Search NASA⌕ Search

SEARCH · Search NASA

Results for “carbonated MgO”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

49 records · Page 3

Post-landing major element quantification using SuperCam laser induced breakdown spectroscopy

The SuperCam instrument on the Perseverance Mars 2020 rover uses a pulsed 1064 nm laser to ablate targets at a distance and conduct laser induced breakdown spectroscopy (LIBS) by analyzing the light from the resulting plasma. SuperCam LIBS spectra are preprocessed to remove ambient light, noise, and the continuum signal present in LIBS observations. Prior to quantification, spectra are masked to remove noisier spectrometer regions and spectra are normalized to minimize signal fluctuations and effects of target distance. In some cases, the spectra are also standardized or binned prior to quantification. To determine quantitative elemental compositions of diverse geologic materials at Jezero crater, Mars, we use a suite of 1198 laboratory spectra of 334 well-characterized reference samples. The samples were selected to span a wide range of compositions and include typical silicate rocks, pure minerals (e.g., silicates, sulfates, carbonates, oxides), more unusual compositions (e.g., Mn ore and sodalite), and replicates of the sintered SuperCam calibration targets (SCCTs) onboard the rover. For each major element (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O), the database was subdivided into five “folds” with similar distributions of the element of interest. One fold was held out as an independent test set, and the remaining four folds were used to optimize multivariate regression models relating the spectrum to the composition. We considered a variety of models, and selected several for further investigation for each element, based primarily on the root mean squared error of prediction (RMSEP) on the test set, when analyzed at 3 m. In cases with several models of comparable performance at 3 m, we incorporated the SCCT performance at different distances to choose the preferred model. Shortly after landing on Mars and collecting initial spectra of geologic targets, we selected one model per element. Subsequently, with additional data from geologic targets, some models were revised to ensure results that are more consistent with geochemical constraints. The calibration discussed here is a snapshot of an ongoing effort to deliver the most accurate chemical compositions with SuperCam LIBS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi-catalytic active site biochar-based catalysts for glucose isomerized to fructose: Experiments and density functional theory study

In this study, this work provides an innovative method for preparing different isomerization catalysts by impregnating different proportions of MgCl 2 and AlCl 3 and combining different K compounds on cellulose-derived biochar, followed by pyrolysis. Results show MgO and Al(OH) 3 existing in 4 Mg- 1 Al-C catalyst can obtain better catalytic effect on glucose isomerization than the singe of Al presenting in 0 Mg- 1 Al-C catalyst. Moreover, the synergism effects of the multi-catalytic active sites such as β-, γ -Al(OH) 3 , KCl, MgO, and K 4 H 2 (CO 3 ) 3 in Mg-Al-KHCO 3 -C catalyst can further lead to an increase in glucose isomerization, compared to the 4 Mg- 1 Al-C catalyst. The X-ray diffraction results present that the value of O/Al in Mg-Al-KHCO 3 -C catalyst is as high as 13.38, which provides many unsaturated acidic catalysis sites and benefits the glucose isomerization. Simultaneously, the TPD results reveal that the main active sites (MgO, Al(OH) 3 , and K 4 H 2 (CO 3 ) 3 ) in Mg-Al-KHCO 3 -C catalyst can provide weakly acidic and basic sites and avoid strongly acidic and basic sites to excessively attack the glucose. Based on the DFT analysis, the results indicate that the MgO has a great effect on the ring-opening reaction to form acyclic glucose, while Al(OH) 3+ has a great effect on promoting acyclic glucose hydrogen transfer isomerized to form fructose. Compared to other carbon-based metal catalysts, the prepared Mg-Al-KHCO 3 -C has excellent catalytic performance, which gives a higher fructose yield (38.7%) and selectivity (87.72%) and glucose conversion (44.12%) at 100 °C in 30 min. In this study, we develop a highly efficient Mg-Al-K-biochar catalyst for glucose isomerization and provide an efficient method for cellulose valorization.

36 MATERIALS SCIENCE↗

Geochemical-hydromechanical couplings during water-serpentinized harzburgite interactions at 20° C and 30 bars

Interaction of groundwater with the serpentinized harzburgites of the upper mantle plays an important role in the geologic carbon cycle and serpentinization processes. Here, in this study, an intact serpentinized harzburgite with more than 60% lizardite from the Semail ophiolite in Oman was reacted with water at near neutral pH and low PCO 2 to observe its dissolution behavior and reaction path within the CaO-MgO-SiO 2 -CO 2 -H 2 O system at 20 °C and 30 bars. In the experiment, mass (i.e. H 2 O, ions) transfer is by diffusion and the selected temperature and pressure conditions mimic water-rock interactions at the shallow portions of most ultramafic rock hosted aquifers. Equilibrium activity-activity diagrams and thermodynamic data were used to compare the experimentally determined reaction path with the theoretical stability boundaries for minerals involved to investigate the evolution of bulk chemical composition, mineralogy, and water composition. The experiments demonstrated that (i) the water-rock interactions increased the pH of the aqueous phase from 5.9 to 7.5 over a period of 18 weeks; (ii) the dissolution of lizardite, orthopyroxene (enstatite), and clinopyroxene (diopside and augite) increased the concentration of Mg, Ca, and Si in the aqueous phase; (iii) the dissolution was incongruent with respect to Mg and Si, favoring Si release at pH > 6 due to (a) breaking of more reactive cation‑oxygen bonds that is consistent with the stoichiometry of magnesium for proton exchange reaction which favors a surface that is enriched in Mg at basic conditions, and (b) preferential dissolution of clinopyroxene Mg 1.30 Ca 0.52 Fe 0.06 Si 2 O 6 ; (iv) the aqueous phase was undersaturated with respect to carbonate (e.g. calcite, magnesite, and hydromagnesite) and hydrous (e.g. lizardite, chrysotile, brucite, and talc) minerals; (v) the bulk chemical composition and mineralogy of the intact serpentinized harzburgite matrix did not change; (vi) the thermodynamic data can successfully predict water-intact serpentinized harzburgite behavior if the water chemical composition can be constrained; and (vii) no detectable macroscopic form of damage (e.g. microcracks forming as a result of differential stress fields due to changes in volume during chemical reaction) was observed.

Carbonation↗

Effect of surface acidity modulation on Pt/Al 2 O 3 single atom catalyst for carbon monoxide oxidation and methanol decomposition

With ideal metal utilization efficiency and homogeneous active sites, single atom catalysts (SACs) have attracted extensive attention in heterogeneous catalysis field. The performance of SACs is highly dependent on the local coordination environment of metal single atoms. However, few works reported the effect of surface acidity modification on the performance of SACs such as Pt SACs which have been widely studied nowadays. In this work, a Pt/Al 2 O 3 SAC has been successfully prepared using a bayerite Al(OH) 3 as support through simple IWI method for Pt loading. Through post-modification of Pt/Al 2 O 3 with acidic WO 3 and basic MgO, the surface acidity of Pt/Al 2 O 3 was tuned. Here, activity of CO oxidation and methanol decomposition on the modified catalysts has been evaluated. It was found that the catalytic performance was highly related to the surface acidity of Pt SACs. Basic MgO modified Pt/Al 2 O 3 performed better in CO oxidation under the reaction condition with H 2 O. Acidic WO 3 modified Pt/Al 2 O 3 showed superior activity in methanol decomposition. Detailed characterization and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study suggested that the positive H 2 O effect on CO oxidation was due to the mitigated formation of bicarbonate species on Pt/Al 2 O 3 and WO 3 /Pt/Al 2 O 3 catalysts and the promoted desorption of carbonate species from MgO/Pt/Al 2 O 3 . The superior methanol decomposition performance on WO 3 /Pt/Al 2 O 3 was owing to its abundant oxygen vacancies and high resistance to carbonate accumulation. This study highlights the importance of surface acidity modulation of Pt SACs in heterogeneous catalysis and suggests that fine-tuning the surface acidity can be an effective strategy in new SACs development.

36 MATERIALS SCIENCE↗

Alkali Vapor Corrosion of Spinel (MgAl 2 O 4 ) and Gahnite (ZnAl 2 O 4 ) Refractories—A Comparative Study

Alkali vapor corrosion is critical for refractories used in the kilns and furnaces of diverse high-temperature processing and manufacturing sectors such as gasifiers, cement production, and glass making. Gahnite (ZnAl 2 O 4 ) is being investigated as a potential chrome-free refractory because of its similarity with the structure and properties of magnesium aluminate (MgAl 2 O 4 ) spinel. The alkali vapor corrosion of ZnAl 2 O 4 , MgAl 2 O 4 , and Mg 0.5 Zn 0.5 Al 2 O 4 was studied, according to ASTM C987-10, at 1371°C for 24 h using sodium carbonate (Na 2 CO 3 ). The surface and the polished cross-sections of the corroded ZnAl 2 O 4 , MgAl 2 O 4 , and Mg 0.5 Zn 0.5 Al 2 O 4 specimens were analyzed using x-ray diffraction (XRD), microscopy, and energy-dispersive spectroscopy (EDS) techniques. MgO in MgAl 2 O 4 , ZnO in ZnAl 2 O 4 , Mg 0.77 Zn 0.23 O, and NaAlO 2 were detected as the corrosion products for these specimens. The extent of corrosion substantially varied among the specimens despite the similarity in the corrosion products. The corrosion resistance increased in the following order: Mg 0.5 Zn 0.5 Al 2 O 4 > MgAl 2 O 4 > ZnAl 2 O 4 . The formation of a dense MgO and Mg 0.77 Zn 0.23 O layer for MgAl 2 O 4 and Mg 0.5 Zn 0.5 Al 2 O 4 , respectively, contributed to their superior resistance to alkali vapor corrosion. The underlying corrosion mechanisms are discussed based on experimental observations supported by thermodynamic analysis. Additionally, the results suggest that a partial Zn 2+ substitution for Mg 2+ in MgAl 2 O 4 can enhance the resistance to alkali vapor corrosion.

alkali corrosion↗

Energetics of CO 2 and H 2 O adsorption on alkaline earth metal doped TiO 2

The process of CO 2 and H 2 O adsorption on the surface of nano-oxide semiconductors is important in the overall performance of artificial photosynthesis and other applications. In this study, we explored the thermodynamics of CO 2 and H 2 O adsorption on TiO 2 as a function of surface chemistry. We applied gas adsorption calorimetry to investigate the energetics of adsorption of those molecules on the surface of anatase nanoparticles. In an attempt to increase TiO 2 surface affinity to CO 2 and H 2 O, TiO 2 was doped with alkaline earth metals (MgO, CaO, SrO, and BaO) by manipulating the chemical synthesis. Adsorption studies using diffuse reflectance infrared spectroscopy at different temperatures indicate that due to the segregation of alkaline earth metals on the surface of TiO 2 nanoparticles, both CO 2 and subsequent H2O adsorption amounts could be increased. CO 2 adsorbs in two different manners, forming carbonates which can be removed at temperatures lower than 700 °C, and a more stable linear adsorption that remains even at 700 °C. Additionally to the surface energetic effects, doping also increased specific surface area, resulting in further improvement in net gas adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pristine Interface between Lithium Lanthanum Zirconate and Lithium Manganese Oxide by Pulsed Laser Deposition

Solid state lithium-ion batteries have garnered increasing interest in recent years due to several potential advantages over liquid-electrolyte based systems. The possibility of integrating the lithium garnet oxide, Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO), with the high voltage cathode, spinel Li x Mn 2 O 4 (LMO), is evaluated here. Thin film bilayer structures are prepared by pulsed laser deposition on MgO (001) substrates and characterized by x-ray diffraction and transmission electron microscopy. The LLZTO is grown by an alternating layer-by-layer deposition of LLZTO and Li 3 N and subsequently annealed for several hours at 575 °C to promote crystallinity. Growth of crystalline LMO with a pristine interface to LLZTO is achieved by gentle heat treatment (500 °C) to remove surface carbonate from the electrolyte and by cathode growth at a low temperature of 250 °C. Higher temperature depositions (330 – 450 °C) result in reaction between the two materials and the appearance of Li 2 MnO 3 , which may be in part due to the presence of excess lithium in the electrolyte layer. Because fully lithiated LiMn 2 O 4 has a voltage of ≈3.7 V versus Li+/Li, the observation of a well-defined interface, free of impurity phases and with no interdiffusion of elements, indicates LLZTO is stable to at least 3.7 V.

Garnet LLZO↗

N 2 O Formation Mechanism and Suppression Strategy on Pt Catalysts for NO x Removal from Hydrogen-Internal Combustion Engines

Pt-based catalysts exhibit excellent low-temperature activity in the selective catalytic reduction of NO x with H 2 (H 2 -SCR), but their tendency to form N 2 O poses a significant challenge for practical use. This issue is further complicated by unclear formation mechanisms, hindering the development of more efficient catalysts. This study explored the N 2 O generation mechanisms on Pt catalysts supported by MgO, Al 2 O 3 , SiO 2 , and TiO 2 , aiming to achieve a deep understanding that could advance the Pt catalysts with high NO x conversion and minimized N 2 O emissions. Through systematic kinetics and characterization analyses, the direct influence of the support acidity and reactant dynamics (O 2 and NO) on N 2 O formation was clearly revealed. Notably, the Pt catalysts with strong NO adsorption capacity showed reduced N 2 O generation, highlighting the critical role of NO adsorption sites in the H 2 -SCR process. By incorporation of NO adsorption sites (i.e., MgO, BaO, CeO 2 ) onto Pt/SiO 2 , both the H 2 -SCR efficiency and N 2 selectivity (reduced N 2 O selectivity) were significantly enhanced, effectively reducing the N 2 O emissions through optimized surface NO adsorption. These findings provide a design framework for more selective Pt-based catalysts, advancing H 2 -SCR systems for effective NO x abatement from hydrogen-internal combustion engines, which is a promising carbon-free transportation technology.

36 MATERIALS SCIENCE↗

Seismic fault weakening via CO 2 pressurization enhanced by mechanical deformation of dolomite fault gouges

Carbon dioxide emissions from dolomite decarbonation play an essential role in the weakening of carbonate faults by lowering the effective normal stress, which is thermally activated at temperatures above 600–700 °C. However, the mechanochemical effect of low-crystalline ultrafine fault gouge on the decarbonation and slip behavior of dolomite-bearing faults remains unclear. In this study, we obtained a series of artificial dolomite fault gouges with systematically varying particle sizes and dolomite crystallinities using a high-energy ball mill. The laboratory-scale pulverization of dolomite yielded MgO at temperatures below 50 °C, indicating that mechanical decarbonation without significant heating occurred due to the collapse of the crystalline structure, as revealed by X-ray diffraction and solid-state nuclear magnetic resonance results. Furthermore, the onset temperature of thermal decarbonation decreased to ~400 °C. Numerical modeling reproduced this two-stage decarbonation, where the pore pressure increased due to low-temperature thermal decarbonation, leading to slip weakening on the fault plane even at 400–500 °C; i.e., 200–300 °C lower than previously reported temperatures. Thus, the presence of small amounts of low-crystalline dolomite in a fault plane may lead to a severely reduced shear strength due to thermal decomposition at ~400 °C with a small slip weakening distance.

58 GEOSCIENCES↗

First-principles equation of state database for warm dense matter computation

We put together a first-principles equation of state (FPEOS) database for matter at extreme conditions by combining results from path integral Monte Carlo and density functional molecular dynamics simulations of the elements H, He, B, C, N, O, Ne, Na, Mg, Al, and Si as well as the compounds LiF , B 4 C , BN , CH 4 , CH 2 , C 2 H 3 , CH , C 2 H , MgO , and MgSiO 3 . For all these materials, we provide the pressure and internal energy over a density-temperature range from ~ 0.5 to 50 g cm - 3 and from ~ 10 4 to 10 9 K, which are based on ~ 5000 different first-principles simulations. We compute isobars, adiabats, and shock Hugoniot curves in the regime of L - and K -shell ionization. Invoking the linear mixing approximation, we study the properties of mixtures at high density and temperature. Furthermore, we derive the Hugoniot curves for water and alumina as well as for carbon-oxygen, helium-neon, and CH-silicon mixtures. We predict the maximal shock compression ratios of H 2 O , H 2 O 2 , Al 2 O 3 , CO , and CO 2 to be 4.61, 4.64, 4.64, 4.89, and 4.83, respectively. Finally we use the FPEOS database to determine the points of maximum shock compression for all available binary mixtures. We identify mixtures that reach higher shock compression ratios than their end members. We discuss trends common to all mixtures in pressure-temperature and particle-shock velocity spaces. In the Supplemental Material, we provide all FPEOS tables as well as computer codes for interpolation, Hugoniot calculations, and plots of various thermodynamic functions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Hydrogen generation via ammonia decomposition on highly efficient and stable Ru-free catalysts: approaching complete conversion at 450 °C

We report Hydrogen (H 2 ) is a prospective zero-carbon and high-energy-density fuel alternative to fossil fuels for generating power and clean energy. Ammonia (NH 3 ) is a promising H 2 (17.7%) carrier, which can easily overcome the challenges associated with H 2 storage and transportation. Thermocatalytic ammonia decomposition reaction (ADR) is an effective way to produce clean H 2 but it relies on the use of expensive and rare ruthenium (Ru)-based catalysts at elevated temperatures (>500 °C), hence is not sustainable and economically feasible. Herein, we report a synergistic strategy to design a heterostructured Ru-free catalyst, consisting of CoNi alloy nanoparticles well-dispersed on a MgO–CeO 2 –SrO mixed oxide support with potassium promotion. The resulting K–CoNi alloy –MgO–CeO 2 –SrO catalyst presents 97.7% and 87.5% NH 3 conversion efficiency at 450 °C at gas hourly space velocities (GHSVs) of 6000- and 12 000-mL h -1 g cat -1 , respectively. At 500 °C, the H 2 production rate (57.75 mmol g cat -1 min -1 ) becomes comparable to that of most of the reported Ru-based catalysts. The catalyst stability has been successfully demonstrated in both a fixed-bed reactor under high pressure (120 h at 5.0 bar) and a membrane reactor prototype (600 h at 1.5 bar) at 500 °C. High-temperature in situ XPS analysis, temperature-programmed desorption/reduction, and density functional theory calculations have been carried out to elucidate the possible active sites and performance enhancement mechanisms. This work highlights the importance of constructing optimal interfaces between active metal nanoparticles and oxide support for boosting the NH 3 to H 2 conversion efficiency and long-term stability.

25 ENERGY STORAGE↗

Grafted nickel-promoter catalysts for dry reforming of methane identified through high-throughput experimentation

High-throughput synthesis of a series of monometallic and bimetallic catalysts (45 bimetallic and 50 monometallic samples) consisting of nickel and one of nine different metal promoters (B, Co, Cu, Fe, Mg, Mn, Sn, V and Zn) supported on one of six different metal oxides alumina, ceria, magnesia, silica and titania) is carried out via organometallic grafting using a robotic platform. The catalysts are evaluated for their activity and selectivity for the dry reforming of methane at a feed ratio of CH 4 :CO 2 of 1 at 650–800 °C in a parallel flow reactor system. The type of oxide support prevails over the type of additive for both catalyst activity and stability. On Al 2 O 3 and MgO, Fe was found to be the best promoter; on SiO 2 , Cu is the best promoter at 700 °C and higher, while on TiO 2 , Mn is found to enhance the conversion at 800 °C. On CeO 2 , all additives except Fe have beneficial effects. Twenty-five catalysts show > 90% methane conversion with ten catalysts showing > 95% conversion at 800 °C with the H 2 :CO ratios ranging from 0.8 to 1.2. Amongst the ten highest performers, NiFe/Al 2 O 3 and NiFe/MgO are more active than Ni/Al 2 O 3 and Ni/MgO, respectively and were stable over a period of 25 h at 800 °C. Characterization on the as-prepared samples reveals highly dispersed phase, while after reduction in H 2 , highly dispersed and reduced nickel particles up to 10 nm are formed. The particles do not increase in size under dry reforming reaction conditions at 800 °C. An increased hydrogen consumption observed during H 2 -TPR of the nickel particles is positively correlated with methane conversion for Al 2 O 3 -based catalysts. The resistance to deactivation by coking and variation in coke structure are investigated by spectroscopic and microscopic methods to identify the relationship between metal promoters, alloy formation, and type of surface carbon deposits. Carbon whiskers were observed on the ten selected spent samples and are preferentially deposited on Ni rather than on the promoters. Carbon nanotube formation and metal particle removal from support were not observed to cause deactivation while amorphous carbon formation was clearly linked to catalyst deactivation, as amorphous carbon could encapsulate nickel, either on the support or at the end of the carbon nanotube. Furthermore, the organometallic grafting technique is an efficient and suitable technique for synthesizing highly dispersed and homogeneous phases which lead to high conversion and high durability for dry reforming of methane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calorimetric Energies and Chemical Potentials of Metal Atoms in Catalytic Nanoparticles on Oxide and Carbon Supports: Improved Size Dependencies and Adhesion Energies

The chemical potential of metal atoms, μM, in supported metal nanoparticles is an important descriptor related to both the catalytic activity and the stability of the nanoparticles. Here, we derive an expression relating μM to the radius of the particle’s contact area with the support and the adhesion energy at the metal/support interface (E adh ) that assumes the particles have the shape of spherical caps but of arbitrary contact angle with the support (θ c ) and includes an empirical correction for the increase in metal surface energy and adhesion energy with decreasing radius of curvature. We then show that, at any assumed contact angle, we can simultaneously fit previously reported measurements of both calorimetric μ M (from heats of metal vapor adsorption during nanoparticle growth by vapor deposition) versus metal coverage data and the He + low-energy ion scattering (LEIS) intensities for the metal and/or support versus metal coverage (using our recently developed spherical cap model for quantitative LEIS intensities), to determine the particle size versus coverage and E adh . Only one choice of contact angle gives a pair of values for contact angle and E adh , which is consistent with the Young–Dupré equation for the equilibrium shape of a spherical particle. At this equilibrium shape, we then applied this spherical cap model (SCM) to reanalyze microcalorimetric metal chemical potentials and LEIS signals versus coverage data for nine metal/support combinations that were previously analyzed by assuming that the particles had the shape of hemispherical caps, i.e., with a contact angle of 90°. We show that this revised approach gives close agreement with the calorimetric and LEIS data; the best-fit contact angles vary from 64 to 84°, correcting the earlier assumption of 90°. Furthermore, these results provide significant accuracy improvements in particle size versus coverage, metal chemical potential versus size and coverage, metal/support adhesion energies and contact angles for Cu, Ag and Au on CeO 2 (111), Ni on MgO(100), Ag on Fe 3 O 4 (111) and TiO 2 (100), and Ag, Ni and Pd on Ni-supported graphene. This revised approach is much more broadly applicable than the earlier hemispherical cap model (HCM).

99 GENERAL AND MISCELLANEOUS↗