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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Metal–Organic Frameworks with Zero and Low‐Valent Metal Nodes Connected by Tetratopic Phosphine Ligands

Abstract Metal–organic frameworks (MOFs) constructed with M 0 nodes are attractive targets due to the reactivity of these low‐valent metals, but examples of these MOFs remain exceedingly rare. The rational design of three‐dimensional MOFs with Pd 0 and Pt 0 nodes using tetratopic phosphine ligands is reported. Five new MOFs have been synthesized by systematic variation of the phosphine ligands and metal precursors employed, and these represent the first examples of MOFs constructed using phosphine–metal bonds as the sole structural component. The MOFs display solid‐state luminescence, with emission maxima that are significantly red‐shifted compared to Pd(PPh 3 ) 4 . In addition, a Rh I low‐valent coordination solid based on the same linker design is reported, which displays solid‐state luminescence that is not observed for the molecular analogue.

Sikma, R. Eric↗
DOE OSTI2020

Boosting the Oxygen Reduction Performance via Tuning the Synergy between Metal Core and Oxide Shell of Metal−Organic Frameworks‐Derived Co@CoO x

Abstract Co core@Co oxide shell (Co@CoO x ) catalysts represent a large family with promising oxygen reduction reaction (ORR) catalytic activity. However, inadequate understanding of Co@CoO x synergy prohibits further pursuit of catalytic performance enhancement. Herein, a Co zeolitic−imidazolate framework was converted into metallic Co, followed by controlled air treatment to form Co@CoO x . The composition and structure evolution as a function of air treatment temperature were studied thoroughly through conventional and synchrotron (both ex‐situ and in‐situ) characterizations, confirming the coexistence of CoO and Co 3 O 4 in the shell. The optimal catalyst showed an ORR half‐wave potential of 0.87 V (vs. RHE) in an alkaline half‐cell and delivered high discharge capacity in an aprotic Li−O 2 battery (7,124 mAh g Cat+C −1 ) and an aqueous Zn−air battery (694 mAh g Zn −1 ) with good performance retention after durability test. Modeling simulation and density functional theory calculation confirmed the charge donation from metal core to oxide shell and shed light on new insights of how metal@metal oxide synergy impacted the ORR via tuning the charge conductivity, oxygen affinity and intermediate transfer pathway. This work opens up a venue to boost ORR catalytic activity from an interfacial synergy perspective.

Wang, Hao↗
DOE OSTI2023

Mesoporous Organosilica Nanoparticles with Internal Metal–Chelating Groups: Transition Metal Uptake and Gd 3+ Relaxivity

We prepared novel mesoporous organosilica nanoparticles with internal metal-chelating diethylenetriametetraacetic acid groups (DTTA-MSNPs) by co-condensation and decorated them with fluorescent moieties. Here, we studied the binding of transition metal ions such as copper(II), cobalt (II) and gadolinium (III) by DTTA-MSNPs, and found high uptake of these metals. In particular, DTTA-MSNPs uptake ~1.1×10 5 Gd 3+ per particle and possess a high r 1 relaxivity of 15.27 mM –1 s –1 . Thus, DTTA-MSNPs may find applications in metal sequestration and in MR imaging and neutron capture therapy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Transition metal carbide catalysts for biomass conversion: A review

The increasing demand for sustainable energy resources has initiated the investigation of biomass conversion over a wide range of catalysts. Among those, transition metal carbides have been extensively studied which demonstrated distinct reactivity and/or selectivity from transition or noble metals in a variety of chemical reactions. In this review, we summarize recent advances in the synthesis of transition metal carbides and their applications in biomass conversion, particularly focusing on the catalytic conversions of (hemi)cellulose, lignin and some typical platform chemicals to fuels or fine chemicals involving C-C, C-O-C and C-O-H bonds cleavages. Perspectives regarding the future research directions on the improvement of transition metal carbide catalysts and detailed reaction mechanism studies are also presented.

Pang, Jifeng↗
DOE OSTI2020

Occupational and dietary differences in hydroxylated and methoxylated PBDEs and metals in plasma from Puget Sound, Washington, USA region volunteers

BACKGROUND: Electronic waste (E-waste) recycling is a rapidly growing occupation in the USA with the potential for elevated exposure to flame retardants and metals associated with electronic devices. We previously measured polybrominated diphenyl ethers (PBDEs) in plasma from E-waste workers and found them similar to non-E-waste workers. OBJECTIVES: This study focused on structurally related PBDE derivatives, the hydroxylated (OH-PBDEs) and methoxylated (MeO-PBDEs) forms along with metals known to occur in E-waste. Humans can metabolize PBDEs and some MeO-PBDEs into OH-PBDEs, which is a concern due to greater health risks associated with OH-PBDEs METHODS: We measured 32 different OH-PBDEs and MeO-PBDEs in plasma samples provided by 113 volunteers living in the greater Puget Sound region of Washington State, USA. We measured 14 metals in a subset of 10 E-waste and 10 non-E-waste volunteers. Volunteers were classified based on occupational and dietary habits: work outdoors and weekly consume = 5 seafood servings (outdoor), electronic waste recycling (E-waste) or non-specific indoor occupations (indoor). A two-week food consumption diary was obtained from each volunteer prior to blood sampling. RESULTS: OH-PBDEs were detected in all volunteers varying between 0.27 – 102 ng/g/g-lipid. The MeO-PBDEs were detected in most, but not all volunteers varying between 0 – 60.4 ng/g/g-lipid. E-waste recyclers had OH-PBDE and MeO-PBDE plasma levels that were similar to the indoor group. The outdoor group had significantly higher levels of MeO-PBDEs, but not OH-PBDEs. Comparison of plasma concentrations of BDE-47 with its known hydroxylated metabolites suggested OH-PBDE levels were likely determined by biotransformation and at least two subpopulations identified differing in their apparent rates of OH-PBDE formation. The metals analysis indicated no significant differences between E-waste workers and non-E-waste workers. CONCLUSIONS: Our results indicate E-waste workers do not have elevated plasma levels of these contaminants relative to non-E-waste workers with similar dietary habits.

Schultz, Irvin↗
DOE OSTI2026

Metal-Centered Photoredox Catalysis using d 6 Transition Metal-based Chromophores

Controlling excited-state reactivity in transition metal chromophores is central to light-driven chemistry, with applications spanning from solar energy conversion to photoredox catalysis. Ru(II) and Ir(III) chromophores currently dominate applications within this field due to their long-lived charge-transfer (CT) excited states, which support bimolecular electron transfer chemistry. However, their elemental scarcity and relative lack of selectivity for differentiating oxidative versus reductive pathways has in part motivated the exploration of alternative platforms that could, in principle, offer distinct mechanistic opportunities. Earth-abundant, valence-isoelectronic 3d 6 complexes of Fe(II) and Co(III) have attracted significant attention due to their electronic similarity to Ru(II) and Ir(III), suggesting the potential for complementary photophysical behavior. In contrast to their heavier congeners, however, the weaker ligand fields of first-row transition metals promote rapid relaxation from initially populated CT states to low-lying metal-centered (MC) excited states, typically of 5 T 2 or 3 T 1 character. Because these MC states involve redistribution of electron density within MC d-orbitals rather than charge separation between metal and ligand orbitals, they were historically considered poor candidates for use in photochemical transformations.

Charge transfer↗
DOE OSTI2021

Strong Magnetocrystalline Anisotropy Arising from Metal–Ligand Covalency in a Metal–Organic Candidate for 2D Magnetic Order

Layered metal–organic frameworks are promising candidates for new two-dimensional magnets, as their synthetic programmability of these materials can provide a route to diverse structural and electronic properties. However, such framework materials typically lack the heavy elements that engender magnetocrystalline anisotropy in the monolayer ferromagnets reported to date. Alternative sources of magnetic anisotropy are therefore needed in these materials. Here, we report the synthesis of single crystals of the framework material (NMe 4 ) 2 [Fe 2 L 3 ] (H 2 L = 3,6-dichloro-2,5-dihydroxybenzoquinone) and evaluate the angular dependence of its magnetic properties. Oriented-crystal magnetization measurements reveal strong uniaxial anisotropy, where the easy axis is aligned with the crystallographic c axis. While the spin carriers of this structure are isotropic $S = ^5/_2$ Fe III metal centers and $S = ^1/_2$ organic linkers, the anisotropy energy of the framework material is comparable to that of reported 2D ferromagnets. Density functional theory calculations indicate that the observed magnetocrystalline anisotropy arises from ligand-to-metal charge transfer that enhances the magnetic anisotropy of the otherwise isotropic Fe centers, suggesting that metal–ligand covalency can be utilized as a general additive for the development of 2D magnets. These results in this study show the possibility for (NMe 4 ) 2 [Fe 2 L 3 ] to retain magnetic order down to the 2D monolayer limit. In addition, the combination of large magnetic anisotropy and semiconducting character in (NMe 4 ) 2 [Fe 2 L 3 ] highlights its potential as a new 2D magnetic semiconductor.

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

Insights into Molecular Magnetism in Metal–Metal Bonded Systems as Revealed by a Spectroscopic and Computational Analysis of Diiron Complexes

A pair of bimetallic compounds featuring Fe–Fe bonds, [Fe( i PrNPPh 2 ) 3 FeR] (R = PMe 3 , ≡N t Bu), have been investigated using High-Frequency Electron Paramagnetic Resonance (HFEPR) as well as field- and temperature-dependent 57 Fe nuclear γ resonance (Mössbauer) spectroscopy. To gain insight into the local site electronic structure, we have concurrently studied a compound containing a single Fe(II) in a geometry analogous to that of one of the dimer sites. Our spectroscopic studies have allowed for the assessment of the electronic structure via the determination of the zero-field splitting and 57 Fe hyperfine parameters for the entire series. We also report on our efforts to correlate structure with physical properties in metal–metal bonded systems using ligand field theory guided by quantum chemical calculations. Through the insight gained in this study, we discuss strategies for the design of single-molecule magnets based on polymetallic compounds linked via direct metal–metal bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Computational Optimization of Room Temperature Usable Capacity for Hydrogen Storage in MFU-4-Type Metal–Organic Frameworks via Pairwise Metal Substitutions

The efficient storage of hydrogen is a critical challenge in the quest for sustainable energy solutions. Current adsorbent-based methods achieve satisfactory storage densities predominantly under cryogenic temperatures and/or high pressures, which imposes problems with cost-efficient and safe implementation of this technology. Materials that can bind hydrogen gas reversibly at ambient temperatures and more moderate pressures could play a pivotal role in enabling hydrogen-powered technologies. In this study, we use reliable computational modeling to investigate two synthetically feasible paths for tuning the enthalpy of H2 binding in MFU-4-type metal–organic frameworks (MOFs), aiming to maximize usable capacity. This study examines MIM4 IICl3(bta)6 (bta– = benzotriazolate) Kuratowski-type clusters as a model for strong binding sites in MFU-4l frameworks. We systematically evaluate the impact of separately tuning the central MII metal ion (which plays a structural role) and the peripheral MI metal ion (which binds the substrate) on the energetics of H2 binding. Our computational study reveals that H2 binding at an MI site mostly follows the trend AgI < CuI < NiI < CoI < AuI while a larger central MII site generally weakens the H2 binding at a MI site. Importantly, we have identified three new combinations of MI and MII to achieve high fractional usable capacities of the total H2 adsorbed under a pressure swing from 5 to 100 bar at room temperature. Additionally, we examine the nature of the binding interaction between the peripheral metal atom and the hydrogen molecule. While charge transfer predominantly induces this interaction, for several atom combinations, a change in the polarization (associated with variations in the ionic radius of the MI binding atom) is another important factor for adjusting the strength of the interaction. We suggest that the proposed compositions of Kuratowski-type clusters are highly desirable synthetic targets for future laboratory study.

Tkachenko, Nikolay V↗