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At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

In silico assessment of the potential of basalt amendments to reduce N 2 O emissions from bioenergy crops

Abstract The potential of large‐scale deployment of basalt to reduce N 2 O emissions from cultivated soils may contribute to climate stabilization beyond the CO 2 ‐removal effect from enhanced weathering. We used 3 years of field observations from maize ( Zea mays ) and miscanthus ( Miscanthus × giganteus ) to improve the nitrogen (N) module of the DayCent model and evaluate the potential of basalt amendments to reduce N losses and increase yields from two bioenergy crops. We found 20%–60% improvement in our N 2 O flux estimates over previous model descriptions. Model results predict that the application of basalt would reduce N 2 O emissions by 16% in maize and 9% in miscanthus. Lower N 2 O emissions responded to increases in the N 2 :N 2 O ratio of denitrification with basalt‐induced increases in soil pH, with minor contributions from the impact of P additions (a minor component of some basalts) on N immobilization. The larger reduction of N 2 O emissions in maize than in miscanthus was likely explained by a synergistic effect between soil pH and N content, leading to a higher sensitivity of the N 2 :N 2 O ratio to changes in pH in heavily fertilized maize. Basalt amendments led to modest increases in modeled yields and the nitrogen use efficiency (i.e., fertilizer‐N recover in crop production) of maize but did not affect the productivity of miscanthus. However, enhanced soil P availability maintained the long‐term productivity of crops with high nutrient requirements. The alleviation of plant P limitation led to enhanced plant N uptake, thereby contributing to lower microbial N availability and N 2 O emissions from crops with high nutrient requirements. Our results from the improved model suggest that the large‐scale deployment of basalt, by reducing N 2 O fluxes of cropping systems, could contribute to the sustainable intensification of agriculture and enhance the climate mitigation potential of bioenergy with carbon capture and storage strategies.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

The structure of CaO–MgO–Al 2 O 3 –SiO 2 melts and glasses doped with FeO X –NiO

Neutron and x-ray diffraction measurements have been performed on CaO–MgO–Al 2 O 3 –SiO 2 (CMAS) glasses doped with NiO–Fe X O at room temperature, along with x-ray measurements on aerodynamically levitated liquids at ≥2000 K. The disordered structures have been modeled using empirical potential structure refinement to investigate the relation between the aluminosilicate network and the modifying cations. The SiO 4 and AlO 4 tetrahedra are found to have wider Si–O and Al–O bond distance distributions in the glass, and the first Ca–O n coordination shell is highly distorted, redistributing different populations of long and short bonds between the liquid and the glass. The addition of Fe and Ni at low aluminosilicate content increases the number of free oxygens not bonded to AlO 4 or SiO 4 . Mg–O and Fe–O are both found to be predominantly fourfold and fivefold in the liquid and glassy states. Despite these low coordination numbers, their bond angle distributions indicate that they are predominantly in nontetrahedral-type geometries, with ferrous and ferric iron possessing similar coordination environments. The Ca–O and Mg–O average coordination numbers and enthalpies of solution are consistent with their higher reactivity within relatively acidic aluminosilicate melts.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Approaches to investigate crop responses to ozone pollution: from O 3 -FACE to satellite-enabled modeling

Ozone (O 3 ) is a damaging air pollutant to crops. As one of the most reactive oxidants known, O 3 rapidly forms other reactive oxygen species (ROS) once it enters leaves through stomata. Those ROS in turn can cause oxidative stress, reduce photosynthesis, accelerate senescence, and decrease crop yield. To improve and adapt our feed, fuel, and food supply to rising O 3 pollution, a number of Free Air Concentration Enrichment (O 3 -FACE) facilities have been developed around the world and have studied key staple crops. In this review, we provide an overview of the FACE facilities and highlight some of the lessons learned from the last two decades of research. We discuss the differences between C 3 and C 4 crop responses to elevated O 3 , the possible trade-off between productivity and protection, genetic variation in O 3 response within and across species, and how we might leverage this observed variation for crop improvement. We also highlight the need to improve understanding of the interaction between rising O 3 pollution and other aspects of climate change, notably drought. Finally, we propose the use of globally modeled O 3 data that are available at increasing spatial and temporal resolutions to expand upon the research conducted at the limited number of global O 3 -FACE facilities.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Investigation of Ga 2 O 3 as a new transparent conductive oxide for photovoltaics applications

This small innovation project intended to leverage recent activity and advances in ultrawide-bandgap oxide power electronics toward the investigation of Ga 2 O 3 as a transparent conductive oxide (TCO) for use in photovoltaics (PV). Ga 2 O 3 ’s theoretical advantage over incumbent TCOs is its very large bandgap of 4.8 eV, ensuring optical transparency of photons with λ ≥ 260 nm, effectively the full terrestrial solar spectrum. At the time of proposal writing, literature on Ga 2 O 3 as a TCO/optical material was relatively sparse — what little existed was focused on for UV sensors and/or emitters, with none related to PV. As such, this project was intended to help determine the potential of Ga 2 O 3 as a PV-oriented TCO by investigating its deposition using tools common to the PV and electronics industries — atomic layer deposition (ALD) and RF sputtering (RS), both of which are already used in PV manufacturing — and its resultant optical and electronic properties. Final project goals were to test its application to Si and III-V solar cells. Controllable film thickness and excellent uniformity was established for both methods deposition methods, with ALD providing higher precision for thinner films and RS more effective for growing thicker films. The as-deposited films were found to be amorphous in nature. Spectroscopic ellipsometry (SE) confirmed bandgaps of at least 4.8 eV and non-parasitic absorption across both AM0 and AM1.5G spectra; a refractive index approaching the expected value of 1.8 was also observed, with some degree of tunability based on process parameters. Using this initial optical data, a transfer matrix model, which interfaces with in-house EQE and LIV models, was developed to simulate Ga 2 O 3 optical effects on various solar cells, included potential in antireflection coatings (ARCs). Despite promising optical properties, the resultant resistivity / conductivity metrics did not meet expectations, regardless of deposition process. Although thick RS-deposited films, using both undoped and 1 at% Ge (n-type) doped sintered targets — demonstrated high net carrier concentrations (via C-V), and low specific resistance Ohmic contacts were demonstrated, transmission line measurements (TLM) showed very high resistivity. Further analysis indicated high vertical film conductivity, but very low lateral conductivity. Deeper characterization revealed a relatively high density of nano/microcrystalline inclusions that were ostensibly the source of the vertical conductivity, with the amorphous matrix serving as an effective insulator (likely due to high concentrations of electronic trap states). Despite extensive work to increase film polycrystallinity — demonstrated via high temperature annealing — sufficient lateral conductivity for TCO use was not achieved. The final phase of the project shifted focus toward investigation of ALD-deposited Ga 2 O 3 ’s potential as a passivant and/or passivating contact for both Si and III-V solar cells, with expectation of performance similar to Al 2 O 3 . However, initial rounds of testing using our baseline ALD process yielded minimal (but not quite zero) passivation of both GaInP and Si surfaces. Dielectric passivation is well-known to be highly process sensitive; given the unoptimized nature of the process used, this work was deemed inconclusive. The final outlook with respect to feasibility of Ga 2 O 3 as a PV-oriented TCO is, ultimately, still uncertain. The work performed in this project confirmed the optical properties and deposition methods, but the achieved electrical properties do not meet technological needs; literature reports in recent years are somewhat inconsistent and potentially untrustworthy, but generally appear to be in line with our results. At the very least it is clear that, should Ga 2 O 3 still be under consideration for PV TCO and/or selective contact applications, a significant amount of optimization and study is still needed.

14 SOLAR ENERGY↗
DOE OSTI2024

Growth and characterization of ferromagnetic Ga 2 O 3 :(Cr, Mn)

The goal of this Exploratory Express project was to explore the possibility of tunable ferromagnetism in Mn or Cr incorporated epitaxial Ga 2 O 3 films. Tunability of magnetic properties can enable novel applications in spintronics, quantum computing, and magnetism-based logics by allowing control of magnetism down to the nanoscale. Carriers (electrons or holes) mediated ferromagnetic ordering in semiconductor can lead to tunable ferromagnetism by leveraging the tunability of carrier density with doping level, gate electric field, or optical pumping of the carriers. The magnetic ions (Cr or Mn) in Ga 2 O 3 act as localized spin centers which can potentially be magnetically coupled through conduction electrons to enable ferromagnetic ordering. Here we investigated tunable ferromagnetism in beta Ga 2 O 3 semiconductor host with various n-doping levels by incorporating 2.4 atomic percent Mn or Cr. The R&D approach involved growth of epitaxial Ga 2 O 3 film on sapphire or Ga 2 O 3 substrate, implantation of Mn or Cr ions, annealing of the samples post implantation, and magnetic measurements. We studied magnetic behavior of Mn:Ga 2 O 3 as a function of different n-doping levels and various annealing temperatures. The vibrating sample magnetometry (VSM) measurement exhibited strong ferromagnetic signals from the annealed Mn:Ga 2 O 3 sample with n-doping level of 5E19 cm -3 . This ferromagnetic behavior disappears from Mn:Ga 2 O 3 when the n-doping level is reduced to 5E16 cm -3 . Although these results are to be further verified by other measurement schemes due to the observation of background ferromagnetism from the growth substrate, these results indicate the possibility of tunable ferromagnetism in Mn:Ga 2 O 3 mediated by conduction electrons.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1993

Clear evidence for the presence of O VI absorption in QSO metal systems

We have detected O VI 1031.93 A, 1037.62 A doublet absorption in a composite QSO spectrum formed from a large number of intervening C IV absorption systems. The detections constitute the first firm evidence for the presence of O VI in intervening QSO metal absorption systems. The equivalent width of the detected O VI absorption implies an O VI column density N(O VI) not less than 2.8 x 10 exp 14/sq cm. This value, together with the nondetection of the N V 1238.82 A, 1242.80 A doublet absorption, suggests that N(O VI)/N(N V) not less than 4.4. For collisionally ionized gas with a solar O to N abundance ratio in thermal equilibrium the above ratio requires a temperature T not less than 2.5 x 10 exp 5 K. It is found that C IV systems which show low-ionization species and those which do not both have associated O VI absorption, suggesting that O VI is probably present in all C IV systems. We also find that C IV systems which show low-ionization species on average have stronger high-ionization absorption lines than those which do not. A simple interpretation was given to explain this trend.

Lu, Limin↗
NASA NTRS1994

The effect of wave-particle interactions on the polar winds O(+)

The escape of the polar wind plasma is an important element in the ionosphere-magnetosphere coupling. Both theory and observations indicate that the wave-particle interactions (WPI) play a significant role in the dynamics of ion outflow along open geomagnetic field lines. A Monte Carlo simulation was developed in order to include the effect of the WPI in addition to the factors that are traditionally included in the 'classical' polar wind (i.e. gravity, electrostatic field, and divergence of geomagnetic field lines). The ion distribution function (f(sub j)), as well as the profiles of its moments (density, drift velocity, temperature, etc.) were found for different levels of WPI, that is, for different values of the normalized diffusion rate in the velocity space (D(tilde) (sub j perpendicular). Although the model included O(=), H(+) and eletrons, we presented only the results related to the O(+) ion. We found that (1) both the density and drift velocity of O(+) increased with the WPI strength, and consequently, the O(+) escape flux was enhanced by a factor of up to 10(exp 5), (2) The O(+) ions could be energized up to a few electron volts; (3) for moderate and high levels of WPI D(tilde) (sub perpendicular) (O(+) greater than (tilde) 1, the distribution function f(O(+)) displayed very pronounced conic features at altitudes around 3 R(sub e). Finally, the interplay between the downward body force, the upward mirror force, and the perpendicular heating resulted in the formation of the 'pressure cooker' effect. This phenomena explained some interesting features of our solution, such as, the peak in the O(=) temperature, and the formation of 'ears' and conics for f(O(+)) around 2.5 R(sub e).

Barakat, A. R.↗
NASA NTRS2006

Evidence in CO3.0 Chondrules for a drift in the O Isotopic Composition of the Solar Nebula

Several recent studies have shown that materials such as magnetite that formed in asteroids tend to have higher Delta O-17 (=delta O-17 -0.52 delta O-18) values than those recorded in unaltered chondrules. Other recent studies have shown that, in sets of chondrules from carbonaceous chondrites, Delta O-17 tends to increase as the FeO contents of the silicates increase. We report a comparison of the O isotopic composition of olivine phenocrysts in low-FeO ( Fal5) type II porphyritic chondrules in the highly primitive C03.0 chondrite Yamato-81020. In agreement with a similar study of chondrules in C03.0 ALH A77307 by Jones et al., Delta O-17 tends to increase with increasing FeO. We find that Delta O-17 values are resolved (but only marginally) between the two sets of olivine phenocrysts. In two of the high-FeO chondrules, the difference between Delta O-17 of the late-formed, high-FeO phenocryst olivine and those in the low-FeO cores of relict grains is well-resolved (although one of the relicts is interpreted to be a partly melted amoeboid olivine inclusion by Yurimoto and Wasson). It appears that, during much of the chondrule-forming period, there was a small upward drift in the Delta O-17 of nebular solids and that relict cores preserve the record of a different (and earlier) nebular environment.

Wasson, John T.↗
NASA NTRS2011

A Contemporary Analysis of the O'Neill-Glaser Model for Space-Based Solar Power and Habitat Construction

In 1975 Gerard O Neill published in the journal Science a model for the construction of solar power satellites. He found that the solar power satellites suggested by Peter Glaser would be too massive to launch economically from Earth, but could be financially viable if the workforce was permanently located in free space habitats and if lunar and asteroid materials were used for construction. All new worldwide electrical generating capacity could be then achieved by solar power satellites. The project would financially break even in about 20 years after which it would generate substantial income selling power below fossil fuel prices. Two NASA / Stanford University led studies at Ames Research center during the summers of 1974 and 1976 found the concept technically sound and developed a detailed financial parametric model. Although the project was not undertaken when suggested in the 1970s, several contemporary issues make pursuing the O Neill -- Glaser concept more compelling today. First, our analysis suggests that if in the first ten years of construction that small habitats (compared to the large vista habitats envisioned by O Neill) supporting approximately 300 people were utilized, development costs of the program and the time for financial break even could be substantially improved. Second, the contemporary consensus is developing that carbon free energy is required to mitigate global climate change. It is estimated that 300 GW of new carbon free energy would be necessary per year to stabilize global atmospheric carbon. This is about 4 times greater energy demand than was considered by the O Neill Glaser model. Our analysis suggests that after the initial investments in lunar mining and space manufacturing and transportation, that the profit margin for producing space solar power is very high (even when selling power below fossil fuel prices). We have investigated the financial scaling of ground launched versus space derived space solar power satellites. We find that for the carbon mitigation case even modernized ground launched space solar power satellites are not financially viable. For space derived solar power satellites, however, the increased demand makes them break even substantially sooner and yield much higher profit. Third, current awareness is increasing about the dangers of humanity remaining a single planet species. Our technological power has been increasing relative to the size of the planet Earth. Since the middle of the 20th century our technological power has grown large relative to our planet's size. This presents a very real potential for human self-extinction. We argue that the potential for human self-extinction is increasing with time in proportion to the exponential growth of our technological power making self-extinction likely within this century if humanity remains a single planet species. The O Neill model of multiple independent free space habitats, it is argued, can protect humanity from extinction in the same way that portfolio diversification protects ones assets from total loss. We show that about 1 million people for the electricity only case, and about 1 billion people for the carbon mitigation case, can be provided with permanent space habitats and transportation from Earth in 30 years and can be funded by the space derived solar power satellite program. 1.2 Scope of this Chapter The goal of this chapter is to illustrate the power and importance of the O'Neill-Glaser concept in the context of human survival and maintaining a healthy planet Earth. We argue that at this point in human history our technological power is too dangerous to our selves and our home planet for us not to expand into space. We show by the models presented in the chapter that the imminent dangers of global warming and human self-extinction mandate that humanity move aggressively into the solar system in this generation. We show that the production of solar power satellites using space resources and with a work foe living in space provides a viable financial model to mitigate CO2 preventing the worst global warming scenarios, and safeguards humanity against self-extinction by providing hundreds of habitats and a billion people living in space within about 35 years. To accomplish this goal we need only consider the classic O'Neill-Glaser model which was parameterized for 1970's technological projections. Only habitat size optimization for the first ten years of production is added. This is a conservative approach since the innovations of the last 30 years will make the financial projections more favorable. However, the classic O'Neill-Glaser model represented a broad technological consensus. The model is well documented in the references and our calculations can be easily reproduced In this chapter the economics of the O Neill - Glaser model is compared with models that rely exclusively on Earth launched materials. Although many studies of Earth launched Solar Power Satellites have been made, we found that the NASA "Fresh Look Study" was the most comprehensive and well documented. It also provided one of the most optimistic Earth launch financial projections. We thus chose it for comparison purposes.

Curreri, Peter A.↗
NASA NTRS2011

Energetic O+ and H+ Ions in the Plasma Sheet: Implications for the Transport of Ionospheric Ions

The present study statistically examines the characteristics of energetic ions in the plasma sheet using the Geotail/Energetic Particle and Ion Composition data. An emphasis is placed on the O+ ions, and the characteristics of the H+ ions are used as references. The following is a summary of the results. (1) The average O+ energy is lower during solar maximum and higher during solar minimum. A similar tendency is also found for the average H+ energy, but only for geomagnetically active times; (2) The O+ -to -H+ ratios of number and energy densities are several times higher during solar maximum than during solar minimum; (3) The average H+ and O+ energies and the O+ -to -H+ ratios of number and energy densities all increase with geomagnetic activity. The differences among different solar phases not only persist but also increase with increasing geomagnetic activity; (4) Whereas the average H+ energy increases toward Earth, the average O+ energy decreases toward Earth. The average energy increases toward dusk for both the H+ and O+ ions; (5) The O+ -to -H+ ratios of number and energy densities increase toward Earth during all solar phases, but most clearly during solar maximum. These results suggest that the solar illumination enhances the ionospheric outflow more effectively with increasing geomagnetic activity and that a significant portion of the O+ ions is transported directly from the ionosphere to the near ]Earth region rather than through the distant tail.

Ohtani, S.↗
NASA NTRS2015

Late-Glacial to Late-holocene Shifts in Global Precipitation Delta(sup 18)O

Reconstructions of Quaternary climate are often based on the isotopic content of paleo-precipitation preserved in proxy records. While many paleo-precipitation isotope records are available, few studies have synthesized these dispersed records to explore spatial patterns of late-glacial precipitation delta(sup 18)O. Here we present a synthesis of 86 globally distributed groundwater (n 59), cave calcite (n 15) and ice core (n 12) isotope records spanning the late-glacial (defined as 50,000 to 20,000 years ago) to the late-Holocene (within the past 5000 years). We show that precipitation delta(sup 18)O changes from the late-glacial to the late-Holocene range from -7.1% (delta(sup 18)O(late-Holocene) > delta(sup 18)O(late-glacial) to +1.7% (delta(sup 18)O(late-glacial) > delta(sup 18)O(late-Holocene), with the majority (77) of records having lower late-glacial delta(sup 18)O than late-Holocene delta(sup 18)O values. High-magnitude, negative precipitation delta(sup 18)O shifts are common at high latitudes, high altitudes and continental interiors.

isotopes↗
NASA NTRS2019

Seasonal, Solar Zenith Angle, and Solar Flux Variations of O+ in the Topside Ionosphere of Mars

Using observations from Mars Atmosphere and Volatile EvolutioN's Neutral Gas and Ion Mass Spectrometer, we characterize the seasonal, solar zenith angle (SZA), and solar flux dependent variations of the O+ peak and the O+/O+2 ratio in the topside ionosphere of Mars.We find that the O+ peak is between 220 and 300 km and forms at a roughly constant neutral atmospheric pressure level of 10(−8.7±0.4) Pa. The O+ peak altitude also decreases with increasing SZA near the terminator and varies sinusoidally with an amplitude of 26 km over a period of one Mars year in response to the changing solar insolation. The O+ peak altitude reaches a maximum near Northern Winter solstice and Mars perihelion. The O+ peak density on the dayside has an average value of (1.1 ± 0.5) × 103 cm−3, has no dependence on SZA for SZAs up to ∼90◦, and is mainly controlled by the thermospheric O/CO2 ratio as predicted by photochemical theory. Above the O+ peak, the O+/O+2 ratio in the dayside ionosphere approaches a constant value of 1.1 ± 0.6, decreases with increasing SZA, and is highly variable on timescales of days or less.We discuss why the O+ peak is different than the main (M2) peak at Mars and why it is similar to the F2 peak at Earth.

Girazian, Z.↗
NASA NTRS2024

EMIC Wave Energy Dissipation as a Source of O + Conics and Warm Plasma Cloak in the Earth's Inner Magnetosphere

This study focuses on a specific source of the O + conics and warm plasma cloak in the Earth's inner magnetosphere due to electromagnetic ion cyclotron (EMIC) wave energy dissipation. We analyze the EMIC wave event observed by Van Allen Probe-A in the early afternoon off equatorial magnetosphere on 18 November 2015, where the two dominant EMIC wave bands, He + -band and H + -band, were observed for ∼4 min. All the wave and plasma parameters, the DC magnetic field, and ion distributions needed for our analysis are taken from the Van Allen Probe-A observations during the event. The major results of our analysis are as follows. (a) The H + and He + heating by EMIC waves is negligible. (b) A strong heating of O + by the wave energy dissipation around the third, fifth, and sixth harmonics of the O + gyrofrequency is revealed, where the majority of energy dissipated goes into heating of O + with the energies ≲100 eV and pitch angles ∼20°–90°. The estimated energy deposition rate is ∼0.1–3.4 eV/s per O + , totaling to the deposition of ∼20–800 eV per O + during the event. (c) EMIC waves substantially contribute to the formation of O + conics and warm plasma cloak by heating the upgoing low-energy ionospheric O + because waves heat ions with the energies and pitch angles that are characteristic of conics and warm plasma cloak, and the energy deposition per O + is comparable to those characteristic energies.

Konstantin V. Gamayunov↗
DOE OSTI2021

First-principles study of the surface properties of LiAl 5 O 8 : Stability and tritiated water formation

LiAl 5 O 8 is an important secondary phase of γ-LiAlO 2 ceramics in tritium ( 3 H, T)-producing burnable absorber rods (TPBARs), present in small quantities in the as-fabricated condition and in larger quantities after irradiation due to Li burnup and mobility in the radiation-damaged lattice. In this work, we performed first-principles calculations to study the stabilities and structures of LiAl 5 O 8 surfaces the possibility of T 2 O formation on the (111) surface. By calculating the surface energies of all possible symmetrical stoichiometric and nonstoichiometric low-index surfaces, we identified the two most stable surfaces, one stoichiometric (001) surface and one nonstoichiometric (111) surface in an O-rich condition. The surface oxygen atoms on the nonstoichiometric (111) surface have remarkable displacements after relaxation, due to the large dangling O bonds. Considering a Li-poor and 3 H-rich condition relevant to TPBARs, we further studied these two stable surfaces with 37.5%, 75%, and 100% surface O atoms covered by 3 H atoms. Our results show that the 3H saturation is favorable for the nonstoichiometric (111) surface but not for the stoichiometric (001) surface. In addition, the structure of nonstoichiometric (111) surface is well stabilized when the surface O atoms are 100% saturated by 3 H atoms. Based on the fully 3H-saturated (111) surface, the 3 H 2 O desorption with an energy barrier of 0.69 eV is preferable in the 3 H-rich condition.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effect of Thermal Oxidation on the Structure, Surface Texturing, and Microstructure Evolution in Nanocrystalline Ga-O-N Films

An extensive examination of the nanoscale, crystallographic growth dynamics of the system, which is impacted by the thermal energy given to the GaN, is carried out to derive a deeper understanding of the growth kinetics, morphology and microstructure evolution, chemical bonding, and optical properties of Ga-O-N films. Thermal annealing of GaN films is performed in the temperature range of 900–1200 °C. Crystal structure, phase formation, chemical composition, surface morphology, and microstructure evolution of Ga-O-N films are investigated as a function of temperature. Increasing temperature induces surface oxidation, which results in the formation of stable β-Ga2O3 phase in the GaN matrix, where the overall film composition evolves from nitride (GaN) to oxynitride (Ga-O-N). While GaN surfaces are smooth, planar, and featureless, oxidation induced granular-to-rod shaped morphology evolution is seen with increasing temperature to 1200 °C. The considerable texturing and stability of the nanocrystalline Ga-O-N on Si substrates can be attributed to the surface and interface driven modification because of thermal treatment. Corroborating with structure and chemical changes, Raman spectroscopic analyses also indicate that the chemical bonding evolution progresses from fully Ga-N bonds to Ga-O-N. While the GaN oxidation process starts with the formation of β-Ga 2 O 3 at an annealing temperature of 1000 °C, higher annealing temperatures induce structural distortion with the potential formation of Ga-O-N bonds. The structure-phase-chemical composition correlation, which will be useful for nanocrystalline materials for selective optoelectronic applications, is established in Ga-O-N films made by thermal treatment of GaN.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Decomposition Kinetics of H 2 O 2 on Pd Nanocrystals with Different Shapes and Surface Strains

Direct synthesis of hydrogen peroxide (H 2 O 2 ) from H 2 and O 2 on a Pd-based catalyst has emerged as a promising route to replace the energy-consuming, highly inefficient anthraquinone process. However, Pd is also a good catalyst for the decomposition of H 2 O 2 , thereby compromising the selectivity toward the desired product. The coupling between the formation and decomposition reactions makes it difficult to single out the most important parameter that controls the selectivity toward direct synthesis of H 2 O 2 . Herein, support-free monometallic Pd nanocrystals with different shapes and surface strains are used to investigate their impacts on the decomposition kinetics of H 2 O 2 . The kinetics are analyzed by tracking the concentration of the remaining H 2 O 2 using infrared spectroscopy. The data indicates that both surface structure and strain affect the decomposition kinetics of H 2 O 2 , but their impacts are inferior to that caused by Br – , a surface capping agent for the Pd{100} facets. The experimental results are consistent with the trend obtained through density functional theory calculations. Furthermore, this work helps shed light on the development of Pd-based catalysts for the direct synthesis of H 2 O 2 by offering strategies to mitigate the decomposition of the desired product.

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

Effect of H 2 O on the ethylene glycol/alkali dismantling of bagasse for high-value conversion

Using a high-boiling alcohol system to dismantle main components of biomass is a feasible technology. Reducing dismantle operating costs and improving dismantle efficiency are essential for promoting the green, economical, and sustainable development of biomass refining. Therefore, based on the low cost and chemical properties of H 2 O at high temperature, the effects of different H 2 O dosages in NaOH-catalyzed ethylene glycol (HBAA) system on the dismantling efficiency of bagasse, surface lignin coverage, recovered-lignin activity and enzymatic hydrolysis efficiency were investigated. Compared with the HBAA dismantling system without H 2 O, the HBAA system with 60% w/v H 2 O can obviously increase the removal rates of lignin and hemicellulose, while recovering up to 99% of cellulose and significantly declining surface lignin coverage, thus enhancing the enzymatic hydrolysis efficiency. Additionally, the results of density functional theory calculations and 2D HSQC NMR analysis prove that the synergy between H 2 O and ethylene glycol can promote the esterification reaction occurrence at the α-C carbon cation in β-O-4 structure of lignin, thereby protecting the β-O-4 aromatic ether bond. Simultaneously, when the H 2 O dosage increase from 0% to 60%, the enzymatic yield increases from 84.51% to 93.74% with an enzyme load of 10 FPU/g. Based on experimental results, this study conducted a techno-economic analysis of bagasse dismantling for ethanol and co-production of lignin, achieving a minimum ethanol selling price of $\$$1.07 per kg. Here, in this study, a green and economical solution for dismantling the main components of bagasse is developed, which is important for the high-value conversion of bagasse.

Ethylene glycol↗
DOE OSTI2020

Catalytic consequences of hydrogen addition events and solvent-adsorbate interactions during guaiacol-H 2 reactions at the H 2 O-Ru(0 0 0 1) interface

Catalytic reactions of biomass-derived phenolics and H 2 occur on transition metal surfaces via competitive C–O cleavage and ring saturation pathways, with both requiring multiple hydrogen addition events before forming their respective rate limiting transition states. These events are markedly affected by solvent chemical identity, with polar protic solvents ionizing hydrogen adatoms (H*) to interfacial protons (H + ) and opening up new catalytic routes. Here, we establish the reaction coordinate space for guaiacol-H 2 reactions on Ru(0 0 0 1) using density functional theory and describe the atomic-scale effect of a polar protic solvent, H 2 O. Coupled H + and H* attack leads to quasi-equilibrated enol and keto intermediates as the precursors for C–O cleavage and ring saturation, respectively. For C–O cleavage, H 2 O solvent enables a lower energy pathway via concomitant transfer of the hydroxyl H + to the methoxy oxygen during C–OCH 3 cleavage, forming a charge separated [Ru(s)–(C 6 H 5 O – )…(H + )…OCH 3 ] transition state and reducing the barrier by up to 0.8 eV as compared to unassisted C–OCH 3 cleavage. For ring saturation, H* attack onto an unsaturated meta carbon is rate limiting with no direct solvent participation, suggesting that protic polar solvents selectively promote the C–O cleavage pathway. Taken together, we show that activating guaiacol for either C–O bond cleavage or ring saturation product formation depends on the reactive hydrogen identity (H* or H + ), enol/keto isomerization equilibrium, and accessibility of the proton assisted Car–OCH 3 cleavage transition state. Here, all such factors are tunable via changes to the solvent or metal identity.

09 BIOMASS FUELS↗