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At least 379 records · Page 21

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NASA NTRS2018

Microphysical Properties of Tropical Tropopause Layer Cirrus

Pervasive cirrus clouds in the tropical tropopause layer (TTL) play an important role in determining the composition of stratospheric air through dehydration of tropospheric air entering the stratosphere. This dehydration affects Earth's energy budget and climate, yet uncertainties remain regarding the microphysical processes that govern TTL cirrus. TTL cirrus were sampled with the NASA Global Hawk UAV for over 30 hr in the Western Pacific in 2014 during the Airborne Tropical TRopopause EXperiment. In situ measurements by a Fast Cloud Droplet Probe and Hawkeye probe (combination Fast Cloud Droplet Probe, Two‐Dimensional Stereo optical array probe, and Cloud Particle Imager) provided particle concentrations and sizing between 1‐ and 1,280‐μm diameter and high resolution images for habit identification. We present the variability in ice concentrations, size distributions, and habits as functions of temperature, altitude, and time since convective influence. Observed ice particles were predominantly small and quasi‐spheroidal in shape, with the percentage of quasi‐spheroids increasing with decreasing temperature. In comparison to the large fraction of the population consisting of quasi‐spheroids, faceted habits (columns, plates, rosettes, and budding rosettes) constituted a smaller percentage of the overall population and exhibited the opposite correlation with temperature. The trend of higher percentages of faceted crystals occurring at warmer temperatures may be due to diffusional growth or aggregation as particles descend through cloud, and/or the more rapid diffusional growth rate at warmer temperatures. Sampling was typically well away from deep convection, however, and very few aggregates were observed, so the trend of higher percentages of faceted habits is likely attributable to diffusional growth.

Woods, Sarah↗

NASA NTRS2015

Overview of the NASA Airborne Tropical TRopopause EXperiment (ATTREX)

The NASA Airborne Tropical TRopopause EXperiment (ATTREX) is a series of airborne campaigns focused on understanding physical processes in the Tropical Tropopause Layer (TTL) and their role in atmospheric chemistry and climate. ATTREX is using the high-altitude, long-duration NASA Global Hawk Unmanned Air System to make in situ and remote-sensing measurements spanning the Pacific. A particular ATTREX emphasis is to better understand the dehydration of air as it passes through the cold tropical tropopause region. The ATTREX payload contains 12 in situ and remote sensing instruments that measure water vapor, clouds, multiple gaseous tracers (CO, CO2, CH4, NMHC, SF6, CFCs, N2O), reactive chemical compounds (O3, BrO, NO2), meteorological parameters, and radiative fluxes.ATTREX flight series have been conducted in the fall of 2011 from Armstrong Flight Research Center (AFRC) in California, in the winter of 2013 from AFRC, and in the winterspring of 2014 from Guam. The first two flight series provided extensive sampling of the central and eastern Pacific, whereas the last flight series permitted sampling in the western Pacific. The sampling strategy has primarily involved repeated ascents and descents through the depth of the TTL (about 13-19 km). Over 100 TTL profiles were obtained on each flight series. The ATTREX dataset includes TTL water vapor measurements with unprecedented accuracy, ice crystal size distributions and habits. The cloud and water measurements provide unique information about TTL cloud formation, the persistence of supersaturation with respect to ice, and dehydration. The plethora of tracers measured on the Global Hawk flights are providing unique information about TTL transport pathways and time scales. The meteorological measurements are revealing dynamical phenomena controlling the TTL thermal structure, and the radiation measurements are providing information about heating rates associated with TTL clouds and water vapor.This presentation will provide an overview of the ATTREX flights, examples of measurements from the flights, and plans for modelinganalysis of the ATTREX dataset.

Jensen, Eric J.↗

NASA NTRS2020

Impact of Convectively Detrained Ice Crystals on the Tropical Upper Troposphere and Lower Stratosphere

The role of convectively detrained ice crystals on the humidity of the tropical upper troposphere and lower stratosphere (UTLS) is investigated in simulations of cirrus clouds along trajectories launched from the 378K potential temperature level in the tropics. The one-dimensional (vertical) cloud model tracks individual ice crystals through their lifecycle beginning with detrainment from convection, followed by deposition growth, sedimentation and sublimation. Convective influence of the parcels is diagnosed by tracing the trajectories through time-dependent fields of convective cloud-top height adjusted to match the CloudSAT and CALIPSO statistics. Model simulations of UTLS water vapor and cloud fields are evaluated and constrained by comparison with Aura MLS and CALIPSO measurements. Preliminary results indicate sensitivity of the detrained ice crystal lifecycle to atmospheric conditions downstream of convection. Specifically, cooling (high relative humidity and supersaturation) downstream of convection leads to deposition growth and sedimentation of detrained ice crystals, resulting in net dehydration of the UTLS. In contrast, warming (low relative humidity and subsaturation) downstream of convection leads to sublimation of detrained ice crystals and subsequent hydration. As such, the impact of detrained ice crystals on the humidity of the UTLS exhibits distinct spatial variability. Detrained ice crystals predominantly dehydrate the UTLS in the tropical mean. Sensitivities to the convectively detrained ice crystal size and concentration are also examined using measurements from the StatoClim aircraft campaign. The importance of convectively detrained ice crystals will be discussed within the context of the overall contribution of convection to the lower stratospheric humidity.

Ueyama, Rei↗

NASA NTRS2020

Stability of Actinolite on Venus

Venus currently has a hostile surface environment with temperatures of ~460 ºC, pres-sures near 92 bars, and an atmosphere composed of super critical CO2 hosting a myriad of other potentially reactive gases (e.g., SO2, HCl, HF). However, it has been proposed that its surface may not have always been so harsh. Models suggest there may have been billions of years of clement conditions allowing an Earth-like environment with liquid water oceans. If such conditions existed, it is possible Venus formed a similar array of hydrous or aqueous minerals as seen on other planets with liquid surface water (e.g., Mars, Earth). Based on thermodynamic modeling, many of these phases would not be stable under the current atmospheric conditions on Venus, dehydrating due to the high temperatures and low concentration of H2O in the atmosphere. However, the rate of decomposition of these phases may allow them to remain present on the surface over geologic time. For example, experiments on the reaction rate of tremolite (Ca2Mg5Si8O22(OH)2) show a 50% decomposition time of 2.7 Gyr for micrometer sized grains in unreactive atmospheres (i.e., without SO2) at 740 K, and a 50% decomposition time of 70 Gyr for crystals several millimeters to centimeters in size. If hydrous minerals can remain on the surface of Venus over geologic time, it has implications for our detection of evidence of these past environments, and also for the overall water budget of the planet. If after surficial dehydration the planet was able to still store water in its crust, possible processes such as subduction or metamorphism could still have operated using stored water long after liquid surface water evaporated. Several previous studies have focused on experimental investigations of mineral stability on Venus. In particular, the works of studied the decomposition rate of tremolite under conditions relevant to Venus. As their focus was on decomposition of the mineral due to lack of water in the atmosphere, their experiments were undertaken using only CO2 or N2 gas at atmospheric pressure. Re-cent experiments have examined reactivity of other minerals with the Venusian atmosphere using more complex gas compositions at similar pressures to those seen on Venus. These studies show reaction of silicate minerals with atmospheric components on relatively short timescales (i.e., on the order of days). The reported reactions of silicate materials in both studies produced iron oxides, Ca sulfates, and Na sulfates. These ions are present in many amphiboles, and Ca was proposed by Johnson and Fegley to potentially have an important role in the decomposition mechanism for tremolite, with the Ca-O bond being the first to break during decomposition. The potential involvement of Ca in both processes raises the question of whether or not the reaction to form a secondary mineral phase will influence the rate of amphibole break-down (e.g., discussion in for tremolite). Additionally, reaction of Ca with atmospheric gases may result in a different secondary mineral assemblage than simple amphibole decomposition, which will need to be recognized when searching for evidence of past hydrated minerals on the Venusian surface. In order to understand the effect of this reaction on the overall preservation potential of amphibole on the surface of Venus, we are conducting experiments in both reactive and nonreactive atmospheres using the mineral actinolite (Ca2(Mg,Fe)5Si8O22(OH)2), an amphibole with similar crystal structure to tremolite that contains both Ca and Fe.

Santos, A. R.↗

NASA NTRSDate not supplied

Constraints on the surface materials of Ryugu from spectral and water analysis of experimentally-heated CI carbonaceous chondrite

We performed heating experiments of the Orgueil CI chondrite in vacuum conditions at fO2 around I/W to evaluate systematic changes in mineralogy, water contents, and visible to infrared spectral features. Our goal is to interpret the spectra of Ryugu, the target C asteroid of the Hayabusa2 mission, because Ryugu shows spectral features similar to partially dehydrated carbonaceous chondrites. However heated carbonaceous chondrites can be easily contaminated by terrestrial water, which makes it almost impossible for laboratory data to be compared with spectra of asteroids directly. Therefore, our heated samples were analyzed without exposure to the air after experimental heating to minimize the effects of terrestrial water. The depth of the 2.7-µm absorption band and the water content of the heated Orgueil form a positive correlation trend which follows the results of experimental heating of CM and Tagish Lake meteorites using our experimental procedures. It is found that 500-°C heated Orgueil sample shows the best spectral match with Ryugu in terms of the low reflectance (~2%) at visible wavelengths and a weak absorption (~10%) at around 2.72 µm owing to survival of Mg-rich phyllosilicates. We suggest that Ryugu might have experienced heating and dehydration at a temperature around 500 °C, after aqueous alteration, and presently contains a small quantity of hydrated minerals equivalent to 1-2 wt.% of water at the surface.

K. Amano↗

NASA NTRS2017

Large Anomalies in Lower Stratospheric Water Vapor and Ice During the 2015–2016 El Niño

The strong and unusual El Niño of 2015-2016 produced a remarkable perturbation to the hydrologic budget of the tropical tropopause layer (14-19 km). This region regulates stratospheric water vapor, which has a direct radiative impact on surface temperatures. To first order, the coldest tropical tropopause temperature regulates the amount of water vapor entering the stratosphere by controlling the amount of dehydration in the rising air. Here we show that tropical convective cloud ice and associated cirrus evaporating at unusually high altitudes might also have a role in stratospheric hydration. The 2015-2016 El Niño produced decadal record water vapor amounts in the tropical Western Pacific, coincident with warm tropopause temperature anomalies. In the Central Pacific, convective cloud ice was observed 2 km above the anomalously cold tropopause. A trajectory-based dehydration model based on two reanalysis temperature and wind fields can account for only about 0.5-0.6 ppmv of the ~0.9 ppmv tropical lower stratospheric moistening observed during this event. This suggests that unresolved convective dynamics and/or associated sublimation of lofted ice particles also contributed to lower stratospheric moistening. These observations suggest that convective moistening could contribute to future climate change-induced stratospheric water vapor increases.

Atmospheric chemistry↗

DOE OSTI2020

Component removal from a gas stream

In a first aspect, the disclosure provides a method for removing a component from a gas stream. A carrier gas stream is cooled by direct contact with a dehydrating solution stream. The dehydrating solution stream removes a portion of water present in the carrier gas stream and produces a dry gas stream and a wet solution stream. A portion of the component is removed from the dry gas stream by direct contact with a cold contact liquid stream. A depleted gas stream and a slurry stream are produced. Removing the portion of the component may include desublimating, freezing, condensing, depositing, or a combination thereof of the portion of the component out of the dry gas stream as a solid product. The slurry stream may include the solid product and a contact liquid. The solid product is separated from the contact liquid, producing a substantially pure solid product stream and the cold contact liquid stream.

42 ENGINEERING↗

DOE OSTI2026

Effect of NO on DME-Methanol HCCI Combustion Using a Reduced Chemical Kinetics Mechanism

Methanol is an attractive fuel for the maritime sector due to its wide availability. Its direct use as a fuel, however, is accompanied by challenges such as high latent heat of vaporization and low cetane number. A potential solution to overcome the ignition properties of methanol could be through on-board generation of dimethyl ether (DME) via catalytic dehydration of methanol. The resulting mixture from dehydration can be mixed in with the intake air to generate a homogenous charge compression ignition (HCCI) preburn for subsequent direct injection (DI) mixing controlled compression ignition (MCCI) of neat methanol. Within that context, complementary experimental work found that the influence of combustion residuals on the heat release rate (HRR) was significant, specifically for residual NO. This finding motivated the present computational and kinetic evaluation of the effects of NO on the low (LTHR) and high (HTHR) temperature heat release rates. The strong influence of small quantities of NO on the combustion process of a DME/methanol/H2O mixture (low catalyst or reactor efficiency) necessitated a kinetics-based investigation into this phenomenon. A mechanism sourced from the existing literature with NO had 172 species and 1375 reactions, making it computationally expensive for use. Hence, a mechanism reduction effort was implemented, and a rate constant (k) tuning effort based on sensitivity analysis was needed to validate experimental results using a zero-dimensional engine model in Cantera. The reduced mechanism was able to successfully capture the negligible influence of NO addition on DME HCCI combustion, whereas an advancement in LTHR and HTHR for a DME/methanol/H2O mixture was kinetically confirmed. Reaction pathway analysis showed that addition of NO chemically counteracted the OH sink created by alcohols like methanol, increasing the effectiveness of DME ignition.

Tyrewala, Daanish [ORNL] (ORCID:0000000208599324)↗

DOE OSTI2026

Effect of NO on DME-Methanol HCCI Experimental Observations

Methanol is an attractive fuel for the maritime sector due to its wide availability. Its direct use as a fuel, however, is accompanied by challenges such as high latent heat of vaporization and low cetane number. A potential solution to overcome the ignition properties of methanol could be through on-board generation of dimethyl ether (DME) via catalytic dehydration of methanol. The resulting mixture from dehydration can be mixed in with the intake air to generate a homogenous charge compression ignition (HCCI) preburn for subsequent direct injection (DI) and successful ignition methanol at diesel–like timescales. However, if the preburn species are treated separately from the complete methanol MCCI approach the preburn heat release rate (HRR) phasing and behavior do not replicate the preburn behavior of the complete approach. Thus, the presence of the main methanol mixing controlled compression ignition (MCCI) combustion event influences the DME/methanol preburn kinetics. Specifically, it was found that trapped residual temperature alone was insufficient alone to be responsible for the observed differences, and that trace species concentrations of NO in the trapped residual gas also influenced DME/methanol kinetics increasing low temperature heat release (LTHR) magnitude and advancing high temperature heat release (HTHR) phasing. NO is not present in HCCI combustion of neat DME or DME/methanol blends nor is elevated gas temperature in the trapped residuals; both of which result in failure to accurately predict the HCCI combustion of DME/methanol blends when coupled with subsequent DI methanol MCCI. This work experimentally explores the effect of trapped residual temperature and NO on DME and DME/methanol HCCI combustion.

Jatana, Gurneesh [ORNL] (ORCID:0000000288903225)↗

DOE OSTI2021

Precise Identification and Characterization of Catalytically Active Sites on the Surface of γ-Alumina

γ-alumina is one of the oldest and most important commercial catalytic materials with high surface area and stability. These attributes enabled its use as the first commercial large-scale heterogeneous catalyst for ethanol dehydration. Despite progress in materials characterization the nature of the specific sites on the surface of γ-alumina that are responsible for its unique catalytic properties has remained obscure and controversial. By using combined infrared spectroscopy, electron microscopy and solid-state nuclear magnetic resonance measurements we identify the octahedral, amphoteric (O) 5 Al(VI)-OH sites on the (100) segments of massively restructured (110) facets on typical rhombus-platelet γ-alumina as well as the (100) segments of irrational surfaces (invariably always present in all γ-alumina samples) responsible for its unique catalytic activity. Such (O) 5 Al(VI)-OH sites are also present on the macroscopically defined (100) facets of γ-alumina with elongated/rod-like geometry. The mechanism by which these sites lose -OH groups upon thermal dehydroxylation resulting in coordinatively unsaturated penta-coordinate Al +3 O 5 sites is clarified. These coordinatively unsaturated penta-coordinate Al sites produce well-defined thermally stable Al-carbonyl complexes. Overall, our findings contribute to the understanding of the nature of coordinatively unsaturated Al sites on the surface of γ-alumina and their role as catalytically active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Maximum Impact of Ionic Strength on Acid‐Catalyzed Reaction Rates Induced by a Zeolite Microporous Environment

Abstract The intracrystalline ionic environment in microporous zeolite can remarkably modify the excess chemical potential of adsorbed reactants and transition states, thereby influencing the catalytic turnover rates. However, a limit of the rate enhancement for aqueous‐phase dehydration of alcohols appears to exist for zeolites with high ionic strength. The origin of such limitation has been hypothesized to be caused by the spatial constraints in the pores via, e.g., size exclusion effects. It is demonstrated here that the increase in turnover rate as well as the formation of a maximum and the rate drop are intrinsic consequences of the increasingly dense ionic environment in zeolite. The molecularly sized confines of zeolite create a unique ionic environment that monotonically favors the formation of alcohol‐hydronium ion complexes in the micropores. The zeolite microporous environment determines the kinetics of catalytic steps and tailors the impact of ionic strength on catalytic rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Cradle-to-Gate greenhouse gas emissions of the production of ethylene from U.S. Corn ethanol and comparison to fossil-derived ethylene production

Conventional ethylene production heavily depends on fossil-derived feedstocks via steam cracking, a very energy- and emission-intensive process. Researchers have been exploring alternatives to reduce CO 2 emissions including producing ethylene from biobased feedstocks. This paper evaluates the cradle-to-gate greenhouse gas (GHG) emissions of bioethylene produced from U.S. corn ethanol. The analysis includes different pathways for the dehydration of corn ethanol to ethylene and co-processing routes via fluid catalytic cracking (FCC) processes. For the FCC co-processing route carbon-14 analysis is used to determine bioethanol yields. A 127% reduction in life cycle GHG emissions of bioethylene is estimated compared to fossil-derived ethylene for the base case. Additional case studies are also discussed to understand the reduction of GHG emissions due to sustainable corn farming and renewable power use, biogenic carbon capture, and fuel switch with biofuels at the ethanol plant, and its impact on bioethylene GHG emissions.

carbon footprint↗

DOE OSTI2024

In situ visualisation of zeolite anisotropic framework flexibility during catalysis

Zeolites exhibit framework flexibility driving their chemical and catalytic properties. Since the zeolitic pores are extremely small, a slight strain generated in the crystal induces compelling changes in shape, connectivity, accessibility, and the framework chemical properties. These modifications affected the adsorption and desorption of reactants/products and the diffusion within the channels during reaction. Using in situ 3D Bragg coherent X-ray diffraction imaging, we unveil the dynamics of the zeolite structure during catalysis, contraction and/or expansion of its framework also known as zeolite framework flexibility. Here, we imaged three-dimensionally a single faujasite zeolite crystal during the ethanol dehydration reaction revealing anisotropic lattice dynamics simultaneously to guest molecules formation. Understanding zeolite flexibility could permit to tune zeolites properties towards potentially higher adsorption and selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Evolution of thermo-mechanical properties of concrete with calcium aluminate cement and special aggregates for energy storage

Highlights: • CAC Concrete with stable aggregates is suitable for high temperatures with cycles. • Concrete suffered performance changes after the first thermal cycle (dehydration). • Subsequent thermal cycles showed stabilization and slight performance decreases. With the ever-expanding presence of solar energy, the design of cost-efficient heat energy storage systems is becoming increasingly relevant. Concrete is a potential solid material for these systems but raises questions of its response at high temperatures in operating conditions. This work studies concrete designed with calcium aluminate cement and three types of aggregates that are stable at high temperatures. The designed concrete mixes were exposed to thermal cycles (290–550 °C), and their thermal fatigue response was evaluated with mechanical, cracking, thermal, and microstructural analyses at room temperature after heat cycles. The obtained results show that the main changes are mostly produced after the first thermal cycle and are stabilized during successive thermal cycles, with only a slight decrease in the thermo-mechanical properties. The results showed stabilization of cracking, crack widths between 10 and 80 μm, reduction of compressive strength, around 50–65%, and reduction of the thermal conductivity by 30%.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Clinkerless ultra-high strength concrete based on alkali-activated slag at high temperatures

This work investigates the degradation mechanisms of clinkerless alkali-activated slag based ultra-high strength concrete (AAS-UHSC) upon exposure to high temperatures up to 800 °C. The heat-induced mechanical, mineralogical, molecular, microstructural, and pore structure alterations of AAS-UHSC prepared with various activator types, water-to-powder ratios, and fiber incorporation are studied. The results demonstrate the beneficial roles of potassium incorporation on improving the thermal stability and integrity of AAS-UHSC, via suppressing deleterious crystallization and transformation of aluminosilicate phases at high temperature. In contrast to Portland cement clinker-based UHSC, no sign of explosive spalling is observed in AAS-UHSC, likely due to the presence of microcracks that enhance the pore network connectivity. The mechanical degradation of AAS-UHSC at high temperature below 600 °C is resulted from dehydration and decomposition of phases and consecutive thermal cracking, together with enlarged porosity and coarsened pore structure. As the temperature rising to 800 °C, crystallization and transformation of phases, as well as formation of porous microstructure, considerably aggravate the mechanical degradation of AAS-UHSC. In contrast to the thermal damage mitigation by polymeric fibers in conventional UHSC, the fiber incorporation has little positive impact on the thermal resistance of AAS-UHSC.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Direct Conversion of Biomass Carbohydrates to Platform Chemicals: 5-Hydroxymethylfurfural (HMF) and Furfural

5-hydroxymethylfurfural (HMF) and furfural are promising platform molecules which can be converted to fuel intermediates and hydrocarbon fuels. Herein, one-step, direct conversion of the carbohydrates in never treated biomass to HMF and furfural in a microwave reactor was investigated. The influence of reaction temperature, time, feedstock, addition of Lewis and Bronsted acids, solvent and solvent to aqueous ratio were studied to find the optimum process conditions to maximize the yields of furfurals. The reaction conditions of 200 degrees C for 5 min with 33 mM HCl and 8 mM AlCl 3 using a dioxane/water (4:1) miscible solvent system were found to be the most conducive for direct dehydration of the glucan and hemicelluloses present in untreated poplar wood to furfural and HMF in yields of 91 and 69%, respectively. Furfural could be easily produced in yields greater than 80%, and once formed, it was found to be stable under the various process conditions explored. In contrast, HMF yields varied with both reaction time and temperature, as it readily underwent rehydration to levulinic acid in yields approaching 25-30% at increased reaction severity. The additions of both Bronsted (HCl) and Lewis (AlCl 3 ) acids in catalytic amounts, i.e., 33 and 8 mM, respectively, were required to maximize the yield of furfurals. Reactions were also performed on other feedstocks (corn stover, switchgrass, loblolly pine, and pure cellulose) to investigate the effect of feedstock type on furfurals yields. Results showed that HMF and furfural yields were primarily dependent on hexosan and pentosan loading regardless of the type of feedstock. In addition, biomass physical features, such as crystallinity or the presence of other biomass constituents, such as lignin, had little influence on furfurals yields.

09 BIOMASS FUELS↗

DOE OSTI2022

How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

Stable hydration in perfluorinated polyelectrolyte membranes such as Nafion is essential to maintain good ion conductivity and manage permeation, especially in vapor-fed devices where water content depends on relative humidity in a gas stream. Extensive studies in the literature have shown that Nafion hydration in water vapor is controlled by its interfacial transport resistance. Nafion forms a fluorine-rich layer at the polymer-gas interface, and it has been proposed that this layer blocks water transport due to its hydrophobicity. To develop a molecular-level description of the physics underlying transport resistance in this system, we have performed a computational reaction-diffusion kinetics study of water evaporation from Nafion. Two distinct models are examined, one mimicking the blocking function proposed in the literature and the other assuming that there is no blocking, treating instead water evaporation as a dynamic balance between uptake from the gas and desorption from the polymer surface. Simulation results are compared to time-dependent infrared data over a range of 100-0% relative humidity from the literature. Only the dynamic model successfully reproduces experimental observations. This indicates that the physical nature of interfacial transport resistance is not slow diffusion across an interfacial layer; rather, it is due to the competition between dehydration and rehydration. The simulation data provide details on the accompanying water distributions throughout the membrane and on interfacial kinetics, showing that they are characterized by strong fluctuations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Dynamically Formed Active Sites on Liquid Boron Oxide for Selective Oxidative Dehydrogenation of Propane

Boron-based catalysts have been shown to be both active and selective for driving the oxidative dehydrogenation of propane (ODHP) without the use of precious metals. This reaction occurs at temperatures that melt the oxide catalyst which challenges our ability to identify the liquid structures of the boron oxide phase under reaction conditions, hindering the understanding of its active sites and reaction mechanism. By combining ab initio molecular dynamics simulation, in-situ Raman characterization, and microkinetic modeling, we propose that the di-coordinated boron sites (BO2) in liquid boron oxide are the active species for O2 activation under reaction conditions. The formed peroxy-like species (>B-O-O-B<) can be viewed as a moderate oxidant for ODHP. The dynamical >B-O* dangling bond originated from >B-O-O-B< site as well as the liquid B2O3 structure itself, plays a critical role in the abstraction of H atoms from propane (C3H7 radical formation). Microkinetic modeling reveals C3H7 radical formation to be the main rate controlling step (~75% degree of rate control) with the dehydration of boron hydroxyls (B-OHs) to recover the di-coordinated boron active sites controlling the remainder of the rate (~25% degree of rate control). Moreover, the activation barriers are found to strongly depend upon the surface B-OH concentration. These findings provide significant insights into the active site and reaction mechanisms on boron-based catalysts for ODHP and underlie the importance of understanding the liquid nature of the catalyst to account for the catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗