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All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Use of Additives to Improve Performance of Methyl Butyrate-Based Lithium-Ion Electrolytes

This work addresses the need for robust rechargeable batteries that can operate well over a wide temperature range. To this end, a number of electrolyte formulations have been developed that incorporate the use of electrolyte additives to improve the high-temperature resilience, low-temperature power capability, and life characteristics of methyl butyrate-based electrolyte solutions. These electrolyte additives include mono-fluoroethylene carbonate (FEC), lithium oxalate, vinylene carbonate (VC), and lithium bis(oxalato)borate (LiBOB), which have been shown to result in improved high-temperature resilience of all carbonate-based electrolytes. Improved performance has been demonstrated of Li-ion cells with methyl butyrate-based electrolytes, including 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %); 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 2% FEC; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 4% FEC; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + lithium oxalate; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 2% VC; and 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 0.10M LiBOB. These electrolytes have been shown to improve performance in MCMB-LiNiCoO2 and graphite-LiNi1/3Co1/3Mn1/3O2 experimental Li-ion cells. A number of LiPF6-based mixed carbonate electrolyte formulations have been developed that contain ester co-solvents, which have been optimized for operation at low temperature, while still providing reasonable performance at high temperature. For example, a number of ester co-solvents were investigated, including methyl propionate (MP), ethyl propionate (EP), methyl butyrate (MB), ethyl butyrate (EB), propyl butyrate (PB), and butyl butyrate (BB) in multi-component electrolytes of the following composition: 1.0M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + X (20:60:20 v/v %) [where X = ester co-solvent]. ["Optimized Car bon ate and Ester-Based Li-Ion Electrolytes", NASA Tech Briefs, Vol. 32, No. 4 (April 2008), p. 56.] Focusing upon improved rate capability at low temperatures (i.e., 20 to 40 C), this approach was optimized further, resulting in the development of 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %), which were demonstrated to operate well over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12(-)LiNiCoAlO2 prototype cells.

Smart, Marshall C.↗
NASA NTRS2017

Constraints on Mechanisms of Chondrule Formation from Chondrule Precursors and Chronology of Transient Heating Events in the Protoplanetary Disk

The mineralogy, petrography, and oxygen-isotope compositions of porphyritic chondrules—dominant chondrule type in most chondrite groups—suggest formation by incomplete melting of isotopically diverse precursors during localized transient heating events in dust-rich regions of the protoplanetary disk characterized by 16O-poor compositions (D17Odust+gas~ –7‰ to +4‰) relative to the inferred Sun’s value (D17O ~ –28 ± 2‰). The chondrule precursors included Ca,Al-rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), chondrules of earlier generations, fine-grained matrix-like material, and possibly fragments of pre-existing planetesimals. Like porphyritic chondrules, igneous CAIs formed by melting of isotopically diverse precursors during transient heating events, but in an isotopically distinct, solar-like reservoir of the protoplanetary disk (D17O dust + gas ~ –24‰), probably near the proto Sun. Based on a narrow range of the initial 26Al/27Alratios inferred from the internal Al-Mg isochrons in igneous CAIs, their melting started at the very beginning of Solar System formation (t0), defined by the CV CAIs with U-corrected Pb-Pb age of 4567.3 ± 0.16 Ma and the canonical 26Al/27Al ratio of (5.25 ± 0.02) ¥ 10–5, and lasted at least 0.3 Ma. The U-corrected Pb-Pb absolute and 26Al-26Mg relative ages of porphyritic chondrules from type 3 ordinary, CO, CV, and CR carbonaceous chondrites (assuming uniform distribution of 26Al in the disk at the canonical level) suggest chondrule formation started at t0 and lasted for about 4 Ma. These observations may preclude formation of the majority of porphyritic chondrules by splashing of differentiated planetesimals and by collisions between planetesimals; instead, they are consistent with melting of dust balls by bow shocks or magnetized turbulence in the disk. Some porphyritic chondrules in equilibrated (petrologic type 4–6) ordinary chondrites contain relict fragments of coarse-grained chromite, ilmenite, phosphates, and albitic plagioclase. The similar mineral assemblage is commonly observed in type 4–6 ordinary chondrites, but is absent in type 3 chondrites, suggesting these chondrules formed by incomplete melting of thermally metamorphosed ordinary chondrite material, possibly by impacts. The CB metal-rich carbonaceous chondrites contain exclusively magnesian non-porphyritic chondrules crystallized from complete melts. These chondrules formed in a gas-melt plume generated by a hypervelocity (≥20 km/s) collision between planetesimals ~4.8 Ma after t0 in a transition or a debris disk. One of the colliding bodies was probably differentiated. The CH metal-rich carbonaceous chondrites contain chondrules formed by different mechanisms. The magnesian non-porphyritic chondrules formed in the CB impact plume ~4.8 Ma after t0. The chemically diverse (magnesian, ferroan, and Al-rich) porphyritic chondrules formed by incomplete melting of isotopically diverse precursors in the protoplanetary disk, most likely prior the CB impact plume event. We conclude that there are multiple mechanisms of chondrule formation that operated over the entire life-time of the disk.

Chondrules↗
DOE OSTI2020

Materials Data on Bi10(Pb2O7)3 by Materials Project

Bi10(Pb2O7)3 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are three inequivalent Pb2+ sites. In the first Pb2+ site, Pb2+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Pb–O bond distances ranging from 2.25–2.59 Å. In the second Pb2+ site, Pb2+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Pb–O bond distances ranging from 2.22–2.58 Å. In the third Pb2+ site, Pb2+ is bonded in a 3-coordinate geometry to three O2- atoms. There are one shorter (2.23 Å) and two longer (2.32 Å) Pb–O bond lengths. There are five inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded to five O2- atoms to form distorted corner-sharing BiO5 square pyramids. There are a spread of Bi–O bond distances ranging from 2.12–2.43 Å. In the second Bi3+ site, Bi3+ is bonded to five O2- atoms to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. There are a spread of Bi–O bond distances ranging from 2.17–2.55 Å. In the third Bi3+ site, Bi3+ is bonded to five O2- atoms to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. There are a spread of Bi–O bond distances ranging from 2.13–2.66 Å. In the fourth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Bi–O bond distances ranging from 2.14–2.67 Å. In the fifth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Bi–O bond distances ranging from 2.13–3.00 Å. There are eleven inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to three Bi3+ atoms. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Pb2+ and two Bi3+ atoms. In the third O2- site, O2- is bonded in a 4-coordinate geometry to one Pb2+ and three Bi3+ atoms. In the fourth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Pb2+ and two Bi3+ atoms. In the fifth O2- site, O2- is bonded to two Pb2+ and two equivalent Bi3+ atoms to form distorted edge-sharing OBi2Pb2 tetrahedra. In the sixth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Pb2+ and two Bi3+ atoms. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to one Pb2+ and three Bi3+ atoms. In the eighth O2- site, O2- is bonded in a trigonal non-coplanar geometry to one Pb2+ and two Bi3+ atoms. In the ninth O2- site, O2- is bonded in a 3-coordinate geometry to one Pb2+ and two Bi3+ atoms. In the tenth O2- site, O2- is bonded in a 4-coordinate geometry to one Pb2+ and three Bi3+ atoms. In the eleventh O2- site, O2- is bonded in a distorted square co-planar geometry to two equivalent Pb2+ and two equivalent Bi3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cu3Pb2Se2(NO7)2 by Materials Project

Cu3Pb2(SeO4)2(NO3)2 crystallizes in the orthorhombic Cmc2_1 space group. The structure is two-dimensional and consists of eight nitric acid molecules and two Cu3Pb2(SeO4)2 sheets oriented in the (0, 0, 1) direction. In each Cu3Pb2(SeO4)2 sheet, there are two inequivalent Cu2+ sites. In the first Cu2+ site, Cu2+ is bonded in a square co-planar geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.92–1.99 Å. In the second Cu2+ site, Cu2+ is bonded in a square co-planar geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.95–1.97 Å. There are two inequivalent Pb4+ sites. In the first Pb4+ site, Pb4+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Pb–O bond distances ranging from 2.42–2.54 Å. In the second Pb4+ site, Pb4+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Pb–O bond distances ranging from 2.47–2.54 Å. There are two inequivalent Se2+ sites. In the first Se2+ site, Se2+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. All Se–O bond lengths are 1.74 Å. In the second Se2+ site, Se2+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. All Se–O bond lengths are 1.74 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded to three Cu2+ and one Pb4+ atom to form distorted corner-sharing OCu3Pb tetrahedra. In the second O2- site, O2- is bonded to three Cu2+ and one Pb4+ atom to form distorted corner-sharing OCu3Pb tetrahedra. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to one Cu2+, one Pb4+, and one Se2+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Cu2+, one Pb4+, and one Se2+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Cu2+, one Pb4+, and one Se2+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Cu2+, one Pb4+, and one Se2+ atom.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Planar Investigation of a CobraMRV Reentry Flowfield Using Pulse-Burst, Cross-Correlation DGV

The flowfield around a Co-Optimization Blunt-body Reentry Analysis Mid-lift/drag-ratio Rigid Vehicle (CobraMRV) vehicle is investigated with a combination of high-speed planar laser Mie scattering (PLMS) and pulse-burst cross-correlation Doppler global velocimetry (PB-CC-DGV). Tests were conducted in the NASA Langley 4-foot Supersonic Unitary Plan Wind Tunnel (UPWT) over a range of different tunnel operating conditions and model configurations. Results indicate a complex shock-boundary layer interaction. Scalar information extracted from the PLMS show the evolution of the bow shock structure, while streamwise velocity measurements indicate the spatial evolution of the shock-boundary layer interaction including the growth of the separation shock foot and eventual reacceleration of the flow at farther downstream locations. Assessment of multiple cases show strong Mach and Reynolds numbers driven effects on the character of the shock-boundary layer interactions. Measurement uncertainties ranged from 50 to 150 m/s throughout the region of interest, driven largely by angular uncertainties and instabilities in the laser pointing. The mean accuracy of the freestream measurements was found to be 5.2-percent of tunnel predicted values.

Laser↗
DOE OSTI2022

Multiplexed Anodic Stripping Voltammetry Detection of Heavy Metals in Water Using Nanocomposites Modified Screen-Printed Electrodes Integrated With a 3D-Printed Flow Cell

In this study, we present multiplexed anodic stripping voltammetry (ASV) detection of heavy metal ions (HMIs)—As(III), Cd(II), and Pb(II)—using a homemade electrochemical cell consisting of dual working, reference and counter screen-printed electrodes (SPE) on polyimide substrate integrated with a 3D-printed flow cell. Working and counter electrodes were fabricated by the screen-printing of graphite paste while the Ag/AgCl paste was screen-printed as a reference electrode (Ag/AgCl quasi-reference electrode). The working electrodes were modified with (BiO) 2 CO 3 -reduced graphene oxide (rGO)-Nafion [(BiO) 2 CO 3 -rGO-Nafion] and Fe 3 O 4 magnetic nanoparticles (Fe 3 O 4 MNPs) decorated Au nanoparticles (AuNPs)-ionic liquid (IL) (Fe 3 O 4 -Au-IL) nanocomposites separately to enhance HMIs sensing. Electrochemical detection was achieved using square wave ASV technique. The desired structure of the flow electrochemical cell was optimized by the computational fluid dynamic (CFD). Different experimental parameters for stripping analysis of HMIs were optimized including deposition time, deposition potential and flow rate. The linear range of calibration curves with the sensing nanocomposites modified SPE for the three metal ions was from 0–50 μg/L. The limits of detection (S/N = 3) were estimated to be 2.4 μg/L for As(III), 1.2 μg/L for Pb(II) and 0.8 μg/L for Cd(II). Furthermore, the homemade flow anodic stripping sensor platform was used to detect HMIs in simulated river water with a 95–101% recovery, indicating high selectivity and accuracy and great potential for applicability even in complex matrices.

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

Benzenesulfonamide Derivatives as Complexants and Extractants for Addressing the Mercury Problem at the Savannah River Site

Mercury (Hg) is a major global pollutant arising from both natural and anthropogenic sources. Its widespread use in medicinal and industrial applications makes it a common chemical exposure and environmental pollutant. It can exist in several forms which include: Metallic mercury (Hg{sup 0}), mercurous (Hg{sub 2}{sup 2+}), mercuric salts (Hg{sup 2+}), and organic mercury (e.g. CH{sub 3}Hg{sup +}), with the latter being the most toxic of all the species. Due to mercury's high toxicity, new approaches towards its detection has received significant attention in the scientific community. Mercury exposure at the Savannah River Site (SRS) has been a recent concern especially with increasing amounts of organic mercury in the saltstone. It originates mainly from its use as an acidic dissolution catalyst of aluminum cladding from target fuels within the uranium and plutonium processing operations [1]. It is present to an amount of about 60 metric tons in the high-level waste (HLW) tanks. Organic Mercury species have been found in low activity waste (LAW) at the site that eventually ends up in the saltstone. Therefore, there is a need for: i) Converting organic mercury to other less toxic forms and ii) Complexation and removal of Hg prior of disposal of LAW in saltstone. Various methods have been developed for selective sensing of mercury in the presence of other toxic metals. These methods include using ligands that can form organo-soluble metal complexes with different optical and spectroscopic properties that can be used for toxic metal sensing. In 2005, our group pioneered an ion-exchange extraction method, in which o-phenylenediamine-derived disulfonamides were used to complex and selectively extract and sense Pb{sup 2+} from aqueous solutions into an organic phase [2,3]. Herein, a disulfonamide and a bis-dansylamide have been shown to extract, complex and sense Hg(II). Ligand 1: The crystal structure of the disulfonamide-Hg complex confirms the complexation of Hg(II) with the ligand. Complexation was corroborated by the {sup 1}H-NMR spectra obtained after contacting solutions of various concentrations of Hg{sup 2+} with 2 mM ligand in chloroform. Distinct resonances are observed at Hg/L ratio of 0.5 that are also observed for the isolated 1:2 complex. In the presence of excess mercury, new resonances, as well as the movement of Et{sub 3}N resonances indicate the formation of a different Hg-sulfonamide-triethylamine complex, presumably having 1:1 Hg:L stoichiometry. The electronic spectra of aqueous phases after extraction show that there was no free ligand absorption at 0.5 eq of Hg, indicating a complete complexation. Complexation was also confirmed by the UV-visible titrations with Hg{sup 2+} at constant ligand concentration. pH-dependent extraction carried out shows that extraction of Hg(II) by ligand 1 was over 90% for most alkaline pHs. Ligand 2: The crystal structure of the Ligand 2 complex formed with Hg(OAc){sub 2} shows a remarkable coordination pattern with 4:2 metal:ligand stoichiometry. The fluorescent bis-dansyl disulfonamide derivative was found to complex and sense HgCl{sub 2} and Hg(OAc){sub 2} by demonstrating fluorescence quenching upon Hg(II) addition in comparison with other metals (Zn(II), Cd(II), Pb(II)). No were observed for Cu(II), Ag(I) and Co(II). We have shown the complexation of Hg(II) by a disulfonamide and a bis-dansyl disulfonamide ligand using several spectroscopic methods. Ligand 1 was able to extract mercury into chloroform and form a complex in the presence of excess mercury by synergistic complexation with triethylamine acting as a co-ligand. X-ray and NMR both confirm a 1:2 HgL{sub 2} stoichiometry. Ligand 2 can be used for sensing of Hg(II) as fluorescence quenching was observed after addition of Hg(II)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Selective Sorbent Design: CaS Aerogel for Rapid Remediation of Aqueous Pb (II)

Heavy metals are a persistent environmental problem due to their high toxicity, even at very low concentrations (parts per billion, ppb). The removal of such diluted heavy metals is challenging because of the competition the counterions (Ca 2+ , Na + , Mg 2+ , etc.) present in natural water bodies. The design of sorbents capable of removing ions below the action limit (15 ppb for Pb 2+ ) requires a strong driving force for selective uptake and rapid removal. In this work, we report the synthesis of porous CaS aerogels (surface area = 143.6 m 2 /g) by oxidative assembly of CaS nanoparticles and describe their use in selective Pb 2+ ion remediation from water. Despite the presence of amorphous CaCO 3 (up to 50 wt %) in the gel network, the gels demonstrated a capacity of 17.1 mmol Pb/g aerogel (3543 mg/g), and this could be augmented to 22.5 mmol Pb/g aerogel (4593 mg/g) by modifying the synthesis to reduce CaCO 3 content to ca. 15 wt %. Moreover, the selectivity of CaS aerogels toward Pb 2+ ions is high, as evidenced by little-to-no change in the distribution constant (K d ∼ 10 4 ) in the presence of competing ions (1 M) such as Na + , Mg 2+ , and Ca 2+ . During remediation with low concentrations (100 ppb) of Pb 2+ with CaS aerogels, the level of Pb 2+ dropped to 5.4 ppb (below the 15 ppb EPA limit) within 1 h with a 95.4% removal efficiency. In contrast to the CO 2 supercritically dried aerogels, lower surface area ambient dried gels (xerogels) only remove 40% of the lead ions from a 100 ppb solution, saturating within 1 h. The efficiency and rapidity of selective Pb 2+ uptake using CdS aerogels arise from a combination of a strong thermodynamic driving force for cation exchange (K eq = 2.5 × 10 27 ) and chemisorption along with favorable kinetics associated with the high surface area porous architecture. These results show that formation of high surface area metal chalcogenide aerogels by oxidative assembly to form nanocrystalline architectures, as previously demonstrated for II−VI and IV−VI semiconductors, can be extended to the more highly ionic alkaline earth sulfides.

Aerogels↗
DOE OSTI2020

Materials Data on NdCoSbPbO6 by Materials Project

NdCoPbSbO6 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic Pc space group. The structure is three-dimensional. Nd3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Nd–O bond distances ranging from 2.38–2.87 Å. Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six equivalent SbO6 octahedra. The corner-sharing octahedra tilt angles range from 22–34°. There are a spread of Co–O bond distances ranging from 2.11–2.20 Å. Pb2+ is bonded in a 3-coordinate geometry to eight O2- atoms. There are a spread of Pb–O bond distances ranging from 2.48–2.91 Å. Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with six equivalent CoO6 octahedra. The corner-sharing octahedra tilt angles range from 22–34°. There are a spread of Sb–O bond distances ranging from 2.01–2.04 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to one Nd3+, one Co2+, two equivalent Pb2+, and one Sb5+ atom. In the second O2- site, O2- is bonded in a 5-coordinate geometry to two equivalent Nd3+, one Co2+, one Pb2+, and one Sb5+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Nd3+, one Co2+, one Pb2+, and one Sb5+ atom. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to one Nd3+, one Co2+, one Pb2+, and one Sb5+ atom. In the fifth O2- site, O2- is bonded in a 5-coordinate geometry to two equivalent Nd3+, one Co2+, one Pb2+, and one Sb5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Nd3+, one Co2+, two equivalent Pb2+, and one Sb5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on FeAs2Pb4(ClO2)4 by Materials Project

FePb4As2(O2Cl)4 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Fe2+ is bonded in a distorted square co-planar geometry to four O2- and two equivalent Cl1- atoms. There is two shorter (1.83 Å) and two longer (1.91 Å) Fe–O bond length. Both Fe–Cl bond lengths are 2.65 Å. There are two inequivalent Pb2+ sites. In the first Pb2+ site, Pb2+ is bonded in a 8-coordinate geometry to four O2- and four Cl1- atoms. There are a spread of Pb–O bond distances ranging from 2.49–2.64 Å. There are a spread of Pb–Cl bond distances ranging from 3.01–3.32 Å. In the second Pb2+ site, Pb2+ is bonded in a 3-coordinate geometry to three O2- atoms. There are a spread of Pb–O bond distances ranging from 2.35–2.54 Å. As5+ is bonded in a distorted T-shaped geometry to three O2- atoms. There are a spread of As–O bond distances ranging from 1.80–1.82 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to three Pb2+ and one As5+ atom. In the second O2- site, O2- is bonded to three Pb2+ and one As5+ atom to form distorted edge-sharing OAsPb3 tetrahedra. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one Fe2+ and one As5+ atom. In the fourth O2- site, O2- is bonded in a distorted water-like geometry to one Fe2+ and one Pb2+ atom. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three equivalent Pb2+ atoms. In the second Cl1- site, Cl1- is bonded in a 1-coordinate geometry to one Fe2+ and one Pb2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LaCoSbPbO6 by Materials Project

LaPbCoSbO6 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic Pc space group. The structure is three-dimensional. La3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of La–O bond distances ranging from 2.43–2.85 Å. Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six equivalent SbO6 octahedra. The corner-sharing octahedra tilt angles range from 21–31°. There are a spread of Co–O bond distances ranging from 2.11–2.18 Å. Pb2+ is bonded in a 3-coordinate geometry to three O2- atoms. There are one shorter (2.48 Å) and two longer (2.53 Å) Pb–O bond lengths. Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with six equivalent CoO6 octahedra. The corner-sharing octahedra tilt angles range from 21–31°. There are a spread of Sb–O bond distances ranging from 2.01–2.03 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to one La3+, one Co2+, and one Sb5+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to one La3+, one Co2+, one Pb2+, and one Sb5+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one La3+, one Co2+, and one Sb5+ atom. In the fourth O2- site, O2- is bonded in a 5-coordinate geometry to two equivalent La3+, one Co2+, one Pb2+, and one Sb5+ atom. In the fifth O2- site, O2- is bonded in a 5-coordinate geometry to two equivalent La3+, one Co2+, one Pb2+, and one Sb5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one La3+, one Co2+, and one Sb5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Cation Data for the East River Watershed, Colorado (2014-2025)

This data package contains mean values for cation concentration for water samples taken from the East River Watershed in Colorado. Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentrations of elements of interest simultaneously for the East River Watershed, Colorado groundwater and surface water samples to inform insights on the biogeochemistry processes within the watershed. The East River is part of the Watershed Function Scientific Focus Area (WFSFA) located in the Upper Colorado River Basin, United States. For samples collected prior to 06-16-2021, the instrumentation, Elan DRC II, PerkinElmer SCIEX, automatically switches among the three models necessary to analyze all 37 elements. These 37 elements include: (1) Lithium (Li), Beryllium (Be), Boron (B), Sodium (Na), Magnesium (Mg), Aluminium (Al), Silicon (Si), Phosphorus (P), Titanium (Ti), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge), Arsenic (As), Rubidium (Rb), Strontium (Sr), Zirconium (Zr), Molybdenum (Mo), Silver (Ag), Cadmium (Cd), Tin (Sn), Antimony (Sb), Caesium (Cs), Barium (Ba), Europium (Eu), Lead (Pb), Thorium (Th), Uranium (U) using standard model, argon Ar as reaction gas, (2) Potassium (K), Calcium (Ca), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe) using dynamic reaction cell (DRC) model, ammonia NH3 as reaction gas, and (3) Phosphorus (P) and Selenium (Se) using DRC model, oxygen O2 as reaction gas. Note for the samples with higher concentrations of chloride (Cl-), asenic (As) concentrations were analysed with DRC model (oxygen O2 as reaction gas) to avoid the interference of chloride. For samples collected on and after 06-16-2021, an advanced Agilent 8900 triple quadrupole inductively coupled plasma mass spectrometry system (Agilent 8900 QQQ ICP-MS, Agilent Technologies) has been used to measure the concentrations of interested 36 elements simultaneously for environmental samples, including (1) Lithium (Li), Beryllium (Be) and Boron (B) using standard no gas mode, (2) Sodium (Na), Magnesium (Mg), Aluminium (Al) Phosphorus (P), Potassium (K), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge), Arsenic (As), Rubidium (Rb), Strontium (Sr), Zirconium (Zr), Molybdenum (Mo), Silver (Ag), Cadmium (Cd), Tin (Sn), Antimony (Sb), Cesium (Cs), Barium (Ba), Europium (Eu), Lead (Pb), Thorium (Th) and Uranium (U) using standard helium (He) collision mode, (3) Titanium (Ti) and Vanadium (V) using high Energy (HEHe) helium (He) collision mode, and (4) Silicon (Si), Calcium (Ca) and Selenium (Se) using standard H2 reaction mode. All samples were prepared/diluted with 2% (v/v) ultrapure nitric acid in Milli-Q water (18.2 mega ohm-cm), and analyzed under a rigorous quality assurance and quality control (QA/QC) process. This data package contains (1) a zip file (cation_data_2014_2025.zip) containing a total of 5,849 files: 5.848 data files of cation data from across the Lawrence Berkeley National Laboratory (LBNL) Watershed Function Scientific Focus Area (SFA) which is reported in .csv files per location and a locations.csv (1 file) with latitude and longitude for each location; (2) a file-level metadata (v6_20260901_flmd.csv) file that lists each file contained in the dataset with associated metadata; (3) a data dictionary (v6_20260901_dd.csv) file that contains terms/column_headers used throughout the files along with a definition, units, and data type; (4) PDF and docx files for the detemination of Method Detection Limits (MDLs) for ICP-MS PerkinElmer DRC II instrumentation (Detemination_of_Method_Detection_Limits__MDLs__for_ICP_MS__PerkinElmer_Elan_DRC_II__LBL_Bldg74_Lab214D) for samples before November 2021; (5) PDF and docx files for the determination of MDLs for ICP-MS Agilent 8900 QQQ instrumentation (ICP_MS_Analysis_detection_limits_and_QA_QC_WenmingDong_updated_2026-08-06) for samples November 2021 and onward. Missing values within the anion data files are noted as either "-9999" or "0.0" for not detectable (N.D.) data. There are a total of 113 locations containing cation data. Update on 2021-04-11: Added Detemination of Method Detection Limits (MDLs) for ICP-MS document, which can be accessed as a PDF or with Microsoft Word. Update on 2022-06-10: versioned updates to this dataset was made along with these changes: (1) updated cation data for all locations up to 2021-12-31, (2) removal of units from column headers in datafiles, (3) added row underneath headers to contain units of variables, (4) removed suffix and prefix on two variables (“aqberylliumion_asberyllium” and “aqlithiumion_aslithium”), (5) added -9999 for empty numerical cells, and (6) the addition of the file-level metadata (flmd.csv) and data dictionary (dd.csv) were added to comply with the File-Level Metadata Reporting Format. Update on 2022-09-09: Updates were made to reporting format specific files (file-level metadata and data dictionary) to correct swapped file names, add additional details on metadata descriptions on both files, add a header_row column to enable parsing, and add version number and date to file names (v2_20220909_flmd.csv and v2_20220909_dd.csv). Update on 2023-08-08: Updates were made to both the data files and reporting format specific files. New available anion data was added, up until 2023-01-05. The file level metadata and data dictionary files were updated to reflect the additional data added. Update on 2024-03-11: Updates were made to both the data files and reporting format specific files. New available anion data was added, up until 2023-10-16. Further, revisions to the data files were made to remove incorrect data points (from 1970 and 2001). The reporting format specific files were updated to reflect the additional data added. Updated versions of the PDF and docx files for determination of MDLs for ICP-MS data were added to this dataset for samples starting in November 2021. Update on 2025-05-15: Updates were made to both the data files and reporting format specific files. New available cation data was added, up until the end of WY2024 (September 30, 2024). International Generic Sample Numbers (IGSNs), when registered, were added to the data files. The reporting format specific files were updated to reflect the additional data added. Update on 2026-09-01: Updates were made to both the data files and reporting format specific files. New available cation data was added, up until the end of WY2025 (September 30, 2025). Updated versions, as of 2026-08-06, of the PDF and docx files for determination of MDLs for ICP-MS data were added to this dataset for samples starting in November 2021.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Materials Data on PPb3 by Materials Project

Pb3P crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Pb sites. In the first Pb site, Pb is bonded in a 4-coordinate geometry to eight Pb atoms. There are four shorter (3.24 Å) and four longer (3.53 Å) Pb–Pb bond lengths. In the second Pb site, Pb is bonded to eight equivalent Pb and four equivalent P atoms to form a mixture of distorted edge, face, and corner-sharing PbP4Pb8 cuboctahedra. All Pb–P bond lengths are 3.24 Å. P is bonded in a square co-planar geometry to four equivalent Pb atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Multiple Slater Determinants and Strong Spin-Fluctuations as Key Ingredients of the Electronic Structure of Electron- and Hole-Doped Pb 10− x Cu x (PO 4 ) 6 O

LK-99, with chemical formula Pb 10−x Cu x (PO 4 ) 6 O, was recently reported to be a room-temperature superconductor. While this claim has met with little support in a flurry of ensuing work, a variety of calculations (mostly based on density-functional theory) have demonstrated that the system possesses some unusual characteristics in the electronic structure, in particular flat bands. We have established previously that within DFT, the system is insulating with many characteristics resembling the classic cuprates, provided the structure is not constrained to the P3(143) symmetry nominally assigned to it. Here we describe the basic electronic structure of LK-99 within self-consistent many-body perturbative approach, quasiparticle self-consistent GW (QSGW) approximation and their diagrammatic extensions. QSGW predicts that pristine LK-99 is indeed a Mott/charge transfer insulator, with a bandgap gap in excess of 3 eV, whether or not constrained to the P3(143) symmetry. When Pb 9 Cu(PO 4 ) 6 O is hole-doped, the valence bands modify only slightly, and a hole pocket appears. However, two solutions emerge: a high-moment solution with the Cu local moment aligned parallel to neighbors, and a low-moment solution with Cu aligned antiparallel to its environment. In the electron-doped case the conduction band structure changes significantly: states of mostly Pb character merge with the formerly dispersionless Cu d state, and high-spin and low spin solutions once again appear. Thus we conclude that with suitable doping, the ground state of the system is not adequately described by a band picture, and that strong correlations are likely. Irrespective of whether this system class hosts superconductivity or not, the transition of Pb 10 (PO 4 ) 6 O from being a band insulator to Pb 9 Cu(PO 4 ) 6 O, a Mott insulator, and multi-determinantal nature of doped Mott physics make this an extremely interesting case-study for strongly correlated many-body physics.

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

Materials Data on Pb3NO6 by Materials Project

(PbO)3NO3 crystallizes in the orthorhombic Pbcm space group. The structure is two-dimensional and consists of four nitric acid molecules and two PbO sheets oriented in the (0, 0, 1) direction. In each PbO sheet, there are three inequivalent Pb sites. In the first Pb site, Pb is bonded in a 4-coordinate geometry to four O atoms. There are two shorter (2.37 Å) and two longer (2.38 Å) Pb–O bond lengths. In the second Pb site, Pb is bonded in a 4-coordinate geometry to four O atoms. There are two shorter (2.29 Å) and two longer (2.52 Å) Pb–O bond lengths. In the third Pb site, Pb is bonded in a 4-coordinate geometry to four O atoms. There are two shorter (2.29 Å) and two longer (2.50 Å) Pb–O bond lengths. There are three inequivalent O sites. In the first O site, O is bonded to four Pb atoms to form a mixture of edge and corner-sharing OPb4 tetrahedra. In the second O site, O is bonded to four Pb atoms to form a mixture of edge and corner-sharing OPb4 tetrahedra. In the third O site, O is bonded in a square co-planar geometry to four Pb atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Synergistic Porosity and Charge Effects in a Supramolecular Porphyrin Cage Promote Efficient Photocatalytic CO 2 Reduction**

Abstract We present a supramolecular approach to catalyzing photochemical CO 2 reduction through second‐sphere porosity and charge effects. An iron porphyrin box ( PB ) bearing 24 cationic groups, FePB‐2(P) , was made via post‐synthetic modification of an alkyne‐functionalized supramolecular synthon. FePB‐2(P) promotes the photochemical CO 2 reduction reaction (CO 2 RR) with 97 % selectivity for CO product, achieving turnover numbers (TON) exceeding 7000 and initial turnover frequencies (TOF max ) reaching 1400 min −1 . The cooperativity between porosity and charge results in a 41‐fold increase in activity relative to the parent Fe tetraphenylporphyrin ( FeTPP ) catalyst, which is far greater than analogs that augment catalysis through porosity ( FePB‐3(N ), 4‐fold increase) or charge (Fe p ‐tetramethylanilinium porphyrin ( Fe‐ p ‐TMA ), 6‐fold increase) alone. This work establishes that synergistic pendants in the secondary coordination sphere can be leveraged as a design element to augment catalysis at primary active sites within confined spaces.

An, Lun↗
DOE OSTI2022

Synergistic Porosity and Charge Effects in a Supramolecular Porphyrin Cage Promote Efficient Photocatalytic CO 2 Reduction**

We present a supramolecular approach to catalyzing photochemical CO 2 reduction through second-sphere porosity and charge effects. An iron porphyrin box (PB) bearing 24 cationic groups, FePB-2(P), was made via post-synthetic modification of an alkyne-functionalized supramolecular synthon. FePB-2(P) promotes the photochemical CO 2 reduction reaction (CO 2 RR) with 97 % selectivity for CO product, achieving turnover numbers (TON) exceeding 7000 and initial turnover frequencies (TOF max ) reaching 1400 min -1 . The cooperativity between porosity and charge results in a 41-fold increase in activity relative to the parent Fe tetraphenylporphyrin (FeTPP) catalyst, which is far greater than analogs that augment catalysis through porosity (FePB-3(N), 4-fold increase) or charge (Fe p-tetramethylanilinium porphyrin (Fe-p-TMA), 6-fold increase) alone. In conclusion, this work establishes that synergistic pendants in the secondary coordination sphere can be leveraged as a design element to augment catalysis at primary active sites within confined spaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Assimilation of Fossil Hydrothermal Sulfide by Early Amazonian Martian Magmas: Implications for Ore Mineralization on Mars

Martian magmas would interact with any hydrosphere present, whether a global ocean [e.g., 1] or an icy (subterranean) hydrosphere [2] creating hydrothermal systems. Volcanogenic massive sulfide (VMS) ores, with Fe-Zn-Pb sulfides, created by hydrothermal deposition associated with a wide range of volcanism would be expected on Mars [3]. Similar to terrestrial komatiites, martian igneous rocks could generate orthomagmatic Ni-sulfide ore deposits by immiscible sulfide liquid segregation [4]. For this to occur, a martian magma would need to flow over (or intrude into) a pre-existing sulfur-rich formation. Here, we elaborate on the first evidence [5-6] of potential orthomagmatic mineralization in two Early Amazonian (2.4 Ga) igneous meteorites [7-8] involving a threestep process: i) formation of Fe-Zn-Pb sulfides, (ii) assimilated by the 2.4 Ga magmas leading to (iii) formation of orthomagmatic Ni-sulfide deposits. These deposits may remain on Mars, but the telltale signs of Zn-Pb enrichment and Ni-Co depletion in the two meteorites provide important insights into martian geology.

M Humayun↗