SEARCH · Engineering Papers
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.
Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations
Yb2CoTe2(SO7)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Yb3+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Yb–O bond distances ranging from 2.30–2.73 Å. Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent SO4 tetrahedra. There are a spread of Co–O bond distances ranging from 1.86–2.03 Å. Te4+ is bonded in a 3-coordinate geometry to three O2- atoms. There are a spread of Te–O bond distances ranging from 1.85–1.99 Å. S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one CoO6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are a spread of S–O bond distances ranging from 1.47–1.53 Å. There are seven inequivalent O2- sites. In the first O2- site, O2- is bonded in a 2-coordinate geometry to one Yb3+ and one S6+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Yb3+ and one S6+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one Yb3+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Co2+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Yb3+, one Co2+, and one Te4+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Yb3+, one Co2+, and one Te4+ atom. In the seventh O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent Yb3+ and one Te4+ atom.
NaAu(SO4)2 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.34–2.79 Å. Au3+ is bonded in a square co-planar geometry to four O2- atoms. There are two shorter (2.03 Å) and two longer (2.05 Å) Au–O bond lengths. S6+ is bonded in a tetrahedral geometry to four O2- atoms. There are a spread of S–O bond distances ranging from 1.44–1.56 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Au3+ and one S6+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Au3+, and one S6+ atom. In the third O2- site, O2- is bonded in a distorted linear geometry to one Na1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Na1+ and one S6+ atom.
KAu(SO4)2 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. K1+ is bonded in a 8-coordinate geometry to ten O2- atoms. There are a spread of K–O bond distances ranging from 2.86–3.39 Å. Au3+ is bonded in a square co-planar geometry to four O2- atoms. There are two shorter (2.04 Å) and two longer (2.05 Å) Au–O bond lengths. S6+ is bonded in a tetrahedral geometry to four O2- atoms. There are a spread of S–O bond distances ranging from 1.44–1.57 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Au3+, and one S6+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent K1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one K1+, one Au3+, and one S6+ atom.
Large-scale stationary storage forms a key sector that can be economically served by sodium-ion batteries. In realizing practical sodium-ion batteries, discovery and development of novel cathodes is essential. In this spirit, alluaudite-type Na 2 Fe 2 (SO 4 ) 3 was reported in 2014 to have the highest Fe 3+ /Fe 2+ redox potential (~3.8 V vs. Na). This finding led to reports on various PO4 3– and SO4 2– based alluaudite compounds exhibiting high energy densities. In 2017, MoO 4 2– based alluaudite, Na 2.67 Mn 1.67 (MoO 4 ) 3 , was found as a 3.45 V cathode material. Exploring molybdenum chemistry further, this work reports alluaudite type Na 3.36 Co 1.32 (MoO 4 ) 3 (NCMo) as a novel versatile electroactive cathode for Li-ion and Na-ion batteries. It was synthesized by a wet solution-combustion route with a restricted annealing duration of 1 min at 600 °C. Calorimetric study revealed the formation enthalpy from component oxides (ΔH° f,ox = –575.49 ± 7.75 kJ/mol) to be highly exothermic. Unlike the sulfate class of alluaudites, this material is highly stable in air and moisture (ΔH ds = 537.42 ± 0.78 kJ/mol). Having an ionic conductivity of 6.065 × 10 –8 S/cm (at 50 °C), it offers a pseudo two-dimensional Na + migration pathway. Without any material optimization, NCMo was found to work as a high-voltage insertion cathode (ca. 4.0 V vs. Na/Na + and 4.1 V vs. Li/Li + ) in sync with theoretically predicted potential of 3.98 V (vs. Na/Na + ). Ex-situ X-ray diffraction and photoelectron spectroscopy studies revealed the occurrence of solid-solution redox mechanism solely involving Co 3+ /Co 2+ redox centre. Finally, it benchmarks Na 3.36 Co 1.32 (MoO 4 ) 3 as a novel electrochemically active Mo-based alluaudite-type polyanionic cathode insertion material.
Ion exchange (IX) resins are used in pump-and-treat (P&T) facilities to remove soluble groundwater contaminants. However, natural anions present at concentrations orders of magnitude higher than contaminants can compete for IX sites and impact resin lifecycles. Here, the Hanford Site’s 200 West Area P&T facility (Washington State, USA) was selected as a case study because it currently uses two IX resins: Purolite® A532E (A532E) to remove pertechnetate (TcO 4 - ) and DOWEX 21K (DOWEX) to remove uranium from groundwater. Nitrate (NO 3 - ), sulfate (SO 4 2- ), chloride (Cl - ), and carbonate (CO 3 2- ) anions have been identified to potentially compete for A532E and DOWEX IX sites. Hanford-relevant anion groundwater concentrations were used to design a series of laboratory-scale batch experiments to evaluate the impact of competing anions on resin performance and potential kinetic effects. These data are then modeled to obtain Cl--normalized equilibrium exchange coefficients (K) needed to predict IX resin performance. The work is presented in two parts, with IX performance evaluated for A532E in Part I and DOWEX in Part II. Part I results demonstrate that TcO 4 - uptake is not impacted by NO 3 - , SO 4 2- , Cl - , CO 3 2- (as HCO 3 - ) and U(VI) carbonate anions, with K TcO4-/Cl- > 4,000, likely due to the high selectivity of A532E trihexylammonium sites for the large, weakly hydrated TcO 4 - anion. Other anion K values were K NO3-/Cl- = 20, K SO4--/Cl- = 0.2, K HCO3-/Cl- = 0.09, K U/Cl- = 370–1000. These K values provide conservative parameters for predicting A532E performance, and demonstrate that, under these test conditions, A532E will remove TcO 4 - from current and future influent streams to meet groundwater treatment objectives.
LiAu(S2O7)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six SO4 tetrahedra. There are a spread of Li–O bond distances ranging from 2.11–2.26 Å. Au3+ is bonded in a square co-planar geometry to four O2- atoms. All Au–O bond lengths are 2.03 Å. There are two inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with two equivalent LiO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 6–42°. There are a spread of S–O bond distances ranging from 1.43–1.64 Å. In the second S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one LiO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. There are a spread of S–O bond distances ranging from 1.43–1.68 Å. There are seven inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Au3+ and one S6+ atom. In the second O2- site, O2- is bonded in a bent 120 degrees geometry to one Au3+ and one S6+ atom. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Li1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a linear geometry to one Li1+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to one Li1+ and one S6+ atom. In the sixth O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the seventh O2- site, O2- is bonded in a single-bond geometry to one S6+ atom.
RbAu(SO4)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Rb1+ is bonded to twelve O2- atoms to form RbO12 cuboctahedra that share corners with four equivalent SO4 tetrahedra, edges with four equivalent RbO12 cuboctahedra, edges with four equivalent SO4 tetrahedra, and faces with two equivalent RbO12 cuboctahedra. There are a spread of Rb–O bond distances ranging from 3.10–3.36 Å. Au3+ is bonded in a square co-planar geometry to four O2- atoms. All Au–O bond lengths are 2.04 Å. S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with two equivalent RbO12 cuboctahedra and edges with two equivalent RbO12 cuboctahedra. There are a spread of S–O bond distances ranging from 1.45–1.56 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to two equivalent Rb1+ and one S6+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to three equivalent Rb1+ and one S6+ atom. In the third O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Au3+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Rb1+, one Au3+, and one S6+ atom.
The selectivity of ion exchange (IX) resins for aqueous contaminant removal can be impacted by changing concentrations of competing natural groundwater ions. In a two-part investigation, the Hanford Site 200 West Area pump-and-treat (P&T) facility in Washington State, USA is used as a case study to evaluate the performance of two IX resins for groundwater treatment: Purolite® A532E for pertechnetate (TcO 4 - ) removal, explored in Part I, and DOWEX 21K (DOWEX) for uranium (U) removal. In Part II, DOWEX selectivity for U, as uranyl carbonate species, and uptake kinetics is quantified in a series of laboratory-scale aqueous batch experiments containing Hanford-relevant concentrations of competing anions nitrate (NO 3 - ), sulfate (SO 4 2- ), chloride (Cl - ), and carbonate (CO 3 2- ), as well as co-mingled contaminant TcO 4 - . Here the results demonstrate that DOWEX trimethylammonium functional groups are highly selective for U carbonate species (85–100 % uptake) under all conditions investigated. Only NO 3 - concentrations of 100 mM were shown to decrease U removal, with the extent (85–99 %) depending on competing anion concentrations present in solution. However, at the highest NO 3 - concentrations reported for groundwaters treated at the P&T facility (25 mM), the effect on U uptake is minimal. The batch sorption results are modeled to obtain chloride normalized equilibrium exchange coefficients (K) for predicting DOWEX performance: K SO4--/Cl- = 2.0, K NO3-/Cl- = 5.0, K HCO3-/Cl- = 1.5, K TcO4-/Cl- = 2,000, and K U/Cl- = 50,000. These K values predict little effect of current and future influent chemistries on U removal by DOWEX, where both uranyl carbonate species and TcO 4 - are removed such that effluent concentrations meet groundwater treatment requirements.
Green rusts (GR) are mixed-valence iron (Fe) hydroxides which form in reducing redox environments like riparian and wetland soils and shallow groundwater. In these environments, silicon (Si) can influence Fe oxides’ chemical and physical properties but its role in GR formation and subsequent oxidative transformation have not been studied starting at initial nucleation. Green rust sulfate [GR(SO 4 )] and green rust carbonate [GR(CO 3 )] were both coprecipitated from salts by base titration in increasing % mol Si (0, 1, 10, and 50). The minerals were characterized before and after rapid (24 h) aqueous air-oxidation by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fe extended x-ray absorption fine structure spectroscopy (EXAFS), and N 2 -BET surface area. Results showed that only GR(SO4) or GR(CO3) was formed at every tested Si concentration. Increasing % mol Si caused decreased plate size and increased surface area in GR(CO3) but not GR(SO4). GR plate basal thickness was not changed at any condition indicating a lack of Si interlayering. Air oxidation of GR(SO4) at all % mol Si contents transformed by dissolution and reprecipitation into lepidocrocite and goethite, favoring ferrihydrite with higher % Si content. Air oxidation of GR(CO3) transformed into magnetite and goethite but increasing Si caused GR to oxidize while retaining its hexagonal plate structure via solid-state oxidation. Our results indicate that Si has the potential to cause GR to form in smaller particles and upon air oxidation, Si can either stabilize the plate structure or alter transformation to ferrihydrite.
CoH2SO5 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent CoO6 octahedra and corners with four equivalent SO4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of Co–O bond distances ranging from 2.06–2.21 Å. H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four equivalent CoO6 octahedra. The corner-sharing octahedra tilt angles range from 43–48°. There is two shorter (1.48 Å) and two longer (1.50 Å) S–O bond length. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Co2+ and one S6+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one Co2+ and one S6+ atom. In the third O2- site, O2- is bonded in a distorted water-like geometry to two equivalent Co2+ and two equivalent H1+ atoms.
Rb2Pd(S4O13)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Rb1+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Rb–O bond distances ranging from 3.03–3.42 Å. Pd2+ is bonded in a square co-planar geometry to four O2- atoms. There are two shorter (2.04 Å) and two longer (2.07 Å) Pd–O bond lengths. There are four inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.43–1.75 Å. In the second S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.42–1.65 Å. In the third S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.43–1.81 Å. In the fourth S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.43–1.65 Å. There are thirteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one Rb1+ and one S6+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one Rb1+ and one S6+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the fourth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd2+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to two equivalent Rb1+ and one S6+ atom. In the sixth O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the seventh O2- site, O2- is bonded in a single-bond geometry to one Rb1+ and one S6+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to one Rb1+ and one S6+ atom. In the ninth O2- site, O2- is bonded in a single-bond geometry to one Rb1+ and one S6+ atom. In the tenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Pd2+ and one S6+ atom. In the eleventh O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the twelfth O2- site, O2- is bonded in a single-bond geometry to one Rb1+ and one S6+ atom. In the thirteenth O2- site, O2- is bonded in a single-bond geometry to two equivalent Rb1+ and one S6+ atom.
K2Pd(S4O13)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. K1+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of K–O bond distances ranging from 2.87–3.27 Å. Pd2+ is bonded in a square co-planar geometry to four O2- atoms. There are two shorter (2.04 Å) and two longer (2.07 Å) Pd–O bond lengths. There are four inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.43–1.75 Å. In the second S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.42–1.65 Å. In the third S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.43–1.80 Å. In the fourth S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.42–1.65 Å. There are thirteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the fourth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd2+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to two equivalent K1+ and one S6+ atom. In the sixth O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the ninth O2- site, O2- is bonded in a single-bond geometry to one K1+ and one S6+ atom. In the tenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Pd2+ and one S6+ atom. In the eleventh O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the twelfth O2- site, O2- is bonded in a single-bond geometry to one K1+ and one S6+ atom. In the thirteenth O2- site, O2- is bonded in a single-bond geometry to one K1+ and one S6+ atom.
Li2CoH8(SO6)2 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with four equivalent SO4 tetrahedra, and an edgeedge with one LiO6 octahedra. The corner-sharing octahedra tilt angles range from 50–63°. There are a spread of Li–O bond distances ranging from 2.14–2.46 Å. Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with four equivalent LiO6 octahedra and corners with two equivalent SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 50–63°. There are four shorter (2.09 Å) and two longer (2.15 Å) Co–O bond lengths. There are four inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the third H1+ site, H1+ is bonded in a distorted single-bond geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.63 Å) H–O bond length. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one CoO6 octahedra and corners with four equivalent LiO6 octahedra. The corner-sharing octahedra tilt angles range from 37–57°. There are a spread of S–O bond distances ranging from 1.48–1.51 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Co2+ and one S6+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Li1+ and one S6+ atom. In the third O2- site, O2- is bonded in a distorted water-like geometry to one Li1+, one Co2+, and two H1+ atoms. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Li1+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a distorted water-like geometry to one Li1+, one Co2+, and two H1+ atoms. In the sixth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Li1+, one H1+, and one S6+ atom.
The utilization of lithium aluminum [Li–Al] layered double hydroxides (LDHs) is explored for direct lithium extraction (DLE) from geothermal brines and minerals. Following extraction, the Li + ions need to be removed from the LDH structure and converted into LiOH or Li 2 CO 3 products, making them suitable for battery applications. The research investigates the delithiation of [Li–Al-X] LDHs (where X = Cl – , OH – , and SO 4 2– ), which were synthesized and dried under different conditions. Herein the study aims to understand how the choice of anions and drying conditions affects the delithiation process. To determine the stability of these [Li–Al] LDHs, high-temperature oxide melt solution calorimetry is employed. The results reveal that the stability of LDHs varies significantly based on postdrying conditions, anion choice, and the water content in the interlayer. The order of stability, as indicated by the enthalpy of formation values, is found to be OH-LDH-O > OH-LDH-A > SO 4 -LDH-O > SO4-LDH-A > Cl-LDH-O > Cl-LDH-A. This trend is attributed to the interactions among the interlayer species and the metal hydroxide layers.