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DOE OSTI2020

Building Durable Multimetallic Electrocatalysts from Intermetallic Seeds

When combined with earth-abundant metals, Pt-based alloy nanoparticles (NPs) can be cost-effective electrocatalysts. However, these NPs can experience leaching of non-noble-metal components under harsh electrocatalytic conditions. In this work, the Skrabalak group has demonstrated a novel NP construct in which Pt-based random alloy surfaces are stabilized against non-noble-metal leaching by their deposition onto intermetallic seeds. These core@shell NPs are highly durable electrocatalysts, with the ability to tune catalytic performance by the core@shell architecture, surface alloy composition, and NP shape. This versatility was demonstrated in a model system in which random alloy (ra-) PtM surfaces were deposited onto ordered intermetallic (i-) PdCu seeds using seed-mediated co-reduction (SMCR). In the initial demonstration, ra-PtCu shells were deposited on i-PdCu seeds, with these core@shell NPs exhibiting higher specific and mass activities for the oxygen reduction reaction (ORR) when compared to similarly sized ra-PtCu NPs. These NPs also showed outstanding durability, maintaining ~85% in specific activity after 5000 cycles. Characterization of the NPs after use revealed minimal loss of Cu. The activity enhancement was attributed to the strained surface that arises from the lattice mismatch between the intermetallic core and random alloy surface. The outstanding durability was attributed to the ordered structure of the intermetallic core. The origin of this durability enhancement was investigated by classical molecular dynamics simulations, where Pt atoms were found to have a lower potential energy when deposited on an intermetallic core than when deposited on a random alloy core. Also, ordering of Cu atoms at the core@shell interface appears to enhance the overall binding between the core and the shell materials. Inspired by this initial demonstration, SMCR has been used to achieve shells of different random alloy compositions, PtM (M = Ni, Co, Cu, or Fe). This advance is significant because ligand effects vary as a function of PtM identity and Pt/M ratio. These features also influence the degree of surface strain imparted from the lattice mismatch between the core and shell materials. Like the initial demonstration, standout features of these core@shell NPs were high durability and resistance to non-noble metal leaching. Moving forward, efforts have been directed toward integrating shape-control to this core@shell NP construct. This integration is motivated by the shape-dependent catalytic performance of NPs derived from the selective expression of specific facets. Considering the initial i-PdCu@ra-PtCu system, NPs with a cubic shape have been achieved by judicious selection of capping ligands during SMCR. Evaluation of these NPs as catalysts for the electrooxidation of formic acid found that the nanocubic shape enhances catalytic performance compared to similar core@shell NPs with a spherical morphology. We envision that SMCR can be applied to other NP systems to achieve highly durable catalysts as the syntheses of monodisperse and shape-controlled intermetallic seeds are advanced. This Account highlights the role of intermetallic cores in providing more durable electrocatalysts. More broadly, the versatility of SMCR is highlighted as a route to integrate architecture, alloy surfaces, and shape within one NP system, and how this achievement is inspiring new high-performance and robust catalysts is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Plasma-assisted atomic layer etching of single-crystal diamond

Applications of near-surface nitrogen-vacancy (NV) centers in diamond are often limited by surface defects created during processing. Understanding and controlling plasma-induced surface damage is important for preserving the optical and spin properties of diamond NV centers. We report molecular dynamics simulations of a novel form of plasma-aided atomic layer etching of diamond. In this proposed scheme, the initial surface modification step consists of Ar + ion bombardment. This creates an amorphous layer at the surface, the thickness of which is controlled by the ion energy. Amorphization is known to help smooth the surface, at least locally, and would also serve to sputter clean an initially contaminated surface. A second step impacts the amorphous carbon layer with O + between about 1 and 5 eV. Simulations show that this energy range will remove the amorphous carbon but will not etch the underlying diamond. Though this energy range is not trivial to achieve in a conventional low-temperature plasma, potential methods for creating these low-energy O + ions are discussed. In addition to a-C etching, the O + impacts are predicted to remove any isolated (100) diamond terraces by selectively attacking the edges of the terraces. The proposed atomic layer etching (ALE) approach reverses the conventional ALE sequence in which the surface modification step is usually chemical modification (oxidation in this case), followed by a removal step using Ar + impacts. This plasma ALE procedure is predicted to create a diamond surface that is atomically flat and defect free.

Draney, J. S. [Princeton University, NJ (United St↗

DOE OSTI2023

Enabling attractive-repulsive potentials in binary-collision-approximation monte-carlo codes for ion-surface interactions

Abstract Binary Collision Approximation (BCA) codes for ion-material interactions, such as SRIM, Tridyn, F-TRIDYN, and SDtrimSP, have historically been limited to screened Coulomb potentials even at low energies due to the difficulty in numerically solving the Distance of Closest Approach (DOCA) problem for attractive-repulsive potentials. Techniques such as direct n-body simulation or modifications to Newton’s method are either prohibitively costly or not guaranteed to work for all potentials. Advanced rootfinding techniques, such as companion matrix solvers, offer a solution. For many attractive-repulsive potentials, however, a companion matrix cannot be used directly, because there is no way to put the associated functions into a monomial basis form. A complementary technique is proxy rootfinding—by finding the best-fit polynomial approximant of a function, the zeros of the approximant can be guaranteed to be close to the zeros of the function. Using the Chebyshev basis and grid offers additional guarantees with regards to the quality of the approximation, the speed of convergence, and the avoidance of Runge’s phenomenon. By finding Chebyshev interpolants and using the Chebyshev-Frobenius companion matrix, the zeros of any real function on a bounded domain can be found. Here we show that using an Adaptive Chebyshev Proxy Rootfinder with Automatic Subdivision (ACPRAS) with appropriate scaling functions, numerical issues presented by attractive-repulsive potentials, including those of scale, can be handled. Using these techniques, we show that it is possible to include any physically reasonable interatomic potential in a BCA code, and to guarantee correctness of the resulting scattering angle calculations.

Materials Science↗

DOE OSTI2026

Influence of Surface Treatment on the Interfacial and Mechanical Performance of Metal-Insert Overmolded Composites

Structural composites with metal inserts are gaining increasing interest enabling light weight design for energy efficiency, provide insulation, corrosion protection without compromising mechanical integrity. Such over molded metal-polymer composites show strong potential in many automotive and aerospace component parts, e.g. car bumper, chassis, door, brackets, fasteners, etc. Despite several advantages, metal-polymer dissimilar interface remains a weak spot in structural design, requiring further investigation to improve interfacial interlocking. The current work focuses on enhancing the metal-polymer adhesion between stainless steel inserts and polymer matrices (e.g. acrylonitrile butadiene styrene resin (ABS), and polyamide 66 (PA66) through surface treatment via chemical etching and mechanical roughening. In the chemical etching process, metal substrates were treated with aqua regia solution for different time intervals to evaluate surface roughness measured by water contact angle and morphology analysis. For mechanical roughening approach, metal inserts were subjected to blasting for surface abrasion. Treated samples were also functionalized with aminosilane coupling agent which showed successful grafting on the surface measured by water contact angle. Metal inserts with micro level surface roughness through etching exhibited significant 21% improvement in adhesion strength compared to untreated inserts; however, the effect of silane treatment on the interfacial strength was found to be highly matrix dependent.

Saha, Subhabrata [ORNL] (ORCID:000000033966064X)↗

NASA NTRS2016

Computational and Experimental Study of Li-doped Ionic Liquids at Electrified Interfaces

We evaluate the influence of Li-salt doping on the dynamics, capacitance, and structure of three ionic liquid electrolytes, [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4], using molecular dynamics and polarizable force fields. In this respect, our focus is on the properties of the electric double layer (EDL) formed by the electrolytes at the electrode surface as a function of surface potential (Psi). The rates of EDL formation are found to be on the order of hundreds of picoseconds and only slightly influenced by the addition of Li-salt. The EDLs of three electrolytes are shown to have different energy storage capacities, which we relate to the EDL formation free energy. The differential capacitance obtained from our computations exhibits asymmetry about the potential of zero charge and is consistent with the camel-like profiles noted from mean field theories and experiments on metallic electrodes. The introduction of Li-salt reduces the noted asymmetry in the differential capacitance profile. Complementary experimental capacitance measurements have been made on our three electrolytes in their neat forms and with Li-salt. The measurements, performed on glassy carbon electrodes, produce U-like profiles, and Li-salt doping is shown to strongly affect capacitance at high magnitudes of Psi. Differences in the theoretical and experimental shapes and magnitudes of capacitance are rationalized in terms of the electrode surface and pseudocapacitive effects. In both neat and Li-doped liquids, the details of the computational capacitance profile are well described by Psi-induced changes in the density and molecular orientation of ions in the molecular layer closest to the electrode. Our results suggest that the addition of Li+ induces disorder in the EDL, which originates from the strong binding of anions to Li+. An in-depth analysis of the distribution of Li+ in the EDL reveals that it does not readily enter the molecular layer at the electrode surface, preferring instead to be localized farther away from the surface in the second molecular layer. This behavior is validated through an analysis of the free energy of Li+ solvation as a function of distance from the electrode. Free energy wells are found to coincide with localized concentrations of Li+, the depths of which increase with Psi and suggest a source of impedance for Li+ to reach the electrode.

Haskins, Justin B.↗

NASA NTRS2011

Synergism of Saturn, Enceladus and Titan and Formation of HCNO Prebiotic Molecules

Saturn as a system has two very exotic moons Titan and Enceladus. Titan, taking in energy from Saturn's magnetosphere, solar UV irradiation, and cosmic rays, can make HCN based molecules as discussed in earlier paper by Raulin and Owen. Space radiation effects at both moons, and as coupled by the Saturn magnetosphere, could cause an unexpected series of events potentially leading to prebiotic chemical evolution at Titan with HCNO from magnetospheric oxygen as the new ingredient. The "Old Faithful" model suggests that Enceladus, highly irradiated by Saturn magnetospheric electrons and thus having a source of chemical energy from radiolytic gas production, has episodic ejections of water vapor, carbon dioxide, and various hydrocarbons into Saturn's magnetosphere. The hydrocarbons do not survive transport through the plasma environment, but oxygen ions from Enceladus water molecules become the dominant ion species in the outer magnetosphere. At Titan, Cassini discovered that 1) keV oxygen ions, evidently from Enceladus, are bombarding Titan's upper atmosphere and 2) heavy positive and negative ions exist in significant abundances within Titan's upper atmosphere. Initial models of heavy ion formation in Titan's upper atmosphere invoked polymerization of aromatics such as benzenes and their radicals to make polycyclic aromatic hydrocarbons (PAH) , while a more recent model by Sittler et al., has raised the possibility of carbon chains forming from the polymerization of acetylene and its radicals to make fullerenes. Laboratory measurements indicate that fullerenes, which are hollow carbon shells, can trap keV oxygen ions. Clustering of the fullerenes with aerosol mixtures from PAHs and the dominant nitrogen molecules could form larger aerosols enriched in trapped oxygen. Aerosol precipitation could then convey these chemically complex structures deeper into the atmosphere and to the moon surface. Ionizing solar UV, magnetospheric electron, and galactic cosmic ray irradiation would provide further energy for processing into more complex organic forms. Further ionizing irradiation from cosmic rays deep in the atmosphere "tho lin" molecules are produced with all the molecular components present from which prebiotic organic molecules can form. This synergy of Saturn system, exogenic irradiation, and molecular processes provides a potential pathway for accumulation of prebiotic chemistry on the surface of Titan. Since fullerenes are also thought to exist in interstellar space, similar processes may also occur there to seed molecular clouds with prebiotic chemical species. We will also discuss possible future laboratory experiments that could be done to investigate fullerene formation at Titan and the trapping of oxygen in fullerenes.

Sittler, Edward C.↗

DOE OSTI2024

Iron Impurity Impairs the CO 2 Capture Performance of MgO: Insights from Microscopy and Machine Learning Molecular Dynamics

Magnesium oxide (MgO) is a promising sorbent for direct air capture (DAC) of carbon dioxide. Iron (Fe) is a common impurity in naturally occurring MgO and minerals used to produce MgO, yet a molecular-scale understanding of Fe-doping effects on carbonation is lacking. Here, in this study, we observed reduced carbonation performance in Fe-doped MgO experimentally. The energetics of adsorbing a (bi)carbonate ion on pristine and Fe-doped MgO(001) surfaces were further investigated using ab initio and machine learning potential molecular dynamics coupled with metadynamics simulations. Both pristine and Fe-doped surfaces exhibited a basic (OH – ) hydration layer, where the (bi)carbonate ion adsorption is thermodynamically favorable. However, the dissolution of surface Fe had smaller energy barriers and was more favorable than Mg. Leached Fe likely neutralized the near-surface basicity, yielding reduced reactivity on Fe-doped MgO. Our observations offer critical insights for material selection and emphasize the importance of evaluating the geologic origin of earth materials used for DAC.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Unveiling the parasitic-reaction-driven surface reconstruction in Ni-rich cathode and the electrochemical role of Li 2 CO 3

Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energy-density lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li 2 CO 3 impurity content on LiNi 0.83 Mn 0.1 Co 0.07 O 2 cathodes using air, tank-air, and O 2 synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li 2 CO 3 impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li 2 CO 3 content and severe performance deterioration of Ni83 cathodes. The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Here, our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Ni-rich cathodes and prepares us for searching for rational strategies.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Hydrogen irradiation-driven computational surface chemistry of lithium oxide and hydroxide

We have investigated, using molecular dynamics, the surface chemistry of hydrogen incident on the amorphous and crystalline lithium oxide and lithium hydroxide surfaces upon being slowed down by a collision cascade and retained in the amorphous surface of either Li 2 O or LiOH. We looked for the bonding of H to the resident structures in the surface to understand a possible chain of chemical reactions that can lead to surface transformation upon H atom impact. Our findings, using Density-Functional Theory (DFT) trained ReaxFF force field/electronegativity equalization method potentials, stress the importance of inclusion of polarization in the dynamics of a Li–O–H system, which is also illustrated by DFT energy minimization and quantum–classical molecular dynamics using tight binding DFT. The resulting polar-covalent chemistry of the studied systems is complex and very sensitive to the instantaneous positions of all atoms as well as the ratio of concentrations of various resident atoms in the surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Switchable wetting of oxygen-evolving oxide catalysts

The surface wettability of catalysts is typically controlled via surface treatments that promote catalytic performance. Here we report on potential-regulated hydrophobicity/hydrophilicity at cobalt-based oxide interfaces with an alkaline solution. The switchable wetting of single particles, directly related to their activity and stability towards the oxygen evolution reaction, was revealed by electrochemical liquid-phase transmission electron microscopy. Analysis of the movement of the liquid in real time revealed distinctive wettability behaviour associated with specific potential ranges. At low potentials, an overall reduction of the hydrophobicity of the oxides was probed. Upon reversible reconstruction towards the surface oxyhydroxide phase, electrowetting was found to cause a change in the interfacial capacitance. At high potentials, the evolution of molecular oxygen, confirmed by operando electron energy-loss spectroscopy, was accompanied by a globally thinner liquid layer. This work directly links the physical wetting with the chemical oxygen evolution reaction of single particles, providing fundamental insights into solid–liquid interfacial interactions of oxygen-evolving oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Residual stress of controlled atmosphere plasma spray blended metal deposits measured via in-situ substrate curvature method

The preliminary use of the in-situ curvature measurement technique for analyzing the planar stress evolution of controlled atmosphere plasma spray (CAPS) refractory metal deposits was performed with SNL-NM org. 1834’s CAPS system. A porous refractory metal exemplar of Ta-Nb was sprayed onto Ni-200, Ti-6Al-4V, and Al 7075-T6 substrates using a constant plasma torch parameter setting and deposition toolpath. Residual stresses of the deposits were found to be largely influenced by the substrate coefficient of thermal expansion and were calculated to be 49, 90, and -136 MPa for Ni 200, Ti-6Al-4V, and Al 7075-T6, respectively. The “Evolving stress” of the Ta-Nb deposits, which more accurately describes the mean intrinsic splat quenching stress of the spray material during deposition, was calculated to be 67, 92, and 129 MPa for Ni-200, Ti-6Al-4V, and Al 7075-T6, respectively. Notable difference in curvature measurement for the 1st coating pass for the Al 7075- T6 substrate was observed, with interface micrograph evidence suggesting potential softening and/or melting of the Al 7075-T6 substrate surface during deposition. Substrate temperature measurements prior to Ta-Nb deposition were used to calculate thermal energy absorbed from the hot gas plume by the different substrates and were found to correlate to the substrate’s thermal effusively. These calculated thermal energies were also found to be ~10 to 15% of the calculated energy output from the plasma torch’s nozzle exit for these experimental conditions.

36 MATERIALS SCIENCE↗

NASA NTRS1972

Extraterrestrial consumables production and utilization

Potential oxygen requirements for lunar-surface, lunar-orbit, and planetary missions are presented with emphasis on: (1) emergency survival of the crew, (2) provision of energy consumables for vehicles, and (3) nondependency on an earth supply of oxygen. Although many extraterrestrial resource processes are analytically feasible, this study has considered hydrogen and fluorine processing concepts to obtain oxygen or water (or both). The results are quite encouraging and are extrapolatable to other processes. Preliminary mission planning and sequencing analysis has enabled the programmatic evaluation of using lunar-derived oxygen relative to transportation cost as a function of vehicle delivery and operational capability.

Sanders, A. P.↗

NASA NTRS1973

Normal and Tangential Momentum Accommodation for Earth Satellite Conditions

Momentum accommodation was determined experimentally for gas-surface interactions simulating in a practical way those of near-earth satellites. Throughout the ranges of gas energies and incidence angles of interest for earth-conditions, two components of force were measured by means of a vacuum microbalance to determine the normal and tangential momentum-accommodation coefficients for nitrogen ions on technical-quality aluminum surfaces. For these experimental conditions, the electrodynamics of ion neutralization near the surface indicate that results for nitrogen ions should differ relatively little from those for nitrogen molecules, which comprise the largest component of momentum flux for near-earth satellites. The experimental results indicated that both normal and tangential momentum-accommodation coefficients varied widely with energy, tending to be relatively well accommodated at the higher energies, but becoming progressively less accommodated as the energy was reduced to and below that for earth-satellite speeds. Both coefficients also varied greatly with incidence angle, the normal momentum becoming less accommodated as the incidence angle became more glancing, whereas the tangential momentum generally became more fully accommodated. For each momentum coefficient, an empirical correlation function was obtained which closely approximated the experimental results over the ranges of energy and incidence angle. Most of the observed variations of momentum accommodation with energy and incidence angle were qualitatively indicated by a calculation using a three-dimensional model that simulated the target surface by a one-dimensional attractive potential and hard sphere reflectors.

Knechtel, Earl D.↗

NASA NTRS2005

Partial Model of Insulator/Insulator Contact Charging

Two papers present a two-phase equilibrium model that partly explains insulator/ insulator contact charging. In this model, a vapor of ions within a gas is in equilibrium with a submonolayer of ions of the same species that have been adsorbed on the surface of an insulator. The surface is modeled as having localized states, each with a certain energy of adsorption for an ion. In an earlier version of the model described in the first paper, the ions do not interact with each other. Using the grand canonical ensemble, the chemical potentials of both vapor and absorbed phases are derived and equated to determine the vapor pressure. If a charge is assigned to the vapor particles (in particular, if single ionization is assumed), then the surface charge density associated with adsorbed ions can be calculated as a function of pressure. In a later version of the model presented in the second paper, the submodel of the vapor phase is extended to include electrostatic interactions between vapor ions and adsorbed ones as well as the screening effect, at a given distance from the surface, of ions closer to the surface. Theoretical values of this model closely match preliminary experimental data on the discharge of insulators as a function of pressure.

Hogue, Michael↗

DOE OSTI2023

The electric fields and “lightning jets” of the Sun and solar wind

A model of electric energization of the solar wind and corona is developed, including electro-magnetic particle effects precluded by traditional magneto-hydro (MHD) assumptions. Using standard 1D radial solar models for particle density and temperature, the core gravito-electric field is calculated; and the range of possible photospheric photo-electric fields is estimated. The extant DC field apparently arises from about 460 C of charge displacement, mainly caused by the immense solar energy flux pushing electrons outward. Energetically, this electric field can accelerate surface protons out of the 2 keV gravity well and up to the 4 keV energies observed in the fast solar wind. The electrical energy is released in pervasive, persistent “proton lightning jets,” which are proton beams, charge-neutralized by co-propagating electrons. The jets are formed by pinched “avalanche breakdown” of the weakly ionized photosphere, probably initiated on the down-welling edges of solar surface granulations. These energetic jets will glow as discrete filamentary surface spicules and will be observed in reflected solar light as the diffuse K-corona. Significantly, the total charge displacement and observed fast wind speed are quantitatively predicted by a novel “virial limit”: the (positive) electrical potential energy at r = 0 is limited in magnitude to the 10 keV gravitational well at r = 0.

Physics↗

DOE OSTI2022

Efficient electrocatalytic conversion of CO 2 to ethanol enabled by imidazolium-functionalized ionomer confined molybdenum phosphide

An effective electrochemical carbon dioxide reduction reaction (eCO 2 RR) requires the discovery of a catalytic system that is highly active and selective for multi-carbon products together with superior CO 2 diffusion at a catalyst layer to minimize the reduction barriers. Here, we found a catalytic system that uses molybdenum phosphide (MoP) nanoparticles covered by imidazolium-functionalized ionomer (Im) that promotes CO 2 diffusion at the catalyst layer toward the catalyst surface, where CO 2 is reduced to ethanol (C 2 H 5 OH). The electrochemical results with the MoP-Im co-catalyst show a C 2 H 5 OH production Faradaic efficiency and a cathodic energy efficiency of 77.4% and 63.3%, respectively, at a potential as low as - 200 mV vs. RHE. The electrochemical experiments along with our physicochemical characterizations indicate that the Im improves CO 2 diffusion and balances water content resulting in a higher CO 2 -to-water ratio at the catalyst layer and fine-tunes the electronic properties of Mo atoms at the MoP surface. Finally, in-situ Raman spectroscopy reveals that a high number of adsorbed *CO intermediates on the surface and a higher binding strength of *CO intermediates on the Mo surface sites in the presence of imidazolium molecules are the main reasons for a superior C-C coupling and thereby the improved C 2 H 5 OH formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Revealing the Predominant Surface Facets of Rough Cu Electrodes under Electrochemical Conditions

Metal electrodes with rough surfaces are frequently found to convert CO or CO 2 to hydrocarbons and oxygenates with high selectivity and at high reaction rates in comparison with their smooth counterparts. The atomic-level morphology of a rough electrode is likely one key factor responsible for its comparatively high catalytic selectivity and activity. However, few methods are capable of probing the atomic-level structure of rough metal electrodes under electrocatalytic conditions. As a result, the nuances in the atomic-level surface morphology that control the catalytic characteristics of these electrodes have remained largely unexplored. Because the C≡O stretching frequency of atop-bound CO (CO atop ) depends on the coordination of the underlying metal atom, the IR spectrum of this reaction intermediate on the copper electrode could, in principle, provide structural information about the catalytic surface during electrolysis. However, other effects, such as dynamic dipole coupling, easily obscure the dependence of the frequency on the surface morphology. Further, in the limit of low CO atop coverage, where coupling effects are small, the C≡O stretching frequencies of CO atop on Cu(111) and Cu(100) facets are virtually identical. Therefore, on the basis of the C≡O stretching frequency, it is not straightforward to distinguish between these two ubiquitous surface facets, which exhibit vastly different CO reduction activities. Herein, we show that key features of the atomic-level surface morphology of rough copper electrodes can be inferred from the potential dependence of the line shape of the C≡O stretching band of CO atop . Specifically, we compared two types of rough copper thin-film electrodes that are routinely employed in the context of surface-enhanced infrared absorption spectroscopy (SEIRAS). We found that copper films that are electrochemically deposited on Si-supported Au films (CuAu–Si) are poor catalysts for the reduction of CO to ethylene in comparison to copper films (Cu–Si) that are electrolessly deposited onto Si crystals. As quantified by differential electrochemical mass spectrometry (DEMS), the onset potential for ethylene is ~200 ± 65 mV more cathodic for CuAu–Si than that for Cu–Si. To reveal the origin of the disparate catalytic properties of Cu–Si and CuAu–Si, we probed the surfaces of the electrodes with cyclic voltammetry (CV) and SEIRAS. The CV characterization suggests that the (111) surface facet predominates on CuAu–Si, whereas the (100) facet is more common on Cu–Si. SEIRAS reveals that the line shape of the C≡O stretching of CO atop is composed of two bands that are attributable to CO atop on terrace and defect sites. The different surface structures manifest themselves in the form of starkly different potential dependences of the line shape of the C≡O stretching mode of CO atop on the two types of electrodes. With a simple Boltzmann model that considers the different adsorption energies of CO atop on terrace and defect sites, and the resulting CO atop populations on terrace and defect sites, we deduced that the observed electrode-specific potential dependence of the line shape is consistent with the presence of different predominant terrace sites on the two types of films. This strategy for assessing the atomic-level morphology is not restricted to SEIRAS but could also be applied to the C≡O stretching bands recorded with surface-enhanced Raman spectroscopy (SERS), which is suitable for probing a wide range of rough copper electrodes. Therefore, with this work, we establish the potential dependence of the C≡O stretching band of CO atop as a probe of the atomic-level surface structure of rough metal electrodes under electrochemical conditions. When it is coupled with complementary techniques, this methodology provides essential structural information for further improvement in the reaction selectivity of rough metal electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1989

The divergence characteristics of constrained-sheath optics systems for use with 5-eV atomic oxygen sources

The potential usefulness of the constrained sheath optics concept as a means of controlling the divergence of low energy, high current density ion beams is examined numerically and experimentally. Numerical results demonstrate that some control of the divergence of typical ion beamlets can be achieved at perveance levels of interest by contouring the surface of the constrained sheath properly. Experimental results demonstrate that a sheath can be constrained by a wire mesh attached to the screen plate of the ion optics system. The numerically predicted beamlet divergence characteristics are shown to depart from those measured experimentally, and additional numerical analysis is used to demonstrate that this departure is probably due to distortions of the sheath caused by the fact that it attempts to conform to the individual wires that make up the sheath constraining mesh. The concept is considered potentially useful in controlling the divergence of ion beamlets in applications where low divergence, low energy, high current density beamlets are being sought, but more work is required to demonstrate this for net beam ion energies as low as 5 eV.

Anderson, John R.↗