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Results for “preferential CO oxidation”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

CO 2 electro-reduction on Cu 3 P: Role of Cu(I) oxidation state and surface facet structure in C 1 -formate production and H 2 selectivity

We report the catalytic activity and mechanism of copper(I) phosphide, Cu 3 P, with predominant [00Ι] facet exposure for the electrochemical reduction of CO 2 (CO 2 RR) to formic acid. Crystalline nanosheets of this compound that show a preferential [00Ι] facet orientation exhibit undiminished CO 2 RR activity after 16 hours with full retention of crystal structure and surface chemical speciation and no detectable corrosion. In contrast to the range of products formed on Cu metal, CuO, and Cu 2 O, the CO 2 RR on Cu 3 P [00Ι] produces mainly hydrogen and formate as the sole carbon product in KHCO 3 electrolyte. Analysis of the Cu 3 P [00Ι] facet by HAADF-STEM was used to determine the surface lattice structure, while both XPS and Auger spectroscopies were used to determine the surface chemical speciation from the kinetic energies of ionized electrons. The presented analysis identifies isolated trigonal CuP 3 sites on the Cu 3 P[00Ι]-Cu 3 P 3 terminated surface and the Cu(I) oxidation state as precursor to the active catalyst. The CO 2 RR selectivity to formate and the higher turnover rate for H 2 production on the [00Ι] facet allows a structure-activity analysis and chemical mechanism to be proposed. Formation of a surface hydride at isolated *H-CuP 3 sites is proposed as the catalytic site in forming both H 2 and formate, while the long Cu—Cu separation retards forming C-C coupling products. In conclusion, these results disprove previously published claims of Cu(I) oxidation state as a sufficient criterion to promote CO 2 RR to C 2+ products, show that stronger bonded hydrides, *H-CuP 3 on Cu 3 P, favor production of the C1 product formate over all other carbon products, and predict that stronger formate binding (bidentate) is needed for CO 2 RR currents to compete with H 2 production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Modulating coordinate site occupancy in high-entropy spinel electrocatalysts

High entropy spinel oxides provide a versatile platform for electrocatalysis because multiple metal cations can be incorporated into a single crystalline lattice, enabling tunable electronic structures. However, controlling how these cations distribute between tetrahedral and octahedral coordination sites remains a major challenge, limiting rational catalyst design. Here, we modulate cation coordination site occupancy between tetrahedral and octahedral sites in a Co–Fe–Cr–Mn–Ni framework by introducing a sixth cation (Zn, Ga, Mg, or Al) with distinct site preference energies. Using density functional theory, synchrotron X-ray absorption spectroscopy, and magnetic circular dichroism, we demonstrate that Zn preferentially occupies tetrahedral sites, driving increased octahedral occupancy of cobalt. This redistribution increases the population of octahedrally coordinated cobalt in mixed oxidation states, enhances electrical conductivity, and improves oxygen evolution reaction activity. Our findings establish coordination site occupancy as a critical design parameter, providing a strategic pathway for tailoring multicomponent spinel electrocatalysts with optimized performance.

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

Three-dimensional strain dynamics govern the hysteresis in heterogeneous catalysis

Understanding catalysts strain dynamic behaviours is crucial for the development of cost-effective, efficient, stable and long-lasting catalysts. Here, we reveal in situ three-dimensional strain evolution of single gold nanocrystals during a catalytic CO oxidation reaction under operando conditions with coherent X-ray diffractive imaging. We report direct observation of anisotropic strain dynamics at the nanoscale, where identically crystallographically-oriented facets are qualitatively differently affected by strain leading to preferential active sites formation. Interestingly, the single nanoparticle elastic energy landscape, which we map with attojoule precision, depends on heating versus cooling cycles. The hysteresis observed at the single particle level is following the normal/inverse hysteresis loops of the catalytic performances. This approach opens a powerful avenue for studying, at the single particle level, catalytic nanomaterials and deactivation processes under operando conditions that will enable profound insights into nanoscale catalytic mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Oxophilicity Drives Oxygen Transfer at a Palladium–Silver Interface for Increased CO Oxidation Activity

A single-layer AgO x phase grown on Ag(111) efficiently transfers oxygen to Pd domains at room temperature, rendering the Pd-decorated surface highly reactive toward CO oxidation. Here, oxygen transfer from AgO x to Pd and the surface reactivity toward CO were investigated as a function of the Pd coverage using X-ray photoelectron spectroscopy, surface infrared spectroscopy of adsorbed CO, temperature-programmed reaction spectroscopy, and density functional theory (DFT) calculations. Our results show that all of the oxygen from the AgO x layer (~0.375 monolayer) migrates to the surface of Pd during formation of a nearly complete Pd bilayer at 300 K and that the oxygen coverages generated on Pd increase as the Pd cluster size decreases, reaching values that exceed the oxygen concentration in the AgO x layer by as much as a factor of 2. Experimental measurements and DFT calculations show that preferential binding of oxygen on the edges of the Pd clusters enhances the oxygen coverage on Pd clusters of decreasing size and produces a heterogeneous spatial distribution of oxygen. CO adsorbs in high coverages at 100 K by binding on both the terraces and O-rich edges of the Pd clusters. During subsequent heating, oxidation of the adsorbed CO consumes nearly all of the oxygen that transferred from AgO x to the Pd domains; in contrast, the pure AgO x layer exhibits limited reactivity toward CO adsorbed at 100 K. These results demonstrate that differences in oxophilicity drive facile oxygen transfer from Ag to the edges of Pd nanoclusters and thereby give rise to an efficient pathway for CO oxidation on bimetallic PdAg surfaces. The cooperation between the Pd and Ag domains results in near-interfacial chemistry that may be broadly important in catalysis by bimetallic alloys.

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

Impact of Mg on Pd-based Methane Oxidation Catalysts for Lean-burn Natural Gas Emissions Control

More efficient lean-burn, natural gas engines are limited by greenhouse gas emissions due to methane oxidation catalysts (MOC) that suffer from water inhibition and high temperature activation. Herein, we report that the addition of Mg to supported 1 wt.% Pd MOCs improved hydrothermal stability even after severe hydrothermal aging. The superior methane oxidation activity compared to the corresponding Mg-free catalyst was attributed to (1) influence of Mg during surface roughening and restructuring at 700 °C on metal-support interaction, (2) reducibility of PdOx sites and (3) preferential stabilization of active Pd (1 0 0) facets in the sample as was evidenced by H 2 TPR and CO TPD characterization experiments. Methane conversion under synthetic exhaust conditions relevant to natural gas, lean-burn engines were investigated. In conclusion, BET, TPR, CO pulse chemisorption followed by TPD provided valuable insights into the surface area, pore volume, reducibility, Pd dispersion and Pd particle size of the selected catalyst samples.

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

Centimeter-Scale Pillared-Layer Metal–Organic Framework Thin Films Mediated by Hydroxy Double Salt Intermediates for CO 2 Sensor Applications

Fabrication of metal–organic framework (MOF) thin films over macroscopic surface areas is a subject of great interest for gas sensor application platforms such as optics and microelectronics. However, a direct synthesis of MOF films at ambient conditions, in particular pillared-layer MOF films due to their anisotropic structures, remains a significant challenge. Herein, we demonstrate for the first time a facile construction of dense and continuous pillared-layer MOF thin films on a centimeter scale via an aluminum-doped zinc oxide template and hydroxy double salt (HDS) intermediates at room temperature. A series of Cu(II)-based pillared MOFs with different 1,4-benzenedicarboxylic acid (bdc) ligands were explored for optimizing MOF film formation for CO 2 sensor applications. Nonpolar ligands with lower water solubility preferentially formed crystalline pillared MOF structures from HDS intermediates. A Cu 2 (ndc) 2 (dabco) (ndc = 1,4-naphthalene-bdc; dabco = 1,4-diazabicyclo[2.2.2]octane) MOF demonstrated the most dense and uniform film growth with micrometer thickness over one square centimeter area. This synthetic approach for growing Cu 2 (ndc) 2 (dabco) MOF thin films was successfully translated toward two sensing platforms: a quartz crystal microbalance and an optical fiber sensor. These Cu 2 (ndc) 2 (dabco) MOF-coated sensors displayed sensitivity toward CO 2 and response/recovery time on the scale of seconds, even at moderate humidity levels. Finally, this work provides a road map for producing continuous and anisotropic crystalline MOF thin films over a centimeter scale area on various substrates, which will greatly facilitate their utilization in MOF-based sensor devices, among other applications.

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

Concentration‐Discharge Relationships of Dissolved Rhenium in Alpine Catchments Reveal Its Use as a Tracer of Oxidative Weathering

Abstract Oxidative weathering of sedimentary rocks plays an important role in the global carbon cycle. Rhenium (Re) has been proposed as a tracer of rock organic carbon (OC petro ) oxidation. However, the sources of Re and its mobilization by hydrological processes remain poorly constrained. Here, we examine dissolved Re as a function of water discharge, using samples collected from three alpine catchments that drain sedimentary rocks in Switzerland (Erlenbach and Vogelbach) and Colorado, USA (East River). The Swiss catchments reveal a higher dissolved Re flux in the catchment with higher erosion rates, but have similar [Re]/[Na + ] and [Re]/[SO 4 2− ] ratios, which indicate a dominance of Re from OC petro . Despite differences in rock type and hydro‐climatic setting, the three catchments have a positive correlation between river water [Re]/[Na + ] and [Re]/[SO 4 2− ] and water discharge. We propose that this reflects preferential routing of Re from a near‐surface, oxidative weathering zone. The observations support the use of Re as a proxy to trace rock‐organic carbon oxidation, and suggest it may be a hydrological tracer of vadose zone processes. We apply the Re proxy and estimate CO 2 release by OC petro oxidation of 5.7 +6.6 / −2.0 tC km −2 yr −1 for the Erlenbach. The overall weathering intensity was ∼40%, meaning that the corresponding export of unweathered OC petro in river sediments is large, and the findings call for more measurements of OC petro oxidation in mountains and rivers as they cross floodplains.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2002

Knowledge of Pest Resistance in SiC/BN/SiC Composites Improved

Ceramic-matrix composites (CMC's) consisting of a silicon carbide matrix reinforced with boron-nitride- (BN-) coated silicon carbide (SiC) fibers are strong contenders for commercial and aerospace applications (in particular, the hot sections of high-performance turbine engines in advanced aircraft and generators). They have very good mechanical properties below approximately 600 C and above approximately 1000 C. Between those temperatures, however, the BN coating oxidizes easily, and the oxidation of the SiC matrix is too sluggish to seal off the composite with a protective layer of silica. In that temperature interval, the preferential oxidation of the BN weakens and embrittles the composite. That phenomenon, referred to as "pest" degradation, is the focus of this work, which aims to identify the causes of and remedies for pesting. Previous work established that pesting in Hi-Nicalon (Nippon Carbon Co., Ltd., Japan)/SiC composites was caused by a layer of free carbon that undermined the oxidation resistance of the BN. New work suggests that composites containing a source of carbon are prone to severe pesting and that those that are free of elemental carbon are resistant pesting. Pest resistance was assessed by exposing machined samples for 100 to 150 hr in an atmospheric burner rig at 600 to 1100 C, followed by a tensile fracture test to measure residual mechanical properties and by characterization of the interphase microstructure. Whether the elemental carbon came from intrinsic or extrinsic sources, its presence induced the tensile strength to drop by over 50 percent in the burner rig, with an even more severe loss of fracture strain. A likely mechanism by which burnoff of the carbon layer exposes the BN to accelerated flank attack by ambient oxidants is shown. The BN is replaced with borosilicates that attack the fiber, and ultimately with silica that embrittles the composites by rigidly bonding components. Thus, the study has shown that pesting can be prevented in SiC/BN/SiC, or at least reduced, by simply excluding free carbon. These studies continue, and plans for future work include investigating the role that carbon may play elsewhere in the interphase region.

Thomas-Ogbuji, Linus U.↗
DOE OSTI2021

Enhancing the inherent catalytic activity and stability of TiO 2 supported Pt single-atoms at CeO x –TiO 2 interfaces

Single-atoms (SAs) with atomically coordinated reaction centers are considered the next generation of catalysts that can exhibit exceptional catalytic efficiency. However, the general concern about thermodynamic vulnerabilities of SAs questions their practical value. Moreover, whether the inherent catalytic nature of SAs is superior compared with that of larger nanoparticles is still under debate. Here, we address two controversies by a comparative study using two catalysts: Pt/TiO 2 and Pt/CeO x –TiO 2 . Based on a hierarchical study of density functional theory, time-resolved catalysis performance test, in situ infrared spectroscopy, and operando X-ray absorption spectroscopy, we could unveil the catalytic nature of Pt-SAs and their stability. By utilizing the heterogeneous interface formed between TiO 2 supporting particles and CeO x clusters formed on the surface of TiO 2 , we preferentially synthesized Pt-SAs pinned at the CeO x –TiO 2 interfaces on CeO x –TiO 2 hybrid-oxide supports. The strong electronic coupling between the Pt-SAs and the Ce ions at the CeO x –TiO 2 interfaces enhanced the catalytic activity toward CO oxidation of Pt-SAs and improved the long-term stability under CO oxidation conditions. The CO oxidation activity of Pt-SAs stabilized at CeO x –TiO 2 was improved by 13.5 times at 200 °C compared with the Pt-SAs on TiO 2 . The results present how to easily improve the activity and stability of Pt-SAs using a simple interface control method. Moreover, we demonstrate that the catalytic activity and the stability of Pt-SAs can be monitored through the chemical state of the interfaces. Finally, our study provides comprehensive understanding about the catalytic nature as well as a novel strategy toward applications of Pt-SAs, enabling sustainable use of Pt in heterogeneous catalysts.

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

Surface Science Studies of Selective Fischer-Tropsch Chemistry on Cobalt Carbide Surfaces

Advances in catalysis science are critical to the progress of the United States. Catalysis is employed, in one way or another, in the production of almost every chemical and product manufactured. The catalysis research that we undertook here, regarding the role of specific facets of cobalt carbide in the Fischer-Tropsch production of low molecular weight olefins (FTO), is motivated by the work of many previous investigators. In particular two research groups from China had discovered FTO catalysts that work very selectively for low molecular weight olefins coupled with low production of methane. These are potentially very important findings that could find significant industrial utility if improvements can be discovered. With the research undertaken here we chose to focus on one of these studies and especially the Co 2 C surfaces that they implicate as being responsible for this exciting FTO catalysis with low production of methane. In this study, Zhong and co-workers investigated cobalt-manganese oxide catalysts for the Fischer-Tropsch to Olefins process. After reaching steady-state their catalyst showed a good selectivity to light olefins and low selectivity to methane with a carbon monoxide conversion of 31.8% at one atmosphere (with a H 2 /CO ratio of two and a temperature of 250°C). Lower H 2 /CO ratios and lower pressures increased the olefin production. Their catalyst characterization studies indicated that cobalt carbide quadrangular nanoprisms with preferentially exposed (101) and (020) facets were important in favoring lower olefin production and inhibiting methane formation. The authors stated that these cobalt carbide nanoprisms are a promising new catalyst system for directly converting synthesis gas to lower olefins. Motivated by the studies of Zhong and co-workers, our goal with the research here was to contribute to a better understanding of catalysis science through the study of surface chemical reactions related to the Fischer-Tropsch to Olefins reaction on specific facets of planar model cobalt carbide catalysts in ultrahigh vacuum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Response of soil nutrient pools and microbiomes to recurrent wildfire disturbance and varying burn severities in a mixed conifer forest

Wildfire is a pervasive disturbance in mixed-conifer forests, yet the relative influence of fire recurrence versus burn severity on soil biogeochemistry and microbial communities remains poorly quantified. We examined a natural gradient of fire history (0–3 prior fires) and burn severity (low–high) spanning 50 yr in a mixed-conifer ecosystem to assess how repeated fire shapes soil carbon (C) and nitrogen (N) pools, their isotopic signatures, mineral and particulate fractions, microbial community composition, carbon-use, CO₂ fluxes, and vegetation cover. Successive fires produced progressively higher bare-ground percentages and lower tree cover, which were tightly linked to declines in microbial diversity and reductions bulk %C, and %N. δ 13 C increased with fire frequency, indicating preferential loss of labile C through combustion or enhanced microbial oxidation, thereby explaining the observed net soil-C decline. Conversely, δ 15 N decreased and pH increased as tree density declined, reflecting altered N cycling and reduced acidification in post-fire soils. Fire recurrence, more than severity, corresponded with a marked shift in the bacterial community: for example, Xanthobacteraceae—key N-fixers and C-cyclers—diminished, while N-fixing Bacillaceae increased, underscoring the tightly coupled nature of soil nutrient dynamics and microbiome composition after repeated burns. Our results demonstrate that fire recurrence appears to be a stronger driver of post-fire soil ecosystem responses in this mixed-conifer forest, influencing both abiotic nutrient pools and the functional potential of the soil microbiome. These findings provide a more enhanced assessment and understanding to date of the biogeochemical consequences of repeated wildfire disturbance that can be used to inform management strategies aimed at preserving soil health in fire-prone landscapes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Deactivation by Potassium Accumulation on a Pt/TiO 2 Bifunctional Catalyst for Biomass Catalytic Fast Pyrolysis

Biomass-derived feedstocks bring significant challenges to the longevity of the catalysts used for their conversion, and alkali metals, for example, K, in the feedstock have been widely ascribed as one of the important factors causing catalyst deactivation. To address this challenge, it is critical to understand the mechanism of catalyst deactivation caused by K accumulation to guide the improvement of catalysts and processes and the development of catalyst regeneration strategies. In this work, we report a deep understanding of the impact of K on a bifunctional Pt/TiO 2 catalyst, which is an efficient catalyst for the ex situ catalytic fast pyrolysis of biomass. We simulated the K-poisoning of Pt/TiO 2 catalysts by purposely loading different amounts of K (100-6000 ppm by weight) on the catalysts. A series of characterization approaches, including scanning transmission electron microscopy, Fourier transform infrared spectroscopy, and chemical titration, were combined with a kinetic assessment of multiple probe reactions to elucidate the mechanism of Pt/TiO 2 deactivation by K accumulation. At low K loadings (<800 ppm), K preferentially poisons the strong Lewis acid sites, leading to significantly reduced activity for acid-catalyzed alcohol dehydration. However, acetone condensation is less sensitive to the poisoning of strong Lewis acid sites. Reactions that occur on Pt sites or at the metal-support interface, including alkene hydrogenation, m-cresol hydrodeoxygenation (HDO), and CO oxidation, were not impacted. At high K loadings (>800 ppm), K starts to accumulate on the Pt-TiO 2 interfacial area, poisoning the interfacial active sites for HDO and CO oxidation reactions. We further found that the poisoning of the Pt/TiO 2 catalyst by K is reversible, and water washing can successfully remove the accumulated K and recover the activities for both alcohol dehydration and m-cresol HDO reactions.

09 BIOMASS FUELS↗
DOE OSTI2024

Metabolite release by nitrifiers facilitates metabolic interactions in the ocean

Microbial chemoautotroph-heterotroph interactions may play a pivotal role in the cycling of carbon in the deep ocean, reminiscent of phytoplankton-heterotroph associations in surface waters. Nitrifiers are the most abundant chemoautotrophs in the global ocean, yet very little is known about nitrifier metabolite production, release, and transfer to heterotrophic microbial communities. To elucidate which organic compounds are released by nitrifiers and potentially available to heterotrophs, we characterized the exo- and endometabolomes of the ammonia-oxidizing archaeon Nitrosopumilus adriaticus CCS1 and the nitrite-oxidizing bacterium Nitrospina gracilis Nb-211. Nitrifier endometabolome composition was not a good predictor of exometabolite availability, indicating that metabolites were predominately released by mechanisms other than cell death/lysis. Although both nitrifiers released labile organic compounds, N. adriaticus preferentially released amino acids, particularly glycine, suggesting that its cell membranes might be more permeable to small, hydrophobic amino acids. We further initiated co-culture systems between each nitrifier and a heterotrophic alphaproteobacterium, and compared exometabolite and transcript patterns of nitrifiers grown axenically to those in co-culture. In particular, B vitamins exhibited dynamic production and consumption patterns in nitrifier-heterotroph co-cultures. We observed an increased production of vitamin B 2 and the vitamin B 12 lower ligand dimethylbenzimidazole by N. adriaticus and N. gracilis, respectively. In contrast, the heterotroph likely produced vitamin B 5 in co-culture with both nitrifiers and consumed the vitamin B 7 precursor dethiobiotin when grown with N. gracilis. Our results indicate that B vitamins and their precursors could play a particularly important role in governing specific metabolic interactions between nitrifiers and heterotrophic microbes in the ocean.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Multimodal correlative imaging and modelling of phosphorus uptake from soil by hyphae of mycorrhizal fungi

Phosphorus (P) is essential for plant growth. Arbuscular mycorrhizal fungi (AMF) aid its uptake by acquiring P from sources distant from roots in return for carbon. Little is known about how AMF colonise soil pore-space, and models of AMF-enhanced P-uptake are poorly validated. We used synchrotron X-ray computed tomography to visualize mycorrhizas in soil and synchrotron X-ray fluorescence/X-ray absorption near edge structure (XRF/XANES) elemental mapping for P, sulphur (S) and aluminium (Al) in combination with modelling. We found that AMF inoculation had a suppressive effect on colonisation by other soil fungi and identified differences in structure and growth rate between hyphae of AMF and nonmycorrhizal fungi. Our results showed that AMF co-locate with areas of high P and low Al, and preferentially associate with organic-type P species over Al-rich inorganic P. We discovered that AMF avoid Al-rich areas as a source of P. Sulphur-rich regions were found to be correlated with higher hyphal density and an increased organic-associated P-pool, whilst oxidized S-species were found close to AMF hyphae. Increased S oxidation close to AMF suggested the observed changes were microbiome-related. Our experimentally-validated model led to an estimate of P-uptake by AMF hyphae that is an order of magnitude lower than rates previously estimated – a result with significant implications for the modelling of plant–soil–AMF interactions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Understanding the effect of organic coatings on 4-nitrostyrene hydrogenation selectivity over Pt/TiO 2 catalysts

The hydrogenation of 4-nitrostyrene was investigated over Pt/TiO 2 catalysts to understand the effects of different catalyst coatings on product selectivity and reaction rates. This reaction is a much-investigated selectivity probe due to difficulty in controlling reactivity between the nitro and vinyl groups of 4-nitrostyrene, with C=C reduction generally being more favorable. 4-Nitrostyrene hydrogenation reactions were carried out in a batch reactor using uncoated, organothiol coated, phosphonic acid (PA) coated, and ion-conducting polymer (ionomer) coated catalysts. Thiols form dense coatings on Pt surfaces, whereas PAs preferentially accumulate on TiO 2 ; ionomer binding preference is unknown for this type of catalyst. The coating densities of the thiols and PAs were varied to observe the effects of loading on catalytic activity and reaction selectivity relative to the uncoated catalyst. Changes in selectivity were observed for catalysts with all coatings, with thiol coatings shifting selectivity towards the nitro reduction product, 4-vinylaniline (4-VA), and both ionomer and PA coatings shifting towards 4-ethylnitrobenzene, the olefin hydrogenation product. It was observed that selectivity toward 4-VA increased with thiol coating density, where 1,2-benzenedithiol (BDT) coated catalysts exhibited a selectivity of >99%. These changes were attributed to the identity of the adsorption sites blocked by the different coatings: blocking of metal sites via thiols decreased the rate of C=C hydrogenation, whereas blocking of TiO 2 sites by PAs decreased the rate of nitro group hydrogenation. The changes observed for ionomer and PA coatings suggested that ionomers, like PAs, bind preferentially to the metal oxide support rather than the active metal. This work provides new support to the proposal that nitro group hydrogenation preferentially occurs on TiO 2 sites after hydrogen spillover and underscores how selection of ligand functionality can be used to tune catalyst selectivity.

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

Polyelectrolyte Complex Coacervation across a Broad Range of Charge Densities

Polyelectrolyte complex coacervates of homologous (co)polyelectrolytes with a near-ideally random distribution of a charged and neutral ethylene oxide comonomer were synthesized. The unique platform provided by these building blocks enabled an investigation of the phase behavior across charge fractions 0.10 ≤ f ≤ 1.0. Experimental phase diagrams for f = 0.30–1.0 were obtained from thermogravimetric analysis of complex and supernatant phases and contrasted with molecular dynamics simulations and theoretical scaling laws. At intermediate to high f, a dependence of polymer weight fraction in the salt-free coacervate phase (w P,c ) of w P,c ~ f 0.37±0.01 was extracted; this trend was in good agreement with accompanying simulation predictions. Below f = 0.50, w P,c was found to decrease more dramatically, qualitatively in line with theory and simulations predicting an exponent of 2/3 at f ≤ 0.25. Preferential salt partitioning to either coacervate or supernatant was found to be dictated by the chemistry of the constituent (co)polyelectrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ammonia-oxidizing bacteria and archaea exhibit differential nitrogen source preferences

Ammonia-oxidizing microorganisms (AOM) contribute to one of the largest nitrogen fluxes in the global nitrogen budget. Four distinct lineages of AOM: ammonia-oxidizing archaea (AOA), beta- and gamma-proteobacterial ammonia-oxidizing bacteria (β-AOB and γ-AOB) and complete ammonia oxidizers (comammox), are thought to compete for ammonia as their primary nitrogen substrate. In addition, many AOM species can utilize urea as an alternative energy and nitrogen source through hydrolysis to ammonia. How the coordination of ammonia and urea metabolism in AOM influences their ecology remains poorly understood. Here we use stable isotope tracing, kinetics and transcriptomics experiments to show that representatives of the AOM lineages employ distinct regulatory strategies for ammonia or urea utilization, thereby minimizing direct substrate competition. The tested AOA and comammox species preferentially used ammonia over urea, while β-AOB favoured urea utilization, repressed ammonia transport in the presence of urea and showed higher affinity for urea than for ammonia. Characterized γ-AOB co-utilized both substrates. Furthermore, these results reveal contrasting niche adaptation and coexistence patterns among the major AOM lineages.

54 ENVIRONMENTAL SCIENCES↗