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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Surface Processes Control the Fate of Reactive Oxidants Generated by Electrochemical Activation of Hydrogen Peroxide on Stainless-Steel Electrodes

Low-cost stainless-steel electrodes can activate hydrogen peroxide (H 2 O 2 ) by converting it into a hydroxyl radical ( • OH) and other reactive oxidants. At an applied potential of +0.020 V, the stainless-steel electrode produced • OH with a yield that was over an order of magnitude higher than that reported for other systems that employ iron oxides as catalysts under circumneutral pH conditions. Decreasing the applied potential at pH 8 and 9 enhanced the rate of H 2 O 2 loss by shifting the process to a reaction mechanism that resulted in the formation of an Fe(IV) species. Significant metal leaching was only observed under acidic pH conditions (i.e., at pH <6), with the release of dissolved Fe and Cr occurring as the thickness of the passivation layer decreased. Despite the relatively high yield of • OH production under circumneutral pH conditions, most of the oxidants were scavenged by the electrode surface when contaminant concentrations comparable to those expected in drinking water sources were tested. The stainless-steel electrode efficiently removed trace organic contaminants from an authentic surface water sample without contaminating the water with Fe and Cr. With further development, stainless-steel electrodes could provide a cost-effective alternative to other H 2 O 2 activation processes, such as those by ultraviolet light.

42 ENGINEERING↗
DOE OSTI2021

Pt 3 Sn nanoparticles enriched with SnO 2 /Pt 3 Sn interfaces for highly efficient alcohol electrooxidation

Pt 3 Sn nanoparticles (NPs) enriched with Pt 3 Sn/ultra-small SnO 2 interfaces (Pt 3 Sn@u-SnO 2 /NG) were synthesized through a thermal treatment of Pt 2 Sn/NG in a H 2 atmosphere, followed by annealing under H 2 and air conditions. The unique structure of Pt 3 Sn NPs enriched with Pt 3 Sn/SnO 2 interfaces was observed on the Pt 3 Sn@u-SnO 2 /NG catalyst based on HRTEM. The optimized Pt 3 Sn@u-SnO 2 /NG catalyst achieves high catalytic activity with an ethanol oxidation reaction (EOR) activity of 366 mA mg Pt -1 and a methanol oxidation reaction (MOR) activity of 503 mA mg Pt -1 at the potential of 0.7 V, which are eight-fold and five-fold higher than those for the commercial Pt/C catalyst (44 and 99 mA mg Pt -1 , respectively). The Pt 3 Sn@u-SnO 2 /NG catalyst is found to be 3 times more stable and have higher CO tolerance than Pt/C. The outstanding performance of the Pt 3 Sn@u-SnO 2 /NG catalyst should be ascribed to the synergetic effect induced by the unique structure of Pt 3 Sn NPs enriched with Pt 3 Sn/SnO 2 interfaces. The synergetic effect between Pt 3 Sn NPs and ultra-small SnO 2 increases the performance for alcohol oxidation because the Sn in both Pt 3 Sn and SnO 2 favors the removal of CO ads on the nearby Pt by providing OH ads species at low potentials. The present work suggests that the Pt 3 Sn@u-SnO 2 is indeed a unique kind of efficient electrocatalyst for alcohol electrooxidation.

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

Carbon Nanospheres Loaded with Ir Single Atoms: Enhancing the Activity toward Formic Acid Oxidation by Increasing the Porosity

Theoretically, single-atom catalysts (SACs) offer 100 % atom utilization, making them strong candidates to replace expensive nanoparticles for catalysis. However, the structural supports used to anchor the SACs dramatically reduce the utilization efficiency of atoms ( i. e ., the percent of atoms actually accessible by reactants) by either encapsulating the SACs completely or creating severe diffusion limitation. Either of which leads to an overall low atom utilization and thus poor electrocatalytic activity similar to that of nanoparticles. In addressing this issue, we systematically investigated how the porous structure of carbon nanospheres affects the activity of Ir-SACs toward formic acid oxidation (FAO). Specifically, we utilized a kinetically-controlled growth strategy to produce uniform carbon nanospheres featuring yolk-shell, mesoporous, and hollow structures with Ir-SACs loaded throughout the structure. At a high specific surface area of 441 m 2 g -1 and exposed metal content of 1.82 wt %, the Ir-SACs based on mesoporous carbon nanospheres showed a remarkable FAO peak current density of 30.6 mA cm -2 , which was 283 and 46 times greater when benchmarked against the catalysts based on solid carbon nanospheres and 20 wt % Ir/C, respectively.

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

Ce x Zr 1– x O 2 -Supported CrO x Catalysts for CO 2 -Assisted Oxidative Dehydrogenation of Propane–Probing the Active Sites and Strategies for Enhanced Stability

CO 2 -assisted oxidative dehydrogenation of propane (CO 2 -ODH) represents an attractive approach for propylene production and CO 2 utilization. As a soft oxidant, CO 2 can minimize overoxidation of the hydrocarbons to enhance the propylene selectivity while increasing the equilibrium yield. However, a major challenge of CO 2 -ODH is the rapid deactivation of the catalysts. The current study focuses on designing Ce x Zr 1–x O 2 -mixed oxide-supported CrO x catalysts for CO 2 -ODH with enhanced product selectivity and catalyst stability. By doping 0–30% Ce in the Ce x Zr 1–x O 2 mixed oxide support, propane conversion of 53–79% was achieved at 600 °C, with propylene selectivity up to 82%. Compared to the pure ZrO 2 -supported catalyst (i.e., 5 wt %Cr/ZrO 2 ), 20–30 %Ce doped catalysts (i.e., 5 wt %Cr/Ce 0.2 Zr 0.8 O 2 and 5 wt %Cr/Ce 0.3 Zr 0.7 O 2 ) inhibited the formation of CH 4 and ethylene and improved propylene selectivity from 57 to 77–82%. Detailed characterizations of the 5%Cr/Ce 0.2 Zr 0.8 O 2 catalyst and density functional theory (DFT) calculations indicated that Cr 3+ is the active species during the CO 2 -ODH reaction, and the reaction follows a non-redox dehydrogenation pathway. Coke formation was determined to be the primary reason for catalyst deactivation, and the addition of Ce to the ZrO 2 support greatly enhanced the coke resistance, leading to superior stability. Furthermore, coke removal by oxidizing the catalyst in air is effective in restoring its activity.

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

Operational Limits of Redox Metal Oxides Performing Thermochemical Water Splitting

Solar thermochemical hydrogen production is an attractive technology that stores intermittent solar energy in the form of chemical bonds. Efficient operation requires the identification of a redox-active metal oxide (MO x ) material that can achieve high conversion of water to hydrogen at minimal energy input. Water splitting occurs by consecutive reduction and reoxidation reactions of MO x . MO x is reduced to MO x-δ and, in the second step, is reoxidized by water recovering the initial MO x and generate H 2 . The material must reduce at temperatures achievable in concentrated solar receiver/reactors, while maintaining a thermodynamic driving force to split water. At equilibrium, extent of reduction depends on temperature and oxygen partial pressure, and in this analysis, a set of thermodynamic properties, namely, enthalpy and entropy of oxygen vacancy formation, is sufficient to represent MO x . Herein, a method to easily classify materials based on these thermodynamic properties under any condition of oxygen partial pressure and temperature is presented. This method is based on fundamental thermodynamic principles and is applicable for any redox material with known thermodynamic properties. Despite the simplicity of the method, it is believed that this analysis will support future research in targeting thermodynamic properties of redox-active metal oxides.

water splitting↗
DOE OSTI2025

Node-Solution Microenvironment Governs the Selectivity of Thioanisole Oxidation within Catalytic Zr-Based Metal–Organic Framework

Lewis acidic metal oxides, including zirconia (ZrO 2 ), are catalytically active toward oxidative reactions in the presence of sacrificial oxidants like t-butyl hydroperoxide (TBHP). The structural ambiguity and heterogeneity of the ZrO 2 surface impose challenges to chemists in understanding the reaction mechanism down to atomic-level precision. The inorganic, Zr-oxo nodes of many crystalline metal–organic frameworks (MOFs) structurally mimic ZrO 2 . Herein, we report three novel findings: (A) Zr-based MOF, Zr-MOF-808 is catalytically competent in activating TBHP to induce oxygen atom transfer (OAT) reactions to a model substrate, thioanisole, at room temperature, (B) its reaction mechanism can be derived with greater structural precision owing to the crystallinity of the MOF, and (C) the node-binding agent and other reaction conditions significantly impact the selectivity between the singly oxidized methyl phenyl sulfoxide vs the doubly oxidized sulfone. These findings suggest that both the activity and selectivity of OAT reactions within Zr-MOF-808 are governed by the chemistry occurring at the interface of the node and the surrounding reaction medium. Implications of these findings in OAT reactions and other MOF/metal oxide-catalyzed relevant catalysis are discussed.

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

Atomically Precise Single Metal Oxide Cluster Catalyst with Oxygen–Controlled Activity

Single cluster catalysts (SCCs) consisting of atomically precise metal nanoclusters dispersed on supports represent a new frontier of heterogeneous catalysis. However, the ability to synthesize SCCs with high loading and to precisely introduce non-metal atoms to further tune their catalytic activity and reaction scope of SCCs have been longstanding challenges. In this work, a new interface confinement strategy is developed for the synthesis of a high density of atomically precise Ru oxide nanoclusters (Ru 3 O 2 ) on reduced graphene oxide (rGO), attributed to the suppression of diffusion-induced metal cluster aggregation. Ru 3 O 2 /rGO exhibits a significantly enhanced activity for oxidative dehydrogenation of 1,2,3,4-tetrahydroquinoline (THQ) to quinoline with a high yield (≈86%) and selectivity (≈99%), superior to Ru and RuO 2 nanoparticles, and homogeneous single/multiple-site Ru catalysts. In addition, Ru 3 O 2 /rGO is also capable of efficiently catalyzing more complex oxidative reactions involving three reactants. The theoretical calculations reveal that the presence of two oxygen atoms in the Ru 3 O 2 motif not only leads to a weak hydrogen bonding interaction between the THQ reactant and the active site, but also dramatically depletes the density of states near the Fermi level, which is attributed to the increased positive valence state of Ru and the enhanced oxidative activity of the Ru 3 O 2 cluster for hydrogen abstraction.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Stable isotopes as tracers of methane dynamics in Everglades marshes with and without active populations of methane oxidizing bacteria

The stable carbon isotopic composition of CH4 is used to study the processes that affect it during transport through plants from sediment to the atmosphere. The enhancement of CH4 flux from Cladium and Eleocharis over the flux from open water or clipped sites indicated that these plants served as gas conduits between the sediments and the atmosphere. Lowering of the water table below the sediment surface caused an Everglades sawgrass marsh to shift from emission of CH4 to consumption of atmospheric CH4. Cladium transported gases passively mainly via molecular diffusion and/or effusion instead of actively via bulk flow. Stable isotropic data gave no evidence that CH4 oxidation was occurring in the rhizosphere of Cladium. Both CH4 stable carbon isotope and flux data indicated a lack of CH4 oxidation at the sediment-water interface in Everglades marl soils and its presence in peat soils where 40 to 92 percent of the flux across the sediment-water interface was oxidized.

Happell, James D.↗
NASA NTRS1990

Phillips CO-oxidation catalyts for long-lived CO2 lasers: Activity and initial characterization studies

Four different catalysts have been developed specifically for use in sealed carbon dioxide lasers. The catalysts have been designed to be low dusting, stable to shock and vibration, have high activity at low temperatures and have long active lifetimes. Measured global CO oxidation rates range from 1.4 to 2.2 cc CO converted per minute per gram of catalyst at ambient temperature. The catalysts also retain substantial activity at temperatures as low as -35 C. The Phillips laser catalysts are prepared in a variety of different shapes to meet the different pressure drop and gas flow profiles present in the many different styles of lasers. Each catalyst has been tested in sealed TEA lasers and has been shown to substantially increase the sealed life of the laser. Activity measurements made on the precious metal catalysts which were prepared with and without activity promoters showed that the promoter materials increase catalyst CO oxidation activity at least an order of magnitude at ambient temperature. Initial studies using H2 and CO chemisorption, X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS) have shown that the activity promoters do not significantly affect the precious metal crystallite size or the electronic structure around the precious metal. In addition, the formation or lack of formation of solid solutions between the precious metal and promoters has also been shown not to affect the activity of the promoted catalyst.

Kolts, J. H.↗
DOE OSTI2025

CO 2 Adsorption and Hydrogenation on Inverse InO x /Cu(111) Catalysts: Active Role of the Oxide–Metal Interface

The direct conversion of carbon dioxide (CO 2 ) into methanol via hydrogenation is essential for industrial applications. Recent studies on catalysts that contain an inverse oxide/metal configuration have shown very good catalytic performance for the CO 2 hydrogenation to methanol process. Here, in this study, we investigated the behavior of indium oxide-Cu(111) interfaces under pure CO 2 and CO 2 /H 2 mixtures using synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). Initially, a single layer of copper oxide (Cu x O) was grown on the Cu(111) surface by controlled oxidation. On this surface, indium was deposited at room temperature. Oxygen atoms transferred from Cu x O/Cu(111) to the indium metal upon deposition, forming In-O-Cu bonds and active interfaces. Although Cu(111) is not very active for the binding and activation of CO 2 , the formed InO x -Cu(111) interfaces had no problem adsorbing and dissociating the molecule at room temperature. Reaction of CO 2 with H 2 on InO x -Cu(111) yielded surface-bound H 3 CO, CO 2 δ− , CO 3 , and CH x species that are typical intermediates in the production of methanol and other oxygenates. The InO x -Cu(111) interface underwent dynamic chemical changes under reaction conditions, forming In-Cu alloys at low indium coverages (< 0.05 monolayer), while at higher indium coverages a mixture of an In-Cu and InO x was detected in XPS. These findings indicate that InO x /In-Cu interfaces can play a key role in processes aimed at the trapping and valorization of CO 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2020

Activating low-temperature diesel oxidation by single-atom Pt on TiO 2 nanowire array

Supported metal single atom catalysts (SACs) present an emerging class of low-temperature catalysts with high reactivity and selectivity, which, however, face challenges on both durability and practicality. Herein, we report a single-atom Pt catalyst that is strongly anchored on a robust nanowire forest of mesoporous rutile titania grown on the channeled walls of full-size cordierite honeycombs. This Pt SAC exhibits remarkable activity for oxidation of CO and hydrocarbons with 90% conversion at temperatures as low as ~160 °C under simulated diesel exhaust conditions while using 5 times less Pt-group metals than a commercial oxidation catalyst. Such an excellent low-temperature performance is sustained over hydrothermal aging and sulfation as a result of highly dispersed and isolated active single Pt ions bonded at the Ti vacancy sites with 5 or 6 oxygen ions on titania nanowire surfaces.

36 MATERIALS SCIENCE↗
NASA NTRS1994

Active chlorine and nitric oxide formation from chemical rocket plume afterburning

Chlorine and oxides of nitrogen (NO(x)) released into the atmosphere contribute to acid rain (ground level or low-altitude sources) and ozone depletion from the stratosphere (high-altitude sources). Rocket engines have the potential for forming or activating these pollutants in the rocket plume. For instance, H2/O2 rockets can produce thermal NO(x) in their plumes. Emphasis, in the past, has been placed on determining the impact of chlorine release on the stratosphere. To date, very little, if any, information is available to understand what contribution NO(x) emissions from ground-based engine testing and actual rocket launches have on the atmosphere. The goal of this work is to estimate the afterburning emissions from chemical rocket plumes and determine their local stratospheric impact. Our study focuses on the space shuttle rocket motors, which include both the solid rocket boosters (SRB's) and the liquid propellant main engines (SSME's). Rocket plume afterburning is modeled employing a one-dimensional model incorporating two chemical kinetic systems: chemical and thermal equilibria with overlayed nitric oxide chemical kinetics (semi equilibrium) and full finite-rate chemical kinetics. Additionally, the local atmospheric impact immediately following a launch is modeled as the emissions diffuse and chemically react in the stratosphere.

Leone, D. M.↗
DOE OSTI2020

Impacts of anthropogenic gadolinium on the activity of the ammonia oxidizing bacterium Nitrosomonas europaea

Widespread use of gadolinium-based contrast agents in medical imaging has resulted in increased Gd inputs to municipal wastewater treatment plants. Others have reported that typical wastewater treatment does not attenuate Gd, resulting in discharges to natural waters. However, whether elevated Gd impacts the performance of biological treatment has not been investigated. We examined whether gadolinium chloride or Gd chelated with diethylenetriaminepentaacetic acid (DTPA) affected the activity of the model nitrifying bacterium Nitrosomonas europaea. At nominal GdCl 3 additions ranging from 1 to 500 µM, no impact was observed compared to the control. Most (>98%) of the added Gd precipitated, and extracellular GdPO 4 nanoparticles were observed. When chelated with DTPA, Gd remained soluble, but no statistically significant impact on ammonia oxidation was observed until the highest concentrations tested. At 300 and 500 µM Gd-DTPA, a temporary reduction of nitrite production relative to the control (effect size 1.3 mg l -1 and 1.5 mg l -1 , respectively, at 24 h) was seen. By itself, DTPA was highly inhibitory. Modeling suggested that DTPA likely chelated other metals, but adjusting the concentrations of the most abundant metals in the medium, calcium and magnesium, indicated that lowering their free ion activities was probably not the cause of inhibition. Complexation of other essential metals was more likely. Furthermore, our studies indicate that while the low bioavailability of Gd may limit its ecosystem impacts, the role of synthetic ligands used with Gd and other rare earth elements should e considered as the production, use and disposal of these elements increases.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Materials Design Directions for Solar Thermochemical Water Splitting

The sustainable, economical production of molecular hydrogen is a crucial component of a net zero-greenhouse-gas-emissions future. Solar thermochemical water splitting (STWS) offers a renewable route to hydrogen with the potential to help decarbonize several industries, including transportation, manufacturing, mining, metals processing, and electricity generation, as well as provide sustainable hydrogen as a chemical feedstock. STWS uses high temperatures generated from concentrated sunlight or other sustainable means for high-temperature heat to produce hydrogen and oxygen from steam. For example, in its simplest form of a two-step thermochemical cycle, a redox-active metal oxide is heated to ≈1700-2000 K, driving off molecular oxygen while producing oxygen vacancies in the material. The reduced metal oxide then cools (ideally with the extracted heat recuperated for re-use) and, in a separate step, comes into contact with steam, which reacts with oxygen vacancies to produce molecular hydrogen while recovering the original state of the metal oxide. Despite its promising use of the entire solar spectrum to split water thermochemically, the current estimated cost of hydrogen produced via STWS is ≈4-6× the U.S. Department of Energy (DOE) Hydrogen Shot target value of $1/kg. One contributing approach to bridging this cost gap is the design of new materials with improved thermodynamic properties to enable higher efficiencies. The state-of-the-art (SOA) redox-active metal oxide for STWS is ceria (CeO 2 ), due to its close to optimal, although too high, oxygen vacancy formation enthalpy and large configurational and electronic entropy of reduction. However, ceria requires high operating temperatures and its efficiency is insufficient. Therefore, efforts to increase the efficiency of STWS cycles have focused on further optimizing oxygen vacancy formation enthalpies and augmenting the reduction entropy via substitution or doping and materials discovery schemes. Examples of the latter include the perovskites BaCe 0.25 Mn 0.75 O 3 and (Ca,Ce)(Ti,Mn)O 3 . These efforts and others have revealed intuitive chemical principles for the efficient and systematic design of more effective materials, such as the strong correlation between the enthalpies of crystal bond dissociation and solid-state cation reduction with the enthalpy of oxygen vacancy formation, as well as configurational entropy augmentation via the coexistence of two or more redox-active cation sublattices. The purpose of this chapter is to prepare the reader with an up-to-date account of STWS redox-active materials, both the SOA and promising newcomers, as well as to provide chemically intuitive strategies for improving their cycle efficiencies through materials design – in conjunction with ongoing efforts in reactor engineering and gas separations – to reach the cost points for commercial viability. First, we will introduce the thermodynamics of STWS using a two-step, metal-oxide, thermochemical cycle with economics in mind. We also will compare the pros and cons of processes that do or do not involve phase changes. Second, we will describe the qualities that make ceria the SOA STWS redox-active material, as well as its limitations. Third, we will survey some of the most promising candidates to date in the search for materials to supplant ceria, emphasizing the post-ternary, metal-oxide-perovskite alloys. Lastly, we will enumerate and discuss the following materials design directions for STWS redox-active materials: crystal reduction potentials as a proxy for oxygen vacancy formation enthalpies, engineering the electronic and configurational entropy of reduction via f-shells and simultaneous redox, and vetting materials stability via temperature-dependent phase diagrams and melting-point prediction.

08 HYDROGEN↗
DOE OSTI2024

Production of Carbon Nanomaterials and Sorbents from Domestic U.S. Coal (Final Report)

The main goal of this project was to produce high-value carbon nanomaterials and carbon sorbents from domestic coal resources in a cost-effective manner. Four types of domestic coal samples were processed through a combination of deashing, devolatilization, oxidation, reduction, and activation treatments to produce graphene oxide (GO), reduced graphene oxide (RGO), and activated carbon (AC). The precursors and developed materials were extensively characterized by various methods to investigate the impact of the coal feedstock type on the yield and quality of each product. A commercial graphite-based GO sample was included in the experimental work as the baseline material for comparison with the coal-based materials developed in this work. The performed work also included a technoeconomic analysis and cost estimation for a plant processing 20 tons/day coal, a market evaluation for the graphene materials, and a technology gap analysis. A simple process by concentrated nitric acid oxidation is used to oxidize coal precursors for the production of GO. Fine oxidized coal particles that were separated from larger oxidized coal particles had significantly higher oxygen contents and were identified as coal-based GO samples. Coarse oxidized coal particles were used as precursors for production of AC. Based on the Raman spectroscopy results, coal-based GO samples exhibited G and D bands similar to those of graphite-based GO samples. X-ray photoelectron spectroscopy revealed that coal-based GO samples had surface oxygen contents of ~26-35% that were higher than the oxygen contents of graphite-based GO samples. Larger particles of oxidized coal samples were activated under different conditions to produce high surface area functionalized AC. Prepared materials had surface areas exceeding 1,500 m 2 /g and pore volumes more than 1 cm 3 /g with different pore size distributions. Reduced graphene oxide samples were prepared by thermal reduction of both coal-based and graphite-based GO samples at 170-2800 ºC. Coal-based and graphite-based RGO samples exhibited similar carbon contents, Raman spectra, and XRD profiles. Heat treatment above 1500 ºC shifted RGO to synthetic graphite. Among anthracite, bituminous, subbituminous, and lignite coals tested, anthracite was the best precursor to produce carbon nanomaterials exhibiting properties similar to those of graphite-based materials. Anthracite-based carbon nanomaterials also had the highest production yields. Technoeconomic analysis estimated the production cost of GO and RGO for anthracite-based samples at about 2,600 and 4,200 $/ton, respectively, which is about two orders of magnitude lower than the current estimated price of graphite-based materials. Several gaps to further develop the proposed technology were identified and discussed that include process and equipment optimization, process integration, need for additional bench- and pilot-scale experiments, and other items to reduce the scale up risk. Market analysis reports suggested a compound annual growth rate of 40% for graphene and related materials. Short-term applications include composites, inks, and coatings. However, energy storage applications appear to be the dominant potential long-term applications. Different applications of coal-based GO and RGO need to be explored and clear metrics and standards for each application need to be developed.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

Hydrogen activation by rhodium under the cover of a copper oxide thin film

Here, the activation of reactants by catalytically active metal sites at metal-oxide interfaces is important for understanding the effect of metal-support interactions on nanoparticle catalysts and for tuning activity and selectivity. Using a combined experimental and theoretical approach, we studied the activation of H 2 and the effect of CO poisoning on isolated Rh atoms completely or partially covered by a copper oxide (Cu 2 O) thin film. Temperature-programmed desorption (TPD) experiments conducted in ultra-high vacuum (UHV) show that neither a partially nor a fully oxidized Cu 2 O layer grown on a Rh/Cu(111) single-atom alloy can activate hydrogen in UHV. However, in situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments performed at elevated H 2 pressures reveal that Rh significantly accelerates the reduction of these Cu 2 O thin films by hydrogen. Remarkably, the fastest reduction rate is observed for the fully oxidized sample with all Rh sites covered by Cu 2 O. Both TPD and AP-XPS data demonstrate that these covered Rh sites are inaccessible to CO, indicating that Rh under Cu 2 O is active for H 2 dissociation but cannot be poisoned by CO. In contrast, an incomplete oxide film leaves some of the Rh sites exposed and accessible to CO, and hence prone to CO poisoning. Density functional theory calculations demonstrate that unlike many reactions in which hydrogen activation is rate limiting, the rate-determining step in the dissociation of H 2 on thin-film Cu 2 O with Rh underneath is the adsorption of H 2 on the buried Rh site, and once adsorbed, the dissociation of H 2 is barrierless. These calculations also explain why H 2 can only be activated at higher pressures. Together, these results highlight how different the reactivity of atomically dispersed Rh in Cu can be depending on its accessibility through the oxide layer, providing a way to engineer Rh sites that are active for hydrogen activation but resilient to CO poisoning.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Mycorrhiza better predict soil fungal community composition and function than aboveground traits in temperate forest ecosystems

We sampled soil in the organic and mineral horizons beneath two AM-associated (Fraxinus americana, Thuja occidentalis) and two ECM-associated tree species (Betula alleghaniensis, and Tsuga canadensis), with an evergreen and deciduous species in each mycorrhizal group. To characterize fungal communities and organic matter decomposition beneath each tree species, we sequenced the ITS1 region of fungal DNA and measured the potential activity of carbon and nitrogen-targeting extracellular enzymes. Each tree species harbored distinct fungal communities, supporting the need to consider both mycorrhizal type and leaf habit. However, between tree characteristics, mycorrhizal type better predicted fungal communities. Across fungal guilds, saprotrophic fungi were the most important group in shaping fungal community differences in soils beneath all tree species. The effect of leaf habit on carbon and nitrogen-targeting hydrolytic enzymes depended on tree mycorrhizal association in the organic horizon, while oxidative enzyme activities were higher beneath EcM-associated trees across both soil horizons and leaf habits. These data include extracellular hydrolytic and oxidative enzyme activities, ITS sequencing fungal community data, soil carbon to nitrogen, and soil pH. Site level data include climate (mean annual temperature, precipitation), elevation, and soil series and order information.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Effect of Ammonia on the Electrocatalysis of Oxygen Reduction Reaction in Base

We investigated the effect of ammonia on the activity of seven benchmark oxygen reduction reaction (ORR) electrocatalysts, Pt/C, Pd/C, Au/C, Ag/C, commercial Fe–N–C, zeolitic imidazolate framework (ZIF)-based Fe–N–C (Fe-ZIF), and ZIF-based Fe,Co–N–C (Fe,Co-ZIF) in alkaline media and direct ammonia fuel cell (DAFC) relevant conditions using a rotating disk electrode. We found that ammonia exposure causes considerable ORR activity loss for all studied electrocatalysts. Should we rank the electrocatalysts in terms of their ORR activity loss and their irreversible ORR activity loss as the result of exposure to ammonia (from the highest loss to the lowest loss), we get Au/C > Pt/C ≈ Pd/C > Ag/C » commercial Fe–N–C > Fe-ZIF ≈ Fe,Co-ZIF and Pd/C > Au/C > Ag/C > commercial Fe–N–C > Fe-ZIF ≈ Fe,Co-ZIF > Pt/C, respectively. The ammonia oxidation reaction activity and adsorptive properties of the Gerisher-Mauerer reaction intermediates do not govern the trend of the ORR activity loss of Pt/C, Pd/C, Au/C, and Ag/C electrocatalysts. Notably, we found that Pt/C electrocatalyst shows the lowest irreversible ORR activity loss, while Fe-ZIF and Fe,Co-ZIF electrocatalysts show the lowest overall ORR activity loss. Our comprehensive study suggests that Pt-based, Fe-ZIF, and Fe,Co-ZIF electrocatalysts are promising cathode candidates for future DAFCs.

Abbasi, Reza (ORCID:0000000249384151)↗