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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Entropy-Driven Porous Liquids Allowing Gas Solubility in Solvent-Filled Imine-Based Porous Organic Cages

Porous liquids offer a promising platform for gas separation by combining fluid processability with intrinsic molecular porosity. Traditional Type II porous liquids are formed by dissolving porous molecular cages in size-excluded solvents, limiting solvent options and practical applications. In this work, we introduce a novel method of creating Type II porous liquids using common small solvents, where intrinsic porosity is achieved at elevated pressures due to the selective displacement of solvent molecules by gas molecules within the cage structures. Using molecular simulations, we investigate the behavior of CO 2 in solutions of the imine-based porous organic cage CC13 dissolved in small molecular solvents such as chloroform and 1,2-dimethoxyethane (DME). Grand canonical Monte Carlo simulations of solid-state CC13 reveal that selectivity reversal, where smaller CO 2 molecules displace larger solvent molecules inside the cage, is achievable at sufficiently high pressures. Temperature quench molecular dynamics simulations confirm that while CO 2 displacement within chloroform-filled cages is limited, DME enables entropy-driven cage CO 2 occupancy at pressures as low as ∼23 bar, setting up the foundation of an alternative way of forming Type II porous liquids.

adsorption↗
DOE OSTI2020

Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal–Organic Framework Material

Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO 4 N] node controlled by the specific host–guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. In this work, we have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H 2 O upon dehydration to give MFM-520. Filling MFM-520 with CO 2 and SO 2 reveals that, while CO 2 has a minimal structural influence, SO 2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO 2 under flue-gas desulfurization conditions, and the facile release of captured SO 2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO 2 .

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

FEED Study of Carbon Capture Inc. DAC and CarbonCure Utilization Using United States Steel's Gary Works Waste Plant

Direct Air Capture (DAC) has been proposed as a means of reducing atmospheric concentrations of CO2. While DAC has been evaluated through lab-scale, bench-scale, and small-scale pilot units, large-scale deployment has not been achieved. Feasibility studies are one tool to understand the potential design, operation, performance, and impact of commercial-scale DAC. This paper presents the results of a feasibility study for a passive DAC system deployed at >100,000 tpy scale in three different regions across the U.S. and awarded to Carbon Collect by the U.S. Department of Energy National Energy Technology Laboratory (DOE NETL). The MechanicalTree™technology has been designed and engineered by Carbon Collect based on the concept initially developed at Arizona State University Center for Negative Carbon Emissions. It uses a tower of stacked, sorbentcontaining disks supported by a lifting mechanism, exposed to the air to capture CO2 during the adsorption phase. The disks are then lowered into a regeneration chamber for vacuum and steam regeneration to produce CO2 product during the desorption step. The modular tree design allows large installations with repeatable, mass-manufactured units connected to common utilities such as steam supply, vacuum, and CO2 processing for compression and geologic storage. The passive DAC system eliminates the equipment and energy of forced air fans by using natural air circulation to contact the sorbent with the CO2 in the air. Because of this, the performance is dependent on the wind speed in addition to the temperature and relative humidity. Performance and flow rate fluctuations were incorporated into equipment and facility design with considerations for turndown to 10% of maximum rated flow to allow operation in all seasons. The feasibility study was undertaken to evaluate the technology in different regions and climates. Three locations were selected for this study representing different climates: Alabama (hot and humid), California (hot and arid), and Wyoming (continental). For each region, the adsorption/desorption cycle was optimized including tuning the heat integration and cycle timings. The performance of individual trees was then scaled to the full facility with the same design of more than 20,000 trees common between all regions. The installations had expected average CO2 capture rates of between 330,000 and 485,000 tonnes of CO2 per year depending on the climate. The initial engineering design for the facility at each location was performed with cost and performance estimates for the trees, carbon purification and compression, and the balance of plant. To supply thermal and electrical energy for the facility, carbon-free or low-carbon power must be considered. Options for low-carbon, continuous thermal and electrical energy were considered. The best-performing option from those considered was identified to be an electrically-heated molten salt energy storage system, powered by an on-site photovoltaic field. During molten salt thermal discharge, steam is produced from heat exchange with the molten salt and used to generate power in a steam turbine as well as steam for regenerating the DAC carbon trees. The thermal and electrical supply and analysis is presented in the context of low-carbon power for carbon removal. Modelling and economics of transportation and geologic storage of the CO2 is considered and presented for each location. The results of the feasibility study are incorporated into the presented techno-economic and life-cycle assessments. This work is intended to provide an understanding of the performance, cost, and impact of capturing CO2 at the commercial scale and the impact of climate and regional siting on the considered passive DAC system.

42 ENGINEERING↗
DOE OSTI2025

Assessing the Performance of Exchange‐Correlation Density Functionals in Describing the Iron‐Catalyzed Ammonia Synthesis System

Density functional theory (DFT) has been widely employed for elucidating mechanistic aspects of heterogeneous catalysis. However, the accuracy of DFT calculations relies heavily on selecting an exchange-correlation (XC) functional that correctly describes the electronic structure of materials involved in the reactions. This study assesses the accuracy of several XC density functionals for modeling the iron-catalyzed ammonia synthesis system. In the assessment of functional accuracy, experimental references are compared to DFT-calculated values for the formation energy of gas-phase ammonia and nitrogen, bulk Fe/Fe-nitride (γ′-Fe 4 N) lattice constants and cohesive/formation energies, and nitrogen and ammonia binding energies on Fe(100), Fe(111), Fe(110), and γ′-Fe 4 N(111). It is observed that the experimental value for each of these descriptors is accurately modeled by at least one functional. RPBE alone provides reliable estimates for both the lattice constant and cohesive energy of Fe and γ′-Fe 4 N. Temperature-programmed desorption experiments led to estimates for N and NH 3 adsorption across several Fe-based facets that are best captured by RPBE. These results highlight the importance of choosing an appropriate XC functional that accurately describes experimental systems and offer insights into effectively modeling the interactions between nitrogen and ammonia on Fe-based surfaces.

adsorption↗
DOE OSTI2025

The Surface Chemistry of Methanol on TiO 2 (110): Effects of Pressure and Temperature on the Stability of C–O and C–H Bonds

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS) was used to study the surface chemistry of methanol on TiO 2 (110), examining the effects of methanol pressure, oxide temperature, and coadsorption with H 2 . At 300 K, the adsorption of methanol on TiO 2 (110) leads to the formation of CH 3 O on the surface with a minor amount of CH 3 OH present. The easy cleavage of the O–H bond in the alcohol agrees with the predictions of theoretical calculations, and most of the adsorbed CH 3 O was not associated with the presence of Ti 3+ sites in the oxide substrate. The adsorbed CH 3 O was removed from the TiO 2 (110) surface by heating to 600 K without the deposition of CH x fragments or C on the oxide. The results of temperature-programmed desorption (TPD) showed the evolution of methanol and formaldehyde at 360 and 490 K as a result of a disproportionation reaction: 2CH 3 O → CH 3 OH + CH 2 O. This surface chemistry, where there is no rupture of the C–O bond, and only selective cleavage of O–H and C–H bonds, is very different from that found on metals used in catalysts for methanol reforming, where massive conversion of the alcohol into CO, CH x and C species is seen. Furthermore, the TPD data indicate that any CH 3 O formed on the oxide surface can be hydrogenated and desorbed as CH 3 OH at temperatures below 550 K. In this respect, titania is an ideal support for catalysts employed to achieve methanol synthesis through CO 2 hydrogenation.

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

Predicting metal–metal interactions. II. Accelerating generalized schemes through physical insights

Operando-computational frameworks that integrate descriptors for catalyst stability within catalyst screening paradigms enable predictions of rates and selectivity on chemically faithful representations of nanoparticles under reaction conditions. These catalyst stability descriptors can be efficiently predicted by density functional theory (DFT)-based models. The alloy stability model, for example, predicts the stability of metal atoms in nanoparticles with site-by-site resolution. In this work, we use physical insights to present accelerated approaches of parameterizing this recently introduced alloy-stability model. These accelerated approaches meld quadratic functions for the energy of metal atoms in terms of the coordination number with linear correlations between model parameters and the cohesive energies of bulk metals. By interpolating across both the coordination number and chemical space, these accelerated approaches shrink the training set size for 12 fcc p- and d-block metals from 204 to as few as 24 DFT calculated total energies without sacrificing the accuracy of our model. We validate the accelerated approaches by predicting adsorption energies of metal atoms on extended surfaces and 147 atom cuboctahedral nanoparticles with mean absolute errors of 0.10 eV and 0.24 eV, respectively. This efficiency boost will enable a rapid and exhaustive exploration of the vast material space of transition metal alloys for catalytic applications.

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

Synergistic Effect of Diatomic Mo-B Site Confined in Graphene-Like C 2 N Enables Electrocatalytic Nitrogen Reduction via Novel Mechanism

Structural modulation of active site with atomic-level precision is of great importance to meet the activity and selectivity challenges that electrocatalysts are commonly facing. In this work, we have designed a metal (M) - nonmetal (NM) diatomic site embedded in graphene-like C 2 N (denoted as Mo-B@C 2 N), where electrocatalytic N 2 reduction reaction (eNRR) was thoroughly explored using density functional theory combined with computational hydrogen electrode method. Compared to M-M diatomic sites, Mo-B site can generate pronounced synergistic effect that led to eNRR proceeding via a novel quasi-dissociative reaction mechanism that has not been reported relative to the conventional enzymatic, consecutive, distal, and alternating associative mechanism. This newly uncovered mechanism in which N-N bond scission takes place immediately after the first proton-coupled electron transfer (PCET) step (i.e., *NH-*N + H + + e – ® *NH 2 *N) has demonstrated much advantage in PCET process over the four conventional mechanism in terms of thermodynamic barrier, except that the adsorption of side-on *N 2 seemed thermodynamically unfavorable (DG ads = 0.61eV). Our results have revealed that the activation of inert NºN triple bond is dominated by π*-backdonation mechanism as a consequence of charge transfers from both B and Mo site, and unexpectedly, from the substrate C 2 N itself as well. Moreover, the hybrid Mo-B diatomic site demonstrated superior performance over either Mo-Mo or B-B site for driving eNRR. Furthermore, our study could provide insight into the delicate relationships among atomic site, substrate and electrocatalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Surface characterization of hydrogen charged and uncharged alpha-2 and gamma titanium aluminide alloys using AES and REELS

The surfaces of selected uncharged and hydrogen charged alpha-2 and gamma titanium aluminide alloys with Nb additions were characterized by Auger electron (AES) and reflected electron energy loss (REELS) spectroscopy. The alloy surfaces were cleaned before analysis at room temperature by ion sputtering. The low energy (500 eV) ion sputtering process preferentially sputtered the surface concentration. The surface concentrations were determined by comparing AES data from the alloys with corresponding data from elemental references. No differences were observed in the Ti or Nb Auger spectra for the uncharged and hydrogen charged alloys, even though the alpha-2 alloy had 33.4 atomic percent dissolved hydrogen. Also, no differences were observed in the AES spectra when hydrogen was adsorbed from the gas phase. Bulk plasmon energy shifts were observed in all alloys. The energy shifts were induced either by dissolved hydrogen (alpha-2 alloy) or hydrogen adsorbed from the gas phase (alpha-2 and gamma alloys). The adsorption induced plasmon energy shifts were greatest for the gamma alloy and cp-Ti metal.

Shanabarger, M. R.↗
DOE OSTI2026

Correlating binding energies of adsorbed CO and H on model surfaces with CO/H 2 selectivity from co-electrolysis of CO 2 and H 2 O over copper–palladium bimetallic catalysts

Binding energies of adsorbed CO and H are key descriptors governing the activity and selectivity of the co-electrolysis of CO 2 and H 2 O to produce syngas with desired CO/H 2 ratios. Palladium hydride (PdH), which forms in situ at negative overpotentials, has been identified as the active Pd phase for CO 2 reduction to syngas. Herein, binding energies of CO and H are determined using temperature programmed desorption (TPD) of CO and H 2 from Pd(111), PdH/Pd(111), and Cu/PdH/Pd(111) under ultra-high vacuum (UHV) conditions. TPD results reveal that desorption of H 2 from subsurface PdH occurs at 460 K, while desorption from surface PdH is more facile at 320 K. CO desorption temperatures shift 20 K lower on PdH/Pd(111) compared to on Pd(111). The presence of 0.7 ML Cu further increases the desorption temperature of H 2 by 30 K while simultaneously reducing CO desorption temperatures by 70 K. Density functional theory (DFT) calculations show that CO adsorption onto Pd sites is hindered on the 0.7 ML Cu/PdH/Pd(111) surface while the kinetic barrier for H 2 desorption is increased. The trends in the binding energies of CO and H on model surfaces are consistent with electrochemical measurements of CuPd powder catalysts in a membrane electrode assembly (MEA), where H 2 evolution is reduced while CO production is enhanced compared to unmodified Pd catalysts. Overall, the results from model surface studies (TPD and DFT) provide a prediction and explanation for the activity and CO/H 2 ratios observed in electrochemical experiments. This study also demonstrates that CuPd is a promising catalyst with reduced Pd-loading to produce CO-rich syngas.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Next Generation Fiber-Encapsulated Nanoscale Hybrid Materials for Direct Air Capture with Selective Water Rejection

Recently, NOHMs sorbents have been demonstrated to be highly stable and tunable for CO2 capture and have negligible vapor pressure, but their main drawbacks are high viscosity and high gas transfer limitation in their neat bulk phase. This project explored gas-assisted electrospinning processing coupled with promising encapsulation matrices such as Polymers with Intrinsic Microporosity (PIM-1) and polyacrylonitrile (PAN)/organopolysilizane (OPSZ) polymer/ceramic hybrid materials, which were demonstrated to be effective novel carriers for the active NOHMs sorbents. These encapsulation materials were evaluated by their thermal stability, hydrophobicity, permeability, and CO2 selectivity. The manufacturing parameters such as component composition and processing solvent were linked to bulk sorbent properties, e.g., surface area, pore volume, fiber thickness, capture capacity, capture kinetics, etc. These investigations resulted in fundamental knowledge and technical know-how that will be useful for scaling up the nanofiber mat contactor design. The encapsulation materials and design has been shown to not only increase the thermal oxidative stability of the NOHMs, but also yield significantly reduced pressure drop and increased performance of large modular air filters. 70 PAN: 30 OPSZ/NIPEI fibers exhibited the highest capture performance with 1.5 mmol CO2/g∙h kinetics the first hour under 100% CO2 condition, followed by 80 PAN: 20 OPSZ/NIPEI and 90 PAN: 10 OPSZ/NIPEI, while 90 PAN: 10 OPSZ/NIPEI fibers performed the best with 0.25 mmol CO2/g∙h of the initial kinetics under 400 ppm CO2 concentration. All the fabricated fibers demonstrated stable capture performances up to 15 cycles of adsorption and desorption. Using encapsulated NOHMs, the study found that the microwave could help regenerate the capture materials within 20 minutes without chemically degrading the materials. A high-level TEA/LCA study was performed to evaluate the feasibility of this technology at scale. These estimates show that the sorbent cost and environmental impact levels are comparable to other existing technologies. Overall, these findings increase the technological feasibility of using liquid-like, low vapor pressure NOHMs as a next generation sorbent for the direct air capture of CO2.

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

Local Environment of Superoxide Radical Formed on the TiO 2 Surface Produced From Ti(OiPr) 4 Exposed to H 2 O 2

A selective heterogeneous catalyst with the superoxide anion O 2 •– stable at room temperature, generated by treating Ti(OR) 4 (R=iPr, nBu) with H 2 O 2 , was previously reported and used for the oxidation of organic compounds. Furthermore, it was proposed that exceptional stability of the O 2 •– is resulted from its stabilization near Ti +4 cation on the TiO 2 surface with participation of water molecules and/or OH groups. In this article, we performed high-resolution pulsed EPR study on the O 2 •– in this catalyst with the aim to obtain quantitative information about its interactions with the surrounding molecules. Our data has shown that the O 2 •– is involved in weak hyperfine interactions with protons in the nearest environment, which do not exceed a value of 2 MHz. It corresponds to an Os…H distance of ≥ 3 Å that exclude the formation of hydrogen bonds. The analysis of possible structures of O 2 •– adsorption on TiO 2 surface taking into account our results and lack of radical mobility at room temperature previously observed in EPR spectra led us to suggest that the O 2 •– is stabilized in the form of superoxo bridge coordinated with two titanium atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

A Revised Calibration Function and Results for the Phoenix Mission TECP Relative Humidity Sensor

The original calibration function of the R(sub H) sensor on the Phoenix Thermal and Electrical Conductivity Sensor (TECP) has been revised in order to extend the range of the valid calibration, and to improve accuracy. The original function returned non-physical R(sub H) values at the lowest temperatures. To resolve this, and because the original calibration was performed against a pair of hygrometers that measured frost point (T(sub f)), the revised calibration equation is also cast in terms of frost point. Because of the complexity of maintaining very low temperatures and high R(sub H) in the laboratory, no calibration data exists at T is greater than 203K. However, sensor response during the mission was smooth and continuous down to 181 K. Therefore we have opted to include flight data in the calibration data set; selection was limited to data acquired during periods when the atmosphere is known to have been saturated. T(sub f) remained below 210 K throughout the mission(P is greater than 0.75 Pa). R(sub H), conversely, ranged from 1 to well under 0.01 diurnally, due to approximately 50 K temperature variations. To first order, both vapor pressure and its variance are greater during daylight hours. Variance in overnight humidity is almost entirely explained by temperature, while atmospheric turbulence contributes substantial variance to daytime humidity. Likewise, data gathered with the TECP aloft reflect higher H2O abundances than at the surface, as well as greater variance. There is evidence for saturation of the atmosphere overnight throughout much of the mission. In virtually every overnight observation, once the atmosphere cooled to T(sub f), water vapor begins to decrease, and tracks air temperature. There is no evidence for substantial decreases in water vapor prior to saturation, as expected for adsorptive exchange. Likewise, there is no evidence of local control of vapor by phases such as perchlorate hydrates hydrated minerals. The daytime average H2O pressure does not change substantially over the course of the mission, although the H2O column abundance varies by a factor of 2. Column abundances calculated from TECP data are lower than orbital measurements if one assumes that H2O is uniformly mixed through a single scale height. These results argue that the vertical distribution of H2O begins to change well in advance of surface concentrations as northern autumn approaches.

Phoenix Thermal and Electrical Conductivity Sensor↗
DOE OSTI2021

Measuring Gas Transport and Sorption in Large Intact Geologic Specimens via the Piezometric Method

Uptake of noble gases into heterogeneous geologic core samples was measured using a piezometric methodology. In addition to measuring accessible porosity—as with gas pycnometry—by monitoring the rate of pressure decay, this method can also be used to estimate the gas effective diffusivity in the sample. In contrast to previous applications of this method, where milligram quantities of fractured grains are characterized, here approximately kilogram core samples were left intact when tested. In doing so, a more representative sample of the heterogeneous field geology is provided. Additionally, alteration of the pore structure and connectivity during sample preparation is avoided. Furthermore, to scale the piezometric method from milligrams to kilograms, the system was designed to operate at medium vacuum (1 to 100 Pa) to restrict transport in pores less than approximately 60 µm to large Knudsen numbers. To test the system performance, two samples of interest were selected: a rhyolitic welded tuff from Blue Canyon Dome at the Energetic Materials Research and Testing Center and a zeolitized non-welded rhyolitic tuff from the Nevada National Security Site. Three noble gases were utilized in this test series; Argon and xenon as they are of direct interest to nuclear monitoring efforts and helium as it is a weakly adsorbing reference standard. Additionally, mercury intrusion porosimetry measurements were made on subsamples of the core to compare the observed porosity by the two methods and to discuss gas transport rates in the context of the measured pore distribution.

58 GEOSCIENCES↗
DOE OSTI2025

Nitrate Reduction Modeling under Acidic Conditions with Late Transition Metals

The electrochemical reduction of nitrate (NO 3 R) to ammonia is a bold yet conceivable way of producing ammonia using renewable electricity. However, serious challenges remain in finding optimal electrocatalysts for the process. An atomistic understanding of the surface energetics behind the NO 3 R is needed in order to design an efficient catalyst. Herein, we combine energetics from density functional theory and microkinetic modeling to demonstrate how surface descriptors can help simplify the search for efficient NO 3 R electrocatalysts. We illustrate the strong correlations between transition-state energetics and O* binding energies for adsorbed nitrate and nitrite on transition metals. For intermediates from NO* and beyond, we compare the benefits of using either the N* or H* binding energies to predict reduction onset potentials. These insights enable us to develop a simple microkinetic model that elucidates the surface coverages of intermediates and the product selectivity of NO 3 R across a range of potentials and transition metals. As a result, we show that the model adequately corroborates with quasi-steady-state rates observed experimentally.

ammonia↗
NASA NTRS1995

Supporting technology for the development of Controlled Ecological Life Support Systems (CELSS)

To support the development of Controlled Ecological Life Support Systems (CELSS) in the space program, a metabolic simulator has been selected for use in a closed chamber to test functions of the CELSS. This metabolic simulator is a catalytic reactor which oxidizes the methyl acetate to produce carbon dioxide and water vapor. In this project, kinetic studies of catalytic oxidation of methyl acetate were conducted using monolithic and pellet catalysts with 0.5% (by weight) platinum (Pt) on aluminum oxide (Al2O3). The reaction was studied at a pressure of one atmosphere and at temperatures varying from 160 C to 420 C. By-products were identified at the exit of the preheater and reactor. For the kinetic study with the monolithic catalyst, a linear regression method was used to correlate the kinetic data with zero-order, first-order and Langmuir-Hinshelwood models. Results indicate that the first-order model represents the data adequately at low concentrations of methyl acetate. For higher concentrations of methyl acetate, the Langmuir-Hinshelwood model best represents the kinetic data. Both rate constant and adsorption equilibrium constants were estimated from the regression. A Taguchi orthogonal array (L(sub 9)) was used to investigate the effects of temperature, flow rate, and concentration on the catalytic oxidation of methyl acetate. For the monolithic catalyst, temperature exerts the most significant effect, followed by concentration of methyl acetate. For the pellet catalyst, reaction temperature is the most significant factor, followed by gas flow rate and methyl acetate concentration. Concentrations of either carbon dioxide or oxygen were seen to have insignificant effect on the methyl acetate conversion process. Experimental results indicate that the preheater with glass beads can accomplish thermal cracking and catalytic reaction of methyl acetate to produce acetic acid, methanol, methyl formate, and 1-propanol. The concentration of all by-products was measured in ppmv (parts per million by volume). At higher temperatures, greater amounts of these products are produced, as expected. In all cases, methanol was the predominant concentration detected, followed by methyl formate. At temperatures lower than 320 C for the P-type monolithic catalyst, methanol, acetic acid, and acetone were detected, whereas, for the E-type monolithic catalyst, only methanol was detected at 160 C. Both P and E types of the monolithic catalyst were specified with the same substrates (ceramic), washcoat (Al2O3), and promoter (Pt). However, the manufacturing and treatment procedures were quite different. It was therefore concluded that the performance of the E-type monolithic catalyst is superior to that of the P-type for oxidation of methyl acetate. At higher reaction temperatures, e.g., above 420 C, all reactants and byproducts were completely oxidized using these two types of monolithic catalyst to produce carbon dioxide and water vapor. A complex heterogenous catalytic reaction mechanism was proposed to explain the formation of the byproducts (methanol, acetic acid, and methyl formate) as the methyl acetate traveled through the preheater packed with glass beads. The by-product, 1-propanol, may be formed only through a homogeneous reaction, since it is difficult to develop a reasonable sequence of heterogeneous reaction steps to explain its formation. The homogeneous thermal decomposition of methyl acetate to form free radicals was proposed to explain the formation of 1-propanol, and also methanol, in the preheater. A dual-site catalytic reaction mechanism was proposed for the oxidation of methyl acetate over Pt/Al2O3 monolithic catalyst. The dual-site mechanism describes the chemisorption of oxygen molecules as well as a physical adsorption of methyl acetate on the active sites. On the active sites, methyl acetate is oxidized rapidly to form carbon dioxide and water vapor. A rate equation derived from this mechanism gives the Langmuir-Hinshelwood rate formula which has been observed from the experimental data obtained in this project for high methyl acetate concentration (greater than 1000 ppmv) over a monolithic catalyst. If the oxygen concentration is very high and methyl acetate concentration is very low, the reaction rate equation is then reduced to a first-order with respect to methyl acetate concentration. The first-order model has also been observed from the experimental data obtained in this project for low methyl acetate concentration (less than 1000 ppmv).

Li, Ku-Yen↗
NASA NTRS2007

Metabolic Heat Regenerated Temperature Swing Adsorption for CO2 and Heat Removal/Rejection in a Martian PLSS

Two of the fundamental problems facing the development of a Portable Life Support System (PLSS) for use on Mars, are (i) heat rejection (because traditional technologies use sublimation of water, which wastes a scarce resource and contaminates the premises), and (ii) rejection of carbon dioxide (CO2) in an environment with a CO2 partial pressure (ppCO2) of 0.4-0.9 kPa. Patent-pending Metabolic heat regenerated Temperature Swing Adsorption (MTSA) technology is being developed to address both these challenges. The technology utilizes an adsorbent that when cooled with liquid CO2 to near sublimation temperatures (~195K) removes metabolically-produced CO2 in the ventilation loop. Once fully loaded, the adsorbent is then warmed externally by the ventilation loop (~300K), rejecting the captured CO2 to Mars ambient. Two beds are used to provide a continuous cycle of CO2 removal/rejection as well as facilitate heat exchange out of the ventilation loop. Any cryogenic fluid can be used in the application; however, since CO2 is readily available on Mars and can be easily produced and stored on the Martian surface, the solution is rather elegant and less complicated when employing liquid CO2. As some metabolic heat will need to be rejected anyway, finding a practical use for metabolic heat is also an overall benefit to the PLSS. To investigate the feasibility of the technology, a series of experiments were conducted which lead to the selection and partial characterization of an appropriate adsorbent. The Molsiv Adsorbents 13X 8x12 (also known as NaX zeolite) successfully removed CO2 from a simulated ventilation loop at the prescribed temperature swing anticipated during PLSS operating conditions on Mars using a cryogenic fluid. Thermal conductivity of the adsorbent was also measured to eventually aid in a demonstrator design of the technology. These results provide no show stoppers to the development of MTSA technology and allow its development to focus on other design challenges as listed in the conclusions section of this paper.

Iacomini, Christine↗
DOE OSTI2020

Oxide-catalyzed self- and cross-condensation of cycloketones. Kinetically relevant steps that determine product distribution

Metal oxides with acid-base properties can be used to catalyze aldol condensation and potentially obtain valuable chemicals from biomass-derived oxygenates. Understanding the reaction mechanisms could enable the development of effective catalysts with controllable selectivity. In this work, we investigate the reaction parameters that affect the kinetics and product distribution of self- and cross-aldol condensation of cyclopentanone (CPO) and cyclohexanone (CHO) over CeO 2 and ZrO 2 catalysts by combining detailed analysis of experiments and DFT calculations. It is well-known that either the deprotonation of an α-C–H that generates an enolate or the C–C coupling that produces the dimers can be rate-limiting step. Indeed, the detailed kinetics analysis shows that the observed data can be fitted by unimolecular or bimolecular Langmuir-Hinshelwood models. Specifically, on the ZrO 2 catalyst, the unimolecular α-C–H activation is the rate limiting step for the CPO self-condensation, while the bimolecular C–C coupling limits the CHO self-condensation. By contrast, on CeO 2 , the bimolecular C–C coupling step seems to be rate-limiting for both CPO and CHO self-condensation reactions. The adsorption parameters derived from kinetics fitting indicate that when the two reactants are co-fed, the surface is preferentially covered by CHO. So, the condensation rate of [CPO]-activated products ([CPO]CPO + [CPO]CHO) decreases in the presence of CHO, due to the competitive adsorption. However, despite a higher surface coverage, CHO is not an effective electrophile because it imposes stronger steric constraints to the formation of the C–C bond than CPO. Therefore, for a given enolate, the product distribution shows that [CPO]CPO > [CPO]CHO and, similarly [CHO]CPO > [CHO]CHO. Likewise, the yields of [CPO]- and [CHO]-activated products in mixed CPO/CHO feeds are similar because the higher surface coverage and stability of the [CHO] enolate is counterbalanced by the inhibition of C–C coupling by steric constraints when CHO is involved. In summary, the overall rank of products observed experimentally can be explained in terms of a combination of the following effects: relative surface coverage of the reactants, steric constraints for the C–C coupling, stability of the enolate, and effectiveness of the electrophile to accept an electron.

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

Electrocatalytic Hydrogen Evolution at Full Atomic Utilization over ITO-Supported Sub-nano-Pt n Clusters: High, Size-Dependent Activity Controlled by Fluxional Pt Hydride Species

A combination of density functional theory (DFT) and experiments with atomically size-selected Pt n clusters deposited on indium-tin oxide (ITO) electrodes was used to examine the effects of applied potential and Pt n size on the electrocatalytic activity of Pt n (n = 1, 4, 7, 8) for the hydrogen evolution reaction (HER). Activity is found to be negligible for isolated Pt atoms on ITO, increasing rapidly with Pt n size, such that Pt 7 /ITO and Pt 8 /ITO have roughly double the activity per Pt atom compared to atoms in the surface layer of polycrystalline Pt. Both DFT and experiment find that hydrogen under-potential deposition (H upd ) results in Pt n /ITO (n = 4, 7, 8) adsorbing ~2 H atoms/Pt atom at the HER threshold potential, equal to ca. double the Hupd observed for Pt bulk or nanoparticles. Here, the cluster catalysts under electrocatalytic conditions are hence best described as a Pt hydride compound, significantly departing from a metallic Pt cluster. The exception is Pt 1 /ITO, where H adsorption at the HER threshold potential is energetically unfavorable. Theory combines global optimization with grand canonical approaches for the influence of potential, uncovering that several metastable structures contribute to HER, changing with the applied potential. It is hence critical to include reactions of the ensemble of energetically accessible Pt n H x /ITO structures to correctly predict the activity vs. Pt n size and applied potential. For the small clusters, spillover of H ads from the clusters to the ITO support is significant, resulting in a competing channel for loss of H ads , particularly at slow potential scan rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗