemical separations, detection, and catalysis.

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

Solution-Phase Growth of Cu Nanowires with Aspect Ratios Greater Than 1000: Multiscale Theory

Penta-twinned metal nanowires are finding widespread application in existing and emerging technologies. However, little is known about their growth mechanisms. Here, we probe the origins of chloride- and alkylamine-mediated, solution-phase growth of penta-twinned Cu nanowires from first principles using multi-scale theory. Using quantum density functional theory (DFT) calculations, we characterize the binding and surface diffusion of Cu atoms on chlorine-covered Cu(100) and Cu(111) surfaces. We find stronger binding and slower diffusion of Cu atoms on chlorinated Cu(111) than on chlorinated Cu(100) – a reversal of the trend for bare Cu surfaces. We also probe inter-facet diffusion and find this proceeds faster from Cu(100) to Cu(111) than the reverse. Using the DFT rates for hopping between individual sites at Ångstrom scales, we calculate coarse-grained, inter-facet rates for nanowires of various lengths – up to hundreds of μm – and diameters in the 10-nm range. We predict nanowires with aspect ratios around 100 based on surface diffusion, alone. We also account for the influence of a self-assembled alkylamine layer that covers most of the {100} facets, but is absent or thin and disordered on the {111} facets and in an “end zone” near the {100}-{111} boundary. With an end zone, we predict a wide range of nanowire aspect ratios in the experimental ranges. Our work reveals the mechanisms by which a halide – chloride – promotes the growth of high-aspect-ratio nanowires.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Transmission electron microscopy of the rapid solidification microstructure evolution and solidification interface velocity determination in hypereutectic Al-20at.%Cu after laser melting

The evolution of rapid solidification (RS) microstructure and solidification interface velocity has been studied experimentally by in-situ transmission electron microscopy and postmortem characterization for hypereutectic Al-20at.%Cu (37 wt.%Cu) after laser melting. Four morphologically distinct regions formed via growth modes changing from θ-Al 2 Cu phase dendrites to eutectic cell growth, possibly α-Al dendrite growth (α-cell), banded growth, and α-Al plane front growth. Tendency for faceting and low capacity for solute trapping limited the θ-phase dendrite growth to solidification interface velocity v < 0.07 m/s. Consequently, formation of pro-eutectic micro-constituent was suppressed, and RS microstructure formation was dominated by eutectic, α-cell, and banded morphology grains for the Al-20at.%Cu alloy. Eutectic growth operated for interface velocity of 0.1 m/s ≤ v < 0.3 m/s, with a transition from regular lamellar, 2-λ and 1-λ mode to a dense irregular morphology dominated by α-phase at v = 0.3 m/s. Interface temperature calculations indicated feasibility of α-cell growth mode for 0.3 m/s ≤ v < 0.7 m/s. Banded growth occurred for 0.7 m/s ≤ v < 1.3 m/s. Plane front α-phase growth was evident for interface velocities v ≥ 1.3 m/s. Previous work on rapid solidification microstructure development in hypereutectic Al-Cu alloys reported a regime of α-cell growth subsequently to eutectic and prior to transition to banded growth for Al-19at.%Cu (36 wt.%Cu), while for Al-22at.%Cu (40 wt.%Cu) eutectic growth transitioned directly to α-plane front growth without emergence of a banded regime. Finally, based on the current study the disappearance of the banded growth regime occurs for a composition larger than 20at.%Cu.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Remarkable enhancement in thermal conductivity of stainless-steel leveraging metal composite via laser powder bed fusion: 316L-Cu composite

This work aimed to significantly enhance the thermal conductivity of the SS matrix by fabricating a metal composite SS-Cu system utilizing a laser powder bed fusion process. The impact of process parameters on the microstructure of SS-Cu samples is investigated. Here, the processing and post-processing factors that influence the effective thermal conductivity of the metal composite SS-Cu system are discussed. Then, the effective thermal conductivity and mechanical properties of the SS-Cu composite are measured at room temperature and operating temperature of 300 °C. The optimized laser powder bed fusion parameters led to low Marangoni convection, high cooling rate, greater macro-segregation, and higher thermal conductivity values albeit at the cost of ductility in SS-Cu metal composite likely due to the presence of the unmelted powder particles. As-printed SS-60 vol % Cu and annealed SS-60 vol % Cu had 2.5X and 6.6X thermal conductivity enhancement, respectively. During annealing, phase separation, partial melting of Cu, and formation of a continuous network of Cu surrounding SS play a key role in enhancing the thermal conductivity of the SS-Cu metal composite structure.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Methanol Partial Oxidation on Cu(111) and PtCu(111) Single-Atom Alloy Surfaces: Effect of Surface Oxygen Coverage on Selectivity

The selective oxidation of methanol to formaldehyde on Cu surfaces is an important and well-studied reaction. However, a systematic analysis of product selectivity as a function of oxygen coverage on Cu(111) and Cu-based single-atom alloys (SAAs) has not been previously reported. In this work, we present a comprehensive investigation of deuterated methanol (CD 3 OH) partial oxidation on Cu(111) and 1% PtCu(111) SAA surfaces as a function of preadsorbed oxygen coverage. Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) reveal that isolated Pt atoms inhibit the initial surface oxidation of Cu(111) under low oxygen exposures. Despite this difference in oxidation kinetics, the product selectivity remains largely unaffected: on both Cu(111) and PtCu(111), formaldehyde (CD 2 O) is the predominant partial oxidation product over a broad range of oxygen coverages. The selectivity toward formaldehyde peaks at intermediate oxygen coverages (∼0.3 monolayers, ML), indicating the existence of an optimal oxygen loading for partial oxidation. Notably, the similar product selectivities on Cu(111) and PtCu(111) over a range of surface oxygen coverage indicate that Pt single atoms do not significantly alter the reaction pathway or shift the optimal oxygen coverage for formaldehyde formation. Control experiments confirm that Cu(111) is unreactive toward methanol in the absence of oxygen, while PtCu(111) surfaces produce a small amount of formaldehyde even when oxygen is not preadsorbed, indicating that isolated Pt atoms facilitate O−H activation at below 150 K, leading to H 2 desorption, followed by C−D activation at higher temperatures (∼350 K). Density functional theory (DFT)-based calculations show that Pt atoms increase the O 2 dissociation barrier relative to Cu(111), consistent with the observed inhibition of oxidation at low exposures. Overall, this work provides the first detailed selectivity map for methanol oxidation on oxidized Cu(111) and PtCu(111) SAA surfaces. By linking classical mechanistic insights such as methoxy- and formate-mediated pathways with single-atom alloy catalyst design, this work demonstrates that while Pt substitution modulates the oxidation kinetics and oxygen binding, the overall selectivity toward formaldehyde is governed primarily by oxygen coverage. These findings underscore the potential of isolated dopants to tune surface oxidation behavior without compromising the intrinsic partial oxidation selectivity of copper-based catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2023

MXene Nanosheets Functionalized with Cu Atoms for Urea Adsorption in Aqueous Media

Ti 3 C 2 T x MXene is an emerging family of two-dimensional materials, and because of its large specific surface area, it has potential for many applications. Herein, a new application using Cu-doped MILD (minimally intensive layer delamination) synthesized Ti 3 C 2 T x MXene for urea removal is demonstrated. The doping of Cu on MXene results in an increase in its affinity for urea adsorption as compared to the pristine MILD synthesized MXene due to the formation of the Cu–urea complex. Previous computational studies have shown that the adsorption energies of urea on the MXene surface can be improved in the presence of Cu. The valence state of Cu in the doped MILD synthesized MXene, which binds on to the surface via Ti–O–Cu linkage, is between 0 and +1 as verified by XAS and XPS. As the optimal urea adsorption occurs on Cu as a single atom site, an increase in Cu doping on MXene does not increase urea removal due to Cu agglomeration. Furthermore, looking at the adsorption behaviour, it seems that Cu-doped MXene follows the monolayer adsorption on homogenous surface model.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Heterogeneous and Framework-Bound Copper Species Contribute to Catalytic Partial Methane Oxidation in Cu–Chabazite Zeolites

The relationship between continuous partial methane oxidation (PMO) rates and Cu site speciation in Cu-CHA zeolite catalysts is explored through differential rate measurements across a series of samples of varying compositions combined with density functional theory, first-principles thermodynamics, and statistical models that characterize Cu speciation. Under continuous PMO conditions (573 K, 0.07 kPa O 2 , 3 kPa H 2 O), Cu ions are shown to anchor to the CHA framework in both monomeric (Z 2 Cu and Z 2 CuH 2 O) and dimeric (O- and OH-bridged Cu) forms that are sensitive to the identity of the local framework anchoring site. Consequently, across the studied compositional range, Cu-CHA catalysts are predicted to contain a mixture of monomeric and dimeric Cu sites. Cu-normalized CH 3 OH formation rates extrapolated to zero conversion reflect contributions from multiple site types. Predicted CH 3 OH formation rates indicate that the Cu site reactivity toward CH 4 is influenced by zeolite composition and is likely limited by the reduction half-cycle.

03 NATURAL GAS↗
DOE OSTI2020

Metal-ion-controlled growth and nanoindentation response of 3D, bicontinuous Cu–Fe thin films

Bicontinuous, nanocomposite thin film morphologies depend largely on the deposition conditions applied during physical vapor deposition. With the introduction of high power impulse magnetron sputtering (HiPIMS), the range of potential morphologies achieved during deposition has been increased. In this work, we compare the deposition outcomes between traditional direct-current magnetron sputtering (DCMS) and HiPIMS for a thin film co deposit of Cu and Fe. Modular control of the columnarity, porosity and roughness was achieved by varying the Cu and Fe metal ion currents during deposition. The directionality of the nanostructured phase-separated morphology was also controlled as the ion current increased. At zero ion current for both Cu and Fe sputtered species during DCMS, the film exhibited lateral concentration modulations of Cu and Fe. The directionality of the Cu- and Fe-rich phases shifted to vertical concentration modulations at low ion currents of I Fe = 1A and I Cu = 0:1A and to lateral concentration modulations at relatively moderate ion currents of I Fe = 5A and I Cu = 2A: At high ion currents of I Fe = 18A and I Cu = 2A; a more randomized phase domain structure was observed on the nanoscale. This structural shift is rationalized using an interdiffusion model. Here, the role of different kinds of phase separated morphologies, achieved during DCMS deposition, on the mechanical properties has also been studied. Results indicated increase in hardness, indentation modulus and flow strength values with the increase in indentation strain rates. Bicontinuous Cu-Fe nanocomposites are found to be stronger than multilayer Cu-Fe samples.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Characterization of electromigration-induced short-range stress development in Al(0.25 at. % Cu) conductor line

Scanning x-ray microbeam topography and fluorescence experiments were conducted in situ to study the electromigration behavior of a 0.5 μm thick, 10 μm wide, and 200 μm long Al(0.25 at. % Cu) conductor line with 1.5 μm-thick SiO2 passivation on a single crystal Si substrate. The strain sensitivity of x-ray topography measurement allowed detailed examination of the electromigration-induced stress distribution and evolution in the conductor line in response to the depletion of Cu solute early in the electromigration process. Upon electromigration at 0.4 MA/cm2 and 303 °C, a short-range stress gradient was quickly induced by Al migration in the Cu-depleted cathode region to counteract further Al flow. The stress gradient was fully developed during the 5.3 h incubation time, extending over the critical Blech length of about 66 μm from the cathode end. Plastic deformation then occurred at the downstream end of the Cu-depleted region. The preferential electromigration of Cu did not cause detectable stress change outside the Cu-depleted region, except for the significant stress development from the Al2Cu precipitation at the anode end which appeared to initiate the fracture in the passivation. Preliminary finite difference modeling was undertaken to simulate the experimental observations, from which important parameters dictating electromigration in Al(Cu) line were extracted: an apparent effective valence of −5.6 and −1.9 for Cu and Al in Al(Cu), respectively, and a critical Cu concentration of 0.16 at. % above which Al grain boundary diffusion is effectively blocked.

Physics↗
DOE OSTI2021

Imaging and dosimetric characteristics of 67 Cu

In recent years the use of beta-emitting radiopharmaceuticals for cancer therapy has expanded rapidly following development of therapeutics for neuroendocrine tumors, prostate cancer, and other oncologic malignancies. One emerging beta-emitting radioisotope of interest for therapy is 67 Cu (t 1/2 : 2.6 d) due to its chemical equivalency with the widely-established positron-emitting isotope 64 Cu (t 1/2 : 12.7 h). Here we evaluate both the imaging and dosimetric characteristics of 67 Cu, as well as producing the first report of SPECT/CT imaging using 67 Cu. To this end, 67 Cu was produced by photon-induced reactions on isotopically-enriched 68 Zn at the Low-Energy Accelerator Facility (LEAF) of Argonne National Laboratory, followed by bulk separation of metallic 68 Zn by sublimation and radiochemical purification by column chromatography. Gamma spectrometry was performed by efficiency-calibrated high-purity germanium (HPGe) analysis to verify absolute activity calibration and establish radionuclidic purity. Absolute activity measurements corroborated manufacturer-recommended dose-calibrator settings and no radionuclidic impurities were observed. Using the Clinical Trials Network anthropomorphic chest phantom, SPECT/CT images were acquired. Medium Energy (ME) SPECT collimation was found to provide the best image quality from the primary 185 keV gamma emission of 67 Cu. Reconstructed images of 67 Cu were similar in quality to images acquired using 177 Lu. Recovery coefficients were calculated and compared against quantitative images of 99m Tc, 177 Lu, and 64 Cu within the same anthropomorphic chest phantom. Production and clinical imaging of 67 Cu appears feasible, and future studies investigating the therapeutic efficacy of 67 Cu-based radiopharmaceuticals are warranted.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2023

Metallization and spin fluctuations in Cu-doped lead apatite

An electronic structure and magnetic properties analysis of the recently proposed Cu-doped lead apatite is performed. Here, we show that electronic structures of differently Cu-substituted structures are characterized by localized molecular Cu-O bands at or near the Fermi level. The Cu substitutions can happen at both Pb1 and Pb2 sites, leading to metallic and semiconducting systems differently. The electronic systems in these bands are highly unstable magnetically and form clusters of rigidly ferromagnetically coupled magnetic moments on Cu and neighboring oxygen atoms with a total moment of about 1µ B . The ground state of uniformly Cu-doped lead apatite appears to be magnetic and semiconducting. The nonuniform distribution of two Cu atoms at the nearest Pb2 sites leads to an antiferromagnetic semiconducting state with formation energy close to uniformly distributed Cu configurations. The inclusion of quantum spin fluctuations confirms the stability of magnetic Cu-O clusters. Our calculations revealed the absence of the long-range magnetic order between uniformly distributed Cu-O clusters, creating the spin glass type of system.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The mitochondrial Cu + transporter PiC2 (SLC25A3) is a target of MTF1 and contributes to the development of skeletal muscle in vitro

The loading of copper (Cu) into cytochrome c oxidase (COX) in mitochondria is essential for energy production in cells. Extensive studies have been performed to characterize mitochondrial cuproenzymes that contribute to the metallation of COX, such as Sco1, Sco2, and Cox17. However, limited information is available on the upstream mechanism of Cu transport and delivery to mitochondria, especially through Cu-impermeable membranes, in mammalian cells. The mitochondrial phosphate transporter SLC25A3, also known as PiC2, binds Cu + and transports the ion through these membranes in eukaryotic cells, ultimately aiding in the metallation of COX. We used the well-established differentiation model of primary myoblasts derived from mouse satellite cells, wherein Cu availability is necessary for growth and maturation, and showed that PiC2 is a target of MTF1, and its expression is both induced during myogenesis and favored by Cu supplementation. PiC2 deletion using CRISPR/Cas9 showed that the transporter is required for proliferation and differentiation of primary myoblasts, as both processes are delayed upon PiC2 knock-out. The effects of PiC2 deletion were rescued by the addition of Cu to the growth medium, implying the deleterious effects of PiC2 knockout in myoblasts may be in part due to a failure to deliver sufficient Cu to the mitochondria, which can be compensated by other mitochondrial cuproproteins. Co-localization and co-immunoprecipitation of PiC2 and COX also suggest that PiC2 may participate upstream in the copper delivery chain into COX, as verified by in vitro Cu + -transfer experiments. These data indicate an important role for PiC2 in both the delivery of Cu to the mitochondria and COX, favoring the differentiation of primary myoblasts.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Composition-Dependent Reconstructions of Titanium Oxide Clusters and Cu(111) Support via Cluster-Adatom Interactions

Mass-selected cluster deposition and scanning tunneling microscopy (STM) were used to investigate the surface structure and thermal stability of Ti 3 O y (y = 5, 6) clusters on a Cu(111) surface. STM imaging shows that the substoichiometric Ti 3 O 5 clusters aggregate into large dendritic assemblies at step edges, while the stoichiometric Ti 3 O 6 clusters are highly dispersed as single or small groupings of clusters. Cluster deposition also results in extensive reconstruction of the Cu(111) surface. The Ti 3 O 5 /Cu(111) surface exhibits one Cu-layer deep pits that are ringed by cluster assemblies that nucleate and grow at the perimeter step edges. By comparison, the Ti 3 O 6 /Cu(111) surface consists of irregular step edges and small one Cu-layer islands that are decorated with clusters. The restructuring of the Cu(111) surface is attributed to strong Cu-cluster interactions that release Cu adatoms from the step edges. This mechanism is supported by density functional theory (DFT) calculations, which predict that the Cu adatom attachment to the clusters is energetically favorable. Annealing the surfaces at elevated temperatures (400-700 K) results in higher densities of irregular steps, pits and isolated Cu islands as well as increased cluster aggregation. In conclusion, this work highlights adatom-cluster interactions as another manifestation of strong cluster-support interactions that can significantly alter the nature of the oxide-metal interface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Materials Data on Cu(Bi4Ir)3 by Materials Project

IrCuBi6(IrBi3)2 crystallizes in the monoclinic Pm space group. The structure is one-dimensional and consists of one IrBi3 ribbon oriented in the (0, 1, 0) direction and one IrCuBi6 ribbon oriented in the (0, 1, 0) direction. In the IrBi3 ribbon, there are two inequivalent Ir sites. In the first Ir site, Ir is bonded in a 9-coordinate geometry to two equivalent Ir and seven Bi atoms. Both Ir–Ir bond lengths are 2.85 Å. There are a spread of Ir–Bi bond distances ranging from 2.80–2.98 Å. In the second Ir site, Ir is bonded in a 9-coordinate geometry to two equivalent Ir and seven Bi atoms. There are a spread of Ir–Bi bond distances ranging from 2.78–2.97 Å. There are six inequivalent Bi sites. In the first Bi site, Bi is bonded in a 3-coordinate geometry to three Ir atoms. In the second Bi site, Bi is bonded in a 3-coordinate geometry to three Ir atoms. In the third Bi site, Bi is bonded in a single-bond geometry to one Ir atom. In the fourth Bi site, Bi is bonded in a distorted single-bond geometry to one Ir atom. In the fifth Bi site, Bi is bonded in a 3-coordinate geometry to three Ir atoms. In the sixth Bi site, Bi is bonded in a 3-coordinate geometry to three Ir atoms. In the IrCuBi6 ribbon, Ir is bonded in a 9-coordinate geometry to two equivalent Cu and seven Bi atoms. Both Ir–Cu bond lengths are 2.74 Å. There are a spread of Ir–Bi bond distances ranging from 2.82–2.86 Å. Cu is bonded in a 9-coordinate geometry to two equivalent Ir and seven Bi atoms. There are a spread of Cu–Bi bond distances ranging from 2.81–3.01 Å. There are six inequivalent Bi sites. In the first Bi site, Bi is bonded in a 2-coordinate geometry to two equivalent Ir and one Cu atom. In the second Bi site, Bi is bonded in a 3-coordinate geometry to one Ir and two equivalent Cu atoms. In the third Bi site, Bi is bonded in a single-bond geometry to one Cu atom. In the fourth Bi site, Bi is bonded in a single-bond geometry to one Ir atom. In the fifth Bi site, Bi is bonded in a 3-coordinate geometry to two equivalent Ir and one Cu atom. In the sixth Bi site, Bi is bonded in a 3-coordinate geometry to one Ir and two equivalent Cu atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu-H: Different Rate-Limiting Steps as a Function of Electrophilicity

In this paper, we report mechanistic studies on the insertion reactions of [(NHC)Cu(H)] 2 complexes with carbonyl substrates by UV-vis and 1 H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X-ray crystallography. The results of these comprehensive studies show that the insertion of Cu-H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu-H monomer from Cu-H dimer for more electrophilic substrates and hydride transfer from a transient Cu-H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu-hemiacetalate and Cu-hemiaminalate moieties from the insertion of an ester and amide into the Cu-H bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A redox model for NO oxidation, NH 3 oxidation and high temperature standard SCR over Cu-SSZ-13

A kinetic model is developed to predict the influence of temperature and hydrothermal aging on the redox of active Cu sites under standard SCR, NO oxidation and NH 3 oxidation conditions over a practically relevant fully-formulated Cu-SSZ-13 catalyst. NO 2 /N 2 production during NO/NH 3 titration of Cu II sites is utilized to identify rate parameters associated with NO-only RHC (reduction half cycle) and NH 3 -only RHC respectively. Integral N 2 formation during subsequent NO + NH 3 titration is consistent with the production of one NO 2 per two CuII sites reduced during NO-only RHC and one N 2 per six Cu II sites reduced during NH 3 -only RHC. Decreased reduction of Cu II sites by NO/NH 3 upon hydrothermal aging, along with the production of one NO 2 per two CuII sites during NO-only RHC, is accordant with the involvement of proximal ZCuOH and oxygen-bridged dimeric Cu II sites. Oxidation of partially solvated and framework coordinated ZCu (Cu I ) sites occurs in presence of O 2 , does not produce N 2 and can lead to the consumption of Brønsted acid sites. A global OHC kinetic model is developed to predict transient and integral N 2 formation during exposure of CuI sites to a mixture of NO and O 2 . The resulting redox kinetic model quantitatively predicts NO and NH 3 consumption during isothermal transient response Cu redox (TRCR) protocols, along with temperature and age dependent steady-state standard SCR and oxidation conditions. The redox model presented in this work synthesizes recent kinetic, spectroscopic and computational findings to provide a foundational description of active site redox during standard SCR, NO oxidation and NH3 oxidation over Cu-SSZ-13.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Elucidating facet dependent electronic and electrochemical properties of Cu 2 O nanocrystals using AFM/SCEM and DFT

Cuprous oxide (Cu 2 O) has extensively been studied owing to its excellent optical, magnetic, and catalytic properties. Many of these properties are facet-dependent and have not been well elucidated. This work synthesized cubic, cuboctahedral, octahedral, and rhombic dodecahedral shaped Cu 2 O nanocrystals of ~300 nm in size to evaluate the facet-dependent electrochemical activities. Here, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were firstly used to reveal the average electrochemical activities at the ensemble level. Atomic force microscopy-scanning electrochemical microscopy (AFM-SECM) was further used to assess the electrochemical activities of different Cu 2 O nanocrystals at the facet level. Hexaammineruthenium (III) chloride ({Ru(NH 3 ) 6 }Cl 3 ) was employed as the probe molecules that reacted with four different Cu 2 O nanocrystals under —400mV and yielded ~300 pA current between the probing tip and the nanocrystal surface. The tip-current mapping results indicate that rhombic dodecahedral Cu 2 O exhibits higher electrocatalytic activity than other shaped Cu 2 O, due to the presence of dominant exposed facet of {110} as indicated by the relatively high tip current. Density-functional theory (DFT) calculations confirmed the facet dependence of local surface energy and electronic structure of Cu 2 O nanocrystals. Besides electrochemical activity, the surface work function and adsorptive properties were both observed to vary with the shape and dominant exposed facets of Cu 2 O. This study presented a unique experimental and computational chemistry approach to analyze surface electrochemical properties of Cu 2 O crystals at a crystalline facet level.

36 MATERIALS SCIENCE↗
DOE OSTI2025

From Micro-environments to Macroscopic Effects: How the Alkaline Hydrogen Evolution Reaction Drives Cu Cathodic Corrosion

Cathodic corrosion of copper (Cu) has posed a significant challenge for over a century, impeding various technological progresses such as electrochemical conversion of CO 2 (eCO 2 RR) into fuels and other value-added carbon products. Here, in this study, employing a combined Density Functional Theory (DFT) and kinetic Monte Carlo (kMC) simulation approach, we delve into the atomistic level mechanism driving this phenomenon in Cu. Our hypothesis posits the pivotal role of alkaline hydrogen evolution reaction (HER) in facilitating cathodic corrosion in Cu. We rigorously develop a pH-dependent hydroxide (OH) adsorption mechanism and calculate the equilibrium OH coverage (𝜃 OH ) at varying pH levels, the thermodynamic stability of subsurface oxygen (O sub ), as well as the Cu-vacancy mediated diffusion of subsurface oxygens (O sub ). Through comprehensive analysis, we establish correlation among various microenvironments, including oxygen diffusion in subsurface layers, pH-dependent OH adsorption, and Cu dissolution into the electrolyte as (Cu-OH) complexes. Furthermore, our investigation explores the correlation between surface coordination environment of active sites and cathodic corrosion of Cu. Finally, by integrating DFT-derived thermodynamic data into a kMC model, we successfully predict the formation of experimentally observed corrosion pits on Cu-surfaces. This combined approach not only advances our fundamental understanding of Cu cathodic corrosion but also offers insights crucial for developing effective corrosion mitigation strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗