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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.

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At least 1,729 records · Page 96
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Mitigating CaCO 3 crystal nucleation and growth through continuous ion displacement via alternating electric fields

Mineral crystal formation poses a challenge on surfaces (e.g., heat exchangers, pipes, membranes, etc.) in contact with super-saturated fluids. Applying alternating currents (AC) to such surfaces can prevent surface crystallization under certain conditions. Here, we demonstrate that ion displacement induced by periodic charging and discharging of the electrical double layer (EDL) inhibits both heterogeneous and homogeneous nucleation (and crystal growth) of CaCO 3 . Titanium sheets (meant to simulate metallic heat exchanger surfaces) are immersed in super-saturated CaCO 3 solutions with a saturation index >11. We show that at relatively high AC frequencies, incomplete EDL formation leads to an alternating electric field that propagates far into the bulk solution, inducing rapid ion migration that overwhelms the Brownian motion of ions. Electrochemical characterization reveals EDL charging/discharging under AC conditions that greatly inhibits precipitation. Operating at 4 V pp , 0.1–10 Hz reduces turbidity by over 96% and reduces CaCO 3 coverage on the metal plates by over 92%. Based on electrokinetic and crystallization models, the ion displacement velocity (exceeding the mean Brownian velocity) and displacement length disrupts ion collision and crystal nucleation. Overall, the technique has potential for preventing mineral crystal formation in heat exchangers and many other industrially relevant systems.

42 ENGINEERING↗
NASA NTRS1992

GPS meteorology - Remote sensing of atmospheric water vapor using the Global Positioning System

We present a new approach to remote sensing of water vapor based on the Global Positioning System (GPS). Geodesists and geophysicists have devised methods for estimating the extent to which signals propagating from GPS satellites to ground-based GPS receivers are delayed by atmospheric water vapor. This delay is parameterized in terms of a time-varying zenith wet delay (ZWD) which is retrieved by stochastic filtering of the GPS data. Given surface temperature and pressure readings at the GPS receiver, the retrieved ZWD can be transformed with very little additional uncertainty into an estimate of the integrated water vapor (IWV) overlying that receiver. Networks of continuously operating GPS receivers are being constructed by geodesists, geophysicists, and government and military agencies, in order to implement a wide range of positioning capabilities. These emerging GPS networks offer the possibility of observing the horizontal distribution of IWV or, equivalently, precipitate water with unprecedented coverage and a temporal resolution of the order of 10 min. These measurements could be utilized in operational weather forecasting and in fundamental research into atmospheric storm systems, the hydrologic cycle, atmospheric chemistry, and global climate change.

Bevis, Michael↗
NASA NTRS1999

Polar Geophysics Products Derived from AVHRR: The "AVHRR Polar Pathfinder

This NOAA/NASA Pathfinder effort was established to locate, acquire, and process Advanced Very High Resolution Radiometer (AVHRR) imagery into geo-located and calibrated radiances, cloud masks, surface clear-sky broadband albedo, clear-sky skin temperatures, satellite viewing times, and viewing and solar geometry for the, high-latitude portions of the northern and southern hemispheres (all area north of 48N and south of 53S). AVHRR GAC data for August 1981 - July 1998 were acquired, with some gaps remaining, and processed into twice-daily 5-km grids, with some products also provided at 25-km resolution. AVHRR LAC data for 3.5 years of coverage in the northern hemisphere and 2.75 years of coverage in the southern hemisphere were processed into 1.25-km grids for the same suite of products. The resulting data sets are presently being transferred to the National Snow and Ice Data Center (NSIDC) for archiving and distribution. Using these data, researchers now have at their disposal an extensive AVHRR data set for investigations of high-latitude processes. In addition, the data lend themselves to development and testing of algorithms. The products are particularly relevant for climate research and algorithm development as applied to relatively long time periods and large areas.

Maslanik, James↗
NASA NTRS2013

Combined Global Navigation Satellite Systems in the Space Service Volume

Besides providing position, velocity, and timing (PVT) for terrestrial users, the Global Positioning System (GPS) is also being used to provide PVT information for earth orbiting satellites. In 2006, F. H. Bauer, et. al., defined the Space Service Volume in the paper GPS in the Space Service Volume , presented at ION s 19th international Technical Meeting of the Satellite Division, and looked at GPS coverage for orbiting satellites. With GLONASS already operational, and the first satellites of the Galileo and Beidou/COMPASS constellations already in orbit, it is time to look at the use of the new Global Navigation Satellite Systems (GNSS) coming into service to provide PVT information for earth orbiting satellites. This presentation extends GPS in the Space Service Volume by examining the coverage capability of combinations of the new constellations with GPS GPS was first explored as a system for refining the position, velocity, and timing of other spacecraft equipped with GPS receivers in the early eighties. Because of this, a new GPS utility developed beyond the original purpose of providing position, velocity, and timing services for land, maritime, and aerial applications. GPS signals are now received and processed by spacecraft both above and below the GPS constellation, including signals that spill over the limb of the earth. Support of GPS space applications is now part of the system plan for GPS, and support of the Space Service Volume by other GNSS providers has been proposed to the UN International Committee on GNSS (ICG). GPS has been demonstrated to provide decimeter level position accuracy in real-time for satellites in low Earth orbit (centimeter level in non-real-time applications). GPS has been proven useful for satellites in geosynchronous orbit, and also for satellites in highly elliptical orbits. Depending on how many satellites are in view, one can keep time locked to the GNSS standard, and through that to Universal Time as long as at least one satellite is in view (the longest duration with no satellites in view is important in determining the maximum clock drift from GNSS time). Instantaneous position requires four satellites in view, but because orbital motion is predictable, it is possible to build up knowledge of the orbital position gradually through time without a need for constant four satellite coverage. However, it is desirable to have four satellite coverage when performing satellite maneuvers, since there can be significant changes in velocity, leading to large changes in orbit parameter, causing substantial divergence in position over time. The Space Service Volume has been defined as the volume between three thousand km altitude and geosynchronous altitude, and can be divided into medium orbit services between three thousand km altitude and eight thousand km altitude, and high orbit services above eight thousand km. The Terrestrial Service Volume includes the Earth s surface, the atmosphere, and space below the altitude of three thousand km. The Terrestrial Service Volume is the volume within which the GNSS systems will have very similar performance to the Earth surface, and satellites need only use the signals specified to provide terrestrial performance. Above three thousand km the use of signals passing by the Earth s limb becomes important, so it is desirable to have additional information on signal strength, phase delay, and group delay covering wider beam angles than are needed for terrestrial service (and which can be obtained by monitoring GNSS signals from the Earth s surface). This presentation will look at each of the new GNSS constellations in combination with GPS (GLONASS with GPS, Galileo with GPS, Beidou/COMPASS with GPS), and also at the combination of all four GNSS systems. The presentation will largely follow the format of GPS in the Space Service Volume , presenting data on the availability of one, two, three, or four of the various combinations of GNSS constellation satelles at approximately two thousand grid points evenly spaced and fixed in longitude and latitude, the duration of the longest single-fold outages (intervals when no satellites are available), and the duration of the longest four-fold outages (intervals when fewer than four satellites are available) at several altitudes. Following the original paper, we will use the altitudes of three hundred km (typical LEO satellite, and within the Terrestrial Service Volume), at three thousand km (border between Terrestrial Service Volume and Space Service Volume), at eight thousand km (the border between medium and high orbit service within the Space Service Volume), at fifteen thousand km (just below the GNSS constellations), at twenty five thousand km (just above the GNSS constellations), at thirty six thousand, five hundred km (limit of Space Service Volume definition, geosynchronous altitude), and at seventy thousand km (to show the potential usefulness of GNSS beyond geosynchronous altitude).

Force, Dale A.↗
DOE OSTI2025

Understanding how defects and dopant atoms in copper surface oxides affect reactivity

Copper and its oxides are key catalytic materials, on which reactions often occur at the metal/oxide interface. Here, in this work, we directly connect the induction period observed during methanol-driven reduction of thin-film copper oxides to their atomic-scale structural order. Using temperature-programmed desorption (TPD) methanol titrations combined with scanning tunneling microscopy, we show that highly ordered oxide phases – particularly the “29” structure with its low defect density – exhibit long induction periods and initially low reactivity. The induction period, defined as the number of methanol TPD cycles required to reach half of the maximum formaldehyde yield, scales with oxide order and oxygen coverage. Enhanced reactivity of well-ordered oxides emerges only after repeated methanol adsorption/desorption cycles generate oxygen vacancies and new Cu(111)/Cu x O interfacial sites. In contrast, disordered or sub-stoichiometric oxides, which contain more intrinsic defects and interfaces, are active from the first TPD cycle. We further examine how dilute Pt and Rh dopants influence oxide order and reactivity: 1% Pt increases defect density and catalytic activity, while 1% Rh promotes oxide ordering and longer induction periods. These findings demonstrate that dilute alloying provides a potential method for tuning the structure and reactivity of Cu(111)/Cu x O interfaces.

Cu(111)Methanol oxidation↗
DOE OSTI2021

Surfactants and cloud droplet activation: A systematic extension of Köhler theory based on analysis of droplet stability

The activation of aerosol particles to form cloud droplets, a necessary first step in cloud formation, controls much of the impact that aerosols have on clouds and climate. Recently, there has been a surge of interest in extending the Köhler theory of cloud droplet activation to include surface active (typically organic) as well as water-soluble (typically inorganic) aerosol components, but a systematic framework for doing this has yet to be developed. Here, we apply a droplet stability analysis to this end. Ideal and Szyszkowski–Langmuir surfactant models are analyzed to demonstrate the new approach, but the underlying theoretical framework is fundamental and model free. A key finding is that superficial densities at the cloud activation threshold (Köhler maximum) are significantly sub-monolayer, with fractional coverage ranging from 69% to 85% for the organic compounds and mixtures studied. The result, significant for model inventories of cloud condensation nuclei, is a weakening of the surfactant effect relative to expectations based on bulk sample measurements. Analytical results are obtained for the loci of Köhler maxima and applied to aerosol mixtures containing an arbitrary number of water-soluble and surfactant components.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Water dissociation at the water–rutile TiO 2 (110) interface from ab initio-based deep neural network simulations

The interaction of water with TiO 2 surfaces is of crucial importance in various scientific fields and applications, from photocatalysis for hydrogen production and the photooxidation of organic pollutants to self-cleaning surfaces and bio-medical devices. In particular, the equilibrium fraction of water dissociation at the TiO 2 –water interface has a critical role in the surface chemistry of TiO 2 , but is difficult to determine both experimentally and computationally. Among TiO 2 surfaces, rutile TiO 2 (110) is of special interest as the most abundant surface of TiO 2 ’s stable rutile phase. While surface-science studies have provided detailed information on the interaction of rutile TiO 2 (110) with gas-phase water, much less is known about the TiO 2 (110)–water interface, which is more relevant to many applications. In this work, we characterize the structure of the aqueous TiO 2 (110) interface using nanosecond timescale molecular dynamics simulations with ab initio-based deep neural network potentials that accurately describe water/TiO 2 (110) interactions over a wide range of water coverages. Simulations on TiO 2 (110) slab models of increasing thickness provide insight into the dynamic equilibrium between molecular and dissociated adsorbed water at the interface and allow us to obtain a reliable estimate of the equilibrium fraction of water dissociation. We find a dissociation fraction of 22 ± 6% with an associated average hydroxyl lifetime of 7.6 ± 1.8 ns. These quantities are both much larger than corresponding estimates for the aqueous anatase TiO 2 (101) interface, consistent with the higher water photooxidation activity that is observed for rutile relative to anatase.

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

Modification of Wool Fibers via Base/Cationic Detergent Pretreatment and Transglutaminase-mediated Reaction of Keratin

The surface modification of wool fibers is an important part of the textile industry to add functionality and stability to wool products. In this study, we developed a process utilizing a base/cationic surfactant solution pretreatment followed by an enzyme-mediated keratin crosslinking reaction to modify the wool fibers. Changes in water contact angle demonstrated the successful transformation of the hydrophobic wool surface to a more hydrophilic one after soaking in sodium carbonate solution containing hexadecyltrimethylammonium bromide (CTAB). The treated fabrics were further characterized by colorimetry and fluorescent spectrometry. Results showed that the pretreatment increased the yellowness of fabrics and caused some structural changes among certain amino acids, such as tryptophan and cystine. Keratin extracted from coarse wool fibers was further applied on pretreated fabrics through a microbial transglutaminase (mTGase) mediated reaction under mild conditions. Morphological characterization via SEM demonstrated the effective coverage of keratin on the scales of wool. The current method may provide an alternative processing protocol to modify wool fibers and improve the quality and performance of wool products.

36 MATERIALS SCIENCE↗
DOE OSTI2021

End-of-Winter Snow Depth, Temperature, Density and SWE Measurements at Kougarok Road Site, Seward Peninsula, Alaska, 2018

Measurements of snow properties were taken in 2018 at the NGEE Arctic Kougarok field site. This dataset contains spatially distributed values of snow depth, integrated snow pack density, snow water equivalent (SWE), temperature at the snow surface and at the bottom of the snow pack, and snow density as a function of depth from top of snow pack. Data was collected toward the end of the winter season, in late March, when snow pack would be near its maximum. Data was collected toward the end of the winter season, in late March, when snow pack would be near its maximum. A Snow-Hydro MagnaProbe (http://www.snowhydro.com/products/column2.html) was used for collection efficiency and enhanced spatial coverage. This package contains four *.csv data files and one *.pdf user guide file. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1990

Planetary circulations in the presence of transient and self-induced heating

The linearized global primitive equation model of Salby and Garcia (1987) was modified to study tropospheric circulations and their interaction with tropical convection. The vertical resolution was increased to approximately 1.5 km, with the effective vertical domain extending the approximately 40 km (higher altitudes in the calculation are used to ensure the radiation upper boundary condition is satisfied). A formal wave conditional instability of the second kind (CISK) parameterization was introduced. That parameterization allows low-frequency disturbances to interact with convection by organizing surface moisture. Boundary layer friction has two important effects in these calculations: it exaggerates surface convergence near the equator by driving the flow out of geostrophic balance; and it introduces a phase shift between the convergence pattern and the circulation, which drives the heating out of quadrature with the temperature field and allows a positive feedback to take place. The observational complement of this theoretical work involves Global Cloud Imagery (GCI) composited from six satellites in the International Satellite Cloud Climatology Project (ISCCP) which were simultaneously observing the Earth's cloud field. Having global coverage, horizontal resolution of half a degree, and produced synoptically every 3 hours, the GCI affords an unprecendented view of global convection. A full year (1983 to 1984) of GCI has now been successfully created. Among other phenomena, that imagery reveals a regular progression of easterly waves in the convective pattern of the Western Pacific. Those disturbances have odd symmetry about the equator and organize convection into a pattern with similar symmetry. In time-mean maps of cloud cover, these propagating disturbances produce a split Inter-Tropical Convergence Zone (ITCZ) in the western Pacific.

Salby, Murry L.↗
NASA NTRS2012

Space-Based Lidar Systems

An overview of space-based lidar systems is presented. from the first laser altimeter on APOLLO 15 mission in 1971 to the Mercury Laser Altimeter on MESSENGER mission currently in orbit, and those currently under development. Lidar, which stands for Light Detection And Ranging, is a powerful tool in remote sensing from space. Compared to radars, lidars operate at a much shorter wavelength with a much narrower beam and much smaller transmitter and receiver. Compared to passive remote sensing instruments. lidars carry their own light sources and can continue measuring day and night. and over polar regions. There are mainly two types of lidars depending on the types of measurements. lidars that are designed to measure the distance and properties of hard targets are often called laser rangers or laser altimeters. They are used to obtain the surface elevation and global shape of a planet from the laser pulse time-of-night and the spacecraft orbit position. lidars that are designed to measure the backscattering and absorption of a volume scatter, such as clouds and aerosols, are often just called lidars and categorized by their measurements. such as cloud and aerosol lidar, wind lidar, CO2 lidar, and so on. The advantages of space-based lidar systems over ground based lidars are the abilities of global coverage and continuous measurements.

Sun, Xiaoli↗
NASA NTRS1992

Temporal variability of the surface and atmosphere of Mars: Viking Orbiter color observations

We are near the final stages in the processing of a large Viking Orbiter global color dataset. Mosaics from 57 spacecraft revolutions (or 'revs' hereafter) were produced, most in both red and violet or red, green, and violet filters. Phase angles range from 13 deg to 85 deg. A total of approximately 2000 frames were processed through radiometric calibration, cosmetic cleanup, geometric control, reprojection, and mosaicking into single-rev mosaics at a scale of 1 km/pixel. All of the mosaics are geometrically tied to the 1/256 deg/pixel Mars Digital Image Mosaic (MDIM). Photometric normalization is in progress, to be followed by production of a 'best coverage' global mosaic at a scale of 1/64 deg/pixel (0.923 km/pixel). Global coverage is near 100 percent in red-filter mosaics and 98 percent and 60 percent in corresponding violet- and green-filter mosaics, respectively. Soon after completion, all final datasets (including single-rev mosaics) will be distributed to the planetary community on compact disks.

Mcewen, A. S.↗
DOE OSTI2021

End-of-Winter Snow Depth, Temperature, Density and SWE Measurements at Teller Road Site, Seward Peninsula, Alaska, 2016-2018

Measurements of end-of-winter snow properties were collected at the NGEE Arctic Teller Road Site at mile marker 27 (TL_MM27) for three consecutive years - 2016, 2017, and 2018. This dataset contains one *.pdf user guide and four *.csv data files spatially distributed values of snow depth, snow water equivalent (SWE), temperature at the snow surface and at the bottom of the snowpack, and snow density as a function of depth from top of snowpack. Data was collected toward the end of the winter season, typically in late March or early April, when the snowpack would be near its maximum. In 2016, snow depth measurements were taken using either a thaw probe or avalanche probe. In 2017 and 2018 a Snow-Hydro MagnaProbe http://www.snowhydro.com/products/column2.html was used to improve collection efficiency and enhance spatial coverage. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1996

Analysis, design and testing of high pressure waterjet nozzles

The Hydroblast Research Cell at MSFC is both a research and a processing facility. The cell is used to investigate fundamental phenomena associated with waterjets as well as to clean hardware for various NASA and contractor projects. In the area of research, investigations are made regarding the use of high pressure waterjets to strip paint, grease, adhesive and thermal spray coatings from various substrates. Current industrial methods of cleaning often use ozone depleting chemicals (ODC) such as chlorinated solvents, and high pressure waterjet cleaning has proven to be a viable alternative. Standard methods of waterjet cleaning use hand held or robotically controlled nozzles. The nozzles used can be single-stream or multijet nozzles, and the multijet nozzles may be mounted in a rotating head or arranged in a fan-type shape. We consider in this paper the use of a rotating, multijet, high pressure water nozzle which is robotically controlled. This method enables rapid cleaning of a large area, but problems such as incomplete coverage (e.g. the formation of 'islands' of material not cleaned) and damage to the substrate from the waterjet have been observed. In addition, current stripping operations require the nozzle to be placed at a standoff distance of approximately 2 inches in order to achieve adequate performance. This close proximity of the nozzle to the target to be cleaned poses risks to the nozzle and the target in the event of robot error or the striking of unanticipated extrusions on the target surface as the nozzle sweeps past. Two key motivations of this research are to eliminate the formation of 'coating islands' and to increase the allowable standoff distance of the nozzle.

Mazzoleni, Andre P.↗
NASA NTRS2018

Tandem LA-ICP-MS & LIBS; A New Micro-Analytical Technique for the Measurement of Every Element in the Periodic Table

Laser Ablation ICP-MS (LA-ICP-MS) has been widely accepted as a microanalytical technique for in-situ trace (ppb) elemental analysis on the micron scale in a variety of geologic materials. LA-ICP-MS (single or multi-collector) provides both elemental and isotopic measurements critical for a wide range of geological research by generating a fine grained aerosol (nm scale) during the laser ablation event and delivering that aerosol to the ICP ion source of the mass spectrometer via an inert carrier gas. LA-ICP-MS, however, suffers from limitations in analyzing high ionization potential elements as well as elements subject to atmospheric and argon based interferences. LA-ICP-MS also has limitations in analyzing major elements due to detector saturation. An alternative laser ablation technique, Laser Induced Breakdown Spectroscopy (LIBS), employs an optical spectrometer integrated into the laser ablation system that analyzes the laser induced plasma at the sample surface across the entire optical spectrum for emission lines of every element in the periodic table. Elements that are difficult or impossible to measure with LA-ICP-MS are now possible to analyze with LIBS down to low ppm levels with CCD and/or ICCD detection. We introduce a new laser based technique, “Tandem LA-LIBS”, that combines LA for ICP-MS and LIBS into one integrated laser ablation system. This system has the effect of expanding the elemental coverage and the dynamic range of the laser ablation experiment as measurements from ppb to % level matrix elements can now be analyzed in a single ablation experiment. We present both femtosecond and nanosecond Tandem LA-LIBS quantitative and qualitative data on wide range of geological materials for those elements that are difficult or impossible by traditional LA-ICP-MS techniques such as F, H, O, N, C, S, halogens, etc. We also demonstrate that the simultaneous measurement of trace, minor and major elements are now possible in a single laser ablation experiment with Tandem LA-LIBS technology.

LA-ICP-MS↗
DOE OSTI2022

Chemical Grafting of Highly Dispersed VO x /CeO 2 for Increased Catalytic Activity in Methanol Oxidative Dehydrogenation

Vanadia supported on well-defned ceria nanocubes are synthesized at various loadings using a liquid-phase chemical grafting technique and are compared to those prepared using traditional incipient wetness impregnation. Raman and IR characterization reveal that, as vanadia loading is increased to near monolayer coverage, vanadia deposited using grafting shows greatly enhanced dispersion (i.e., improved VO x monomer/dimer distribution). Methanol is used as a probe molecule to explore the redox behavior of the catalysts. IR and temperature programmed desorption of methanol show increased CO 2 formation occurs on the bare ceria support and increasing the dispersion of vanadia promotes dehydrogenation to formaldehyde due to the inhibited oxygen vacancy formation on VO x /CeO 2 . Hydrogen temperature programmed reduction demonstrates that the catalyst reducibility and formation of surface oxygen vacancy are directly related to the degree of vanadia oligomerization. In conclusion, the samples prepared using grafting exhibit superior catalytic performance for methanol oxidative dehydrogenation to formaldehyde compared to the impregnated samples, due to the presence of highly dispersed VO x species (i.e., monomers and dimers).

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

Effect of Pressure and Temperature on Carbon Dioxide Reduction at a Plasmonically Active Silver Cathode

Here, carbon dioxide reduction at a plasmonically active silver cathode was investigated by varying the pressure and temperature at multiple applied potentials under both dark and illuminated conditions to understand the mechanism of selectivity changes driven by plasmon-enhanced electrochemical conversion. Carbon dioxide partial pressures (P Co 2 ) from 0.2 to 1 atm were studied during linear sweep voltammetry and chronoamperometry at -0.7, -0.9, and -1.1 V RHE . At a given applied overpotential the total current density increased with increasing P Co 2 in both the dark and the light, but there were significant differences in the Tafel behavior between dark and illuminated conditions. The reduction of CO 2 to carbon monoxide (CO) was found to have first-order behavior with respect to P Co 2 at all applied potentials in both the dark and the light, likely indicating no change in the rate-determining step upon illumination. Activity for the hydrogen (H 2 ) evolution reaction decreased with increasing P Co 2 at slightly different rates in the dark and the light at each applied potential, making it unclear if light is influencing CO or H 2 intermediate adsorbate coverage. Both formate and methanol production showed no dependence on P Co 2 under any conditions, but the true reaction orders may be masked by the much higher activity for CO and H 2 at the silver cathode. The investigation of product distribution with temperature at 14, 22, and 32°C at -0.7, -0.9, and -1.1 V RHE in both the dark and the light demonstrated that the selectivity changes observed upon illumination are not caused by local heating of the cathode surface.

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

Stabilization of Cu 2 O through Site-Selective Formation of a Co 1 Cu Hybrid Single-Atom Catalyst

Single-atom catalysts (SACs) consist of a low coverage of isolated metal atoms dispersed on a metal substrate, called single-atom alloys (SAAs), or alternatively single metal atoms coordinated to oxygen atoms on an oxide support. We present the synthesis of a new type of Co 1 Cu SAC centers on a Cu 2 O(111) support by means of a site-selective atomic layer deposition technique. Isolated metallic Co atoms selectively coordinate to the native oxygen vacancy sites (Cu sites) of the reconstructed Cu 2 O(111) surface, forming a Co 1 Cu SAA with no direct Co–O x bonds. The centers, here referred to as Co 1 Cu hybrid SACs, are found to stabilize the active Cu + sites of the low-cost Cu 2 O catalyst that otherwise is prone to deactivation under reaction conditions. The stability of the Cu 2 O(111) surface was investigated by synchrotron radiation-based ambient-pressure X-ray photoelectron spectroscopy under reducing CO environment. The structure and reduction reaction are modeled by density functional theory calculations, in good agreement with experimental results.

36 MATERIALS SCIENCE↗