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Results for “Metal organic frameworks (MOF)”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Incorporation of free halide ions stabilizes metal–organic frameworks (MOFs) against pore collapse and renders large-pore Zr-MOFs functional for water harvesting

Chemically and hydrolytically stable MOFs have shown promising water-vapor adsorption properties. However, MOFs that can simultaneously satisfy the following three requirements for effective water harvesting from low-humidity air are quite rare: (1) high water-uptake capacity; (2) hydrolytic and mechanical stability; (3) complete uptake at ~20–30% relative humidity (RH). Here we show that incorporating free halide ions is effective for enabling a representative Zr-MOF to meet these requirements for water harvesting. As-synthesized MOF-808 initially exhibits very good capacity at RH ≥ 30%, but quickly suffers large capacity losses due to water-evacuation-induced pore collapse. Via a framework-charging and free counter-ion inclusion approach, we were able to replace node-ligated formate anions with charge-neutral aqua ligands and site desired water-sorbing free-halide ions within the large pores of MOF-808 . In this study, altered samples show increased gravimetric water uptake, show beneficial shifts of water sorption isotherms toward lower water-vapor partial pressure, eliminate undesirable sorption/desorption isotherm hysteresis, and render MOF-808-Br indefinitely recyclable for ambient-temperature uptake of water vapor and lower-temperature liquid-water release.

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

Metal–Organic Frameworks and Metal–Organic Gels for Oxygen Electrocatalysis: Structural and Compositional Considerations

Increasing demand for sustainable and clean energy is calling for the next-generation energy conversion and storage technologies such as fuel cells, water electrolyzers, CO 2 /N 2 reduction electrolyzers, metal–air batteries, etc. All these electrochemical processes involve oxygen electrocatalysis. Boosting the intrinsic activity and the active-site density through rational design of metal–organic frameworks (MOFs) and metal–organic gels (MOGs) as precursors represents a new approach toward improving oxygen electrocatalysis efficiency. MOFs/MOGs afford a broad selection of combinations between metal nodes and organic linkers and are known to produce electrocatalysts with high surface areas, variable porosity, and excellent activity after pyrolysis. Some recent studies on MOFs/MOGs for oxygen electrocatalysis and their new perspectives in synthesis, characterization, and performance are discussed in this review. New insights on the structural and compositional design in MOF/MOG-derived oxygen electrocatalysts are summarized. Critical challenges and future research directions are also outlined.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Competitive Adsorption of NH 3 and H 2 O in Metal–Organic Framework Materials: MOF-74

Elucidating the interaction between coadsorbed H 2 O and NH 3 in metal–organic frameworks (MOFs) is of paramount importance to uncover mechanistic details of their competitive coadsorption behavior as well as to guide the design of new materials for enhanced NH 3 adsorption in humid environments. Nevertheless, molecular competition between NH 3 and H 2 O within the confined nanopores of MOFs was rarely explored and is poorly understood due to challenges in characterization. Here, we combine in situ infrared spectroscopy with ab initio calculations to unveil the competition of NH 3 and H 2 O for occupying active adsorption sites in the representative MOF-74 material by analyzing the kinetics and energetics of the molecular exchange process. We find that at a high NH 3 /H 2 O ratio, the incoming NH 3 is capable of displacing metal-bound H 2 O and moving it to secondary adsorption sites due to the stronger binding of NH 3 compared with H 2 O. Interestingly, the reverse process of H 2 O displacing metal-bound NH 3 is also possible upon increasing water concentration. Our calculations show that H 2 O exchanging the preabsorbed NH 3 at the metal site is driven not only by a reduced kinetic barrier but also by a favorable energetical state resulting from the formation of water clusters at metal sites and intermolecular H-bonding between the metal-coordinated H 2 O and displaced NH 3 . Our finding emphasizes that the description of molecular occupation in MOFs at equilibrium cannot simply be established by comparing molecules’ binding energies at their strongest binding sites derived by single-component measurements; rather, intermolecular interactions can greatly affect molecular distribution at equilibrium. Furthermore, we show that vibrational modes of adsorbed NH 3 are markedly perturbed upon contact with water molecules, accompanied by a large frequency shift (>30 cm –1 ) and considerable intensity decrease, which arises from the freezing of NH 3 vibrations by coadsorbed H 2 O. As a result, the mechanistic insight obtained through our study sheds light on molecular coadsorption processes in MOFs and helps to assess NH 3 removal efficiency of MOFs containing open-metal sites under realistic conditions, particularly in the presence of humidity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhancing Dihydrogen Interaction of a Zirconium Metal–Organic Framework by Metal Doping

Advancing efficient hydrogen storage technologies is essential for enabling a sustainable energy future, especially in onboard applications. While hydrogen offers high gravimetric energy density and zero-emission combustion, its low volumetric energy density presents significant storage challenges. Metal-organic frameworks (MOFs), well known for their tunable porosity and high surface areas, have emerged as promising candidates for adsorption-based hydrogen storage. This study investigated a chemically robust zirconium-based MOF, MOF-808, as a representative platform for hydrogen storage enhancement through metal ion doping. Various divalent metal ions were introduced into MOF-808 via one-pot synthesis or post-synthetic modification (PSM) to evaluate their effects on metal doping efficiency, framework stability, and hydrogen adsorption performance. Our findings demonstrate that metal doping enhanced the hydrogen binding affinity of MOF-808 while preserving its structural integrity and excellent stability. A Mg-doped MOF, MOF-808@Mg 2:1, showed a 59% increase in hydrogen uptake, and a Cu-doped MOF, MOF-808-ZrCu, exhibited a 33% increase in isosteric heat of adsorption for H 2 compared to the pristine MOF-808 activated at the same temperature. This work highlights the potential of metal-functionalized stable MOFs for practical hydrogen storage applications. Furthermore, these materials are also being studied for their potential to enhance CO 2 adsorption.

Adsorption↗
DOE OSTI2021

The Surge of Metal–Organic-Framework (MOFs)-Based Electrodes as Key Elements in Electrochemically Driven Processes for the Environment

Metal–organic-frameworks (MOFs) are emerging materials used in the environmental electrochemistry community for Faradaic and non-Faradaic water remediation technologies. It has been concluded that MOF-based materials show improvement in performance compared to traditional (non-)faradaic materials. In particular, this review outlines MOF synthesis and their application in the fields of electron- and photoelectron-Fenton degradation reactions, photoelectrocatalytic degradations, and capacitive deionization physical separations. This work overviews the main electrode materials used for the different environmental remediation processes, discusses the main performance enhancements achieved via the utilization of MOFs compared to traditional materials, and provides perspective and insights for the further development of the utilization of MOF-derived materials in electrified water treatment.

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

Metal–Organic Framework Integrating Ionic Framework and Bimetallic Coupling Effect for Highly Efficient Oxygen Evolution Reaction

Metal–organic frameworks (MOFs) are recognized as promising electrocatalysts for the oxygen evolution reaction (OER) because of their permanent porosity and rich architectural diversity; however, ionic MOFs enabling fast ions exchange during OER are rarely explored. Here, an ionic MOF (Ni-btz) constructed with an azolate ligand is selected, and continuous 3D bimetallic MOF (NiFe-btz) films deriving from high-degree intergrowth of microsized MOFs particles are fabricated. The as-prepared NiFe-btz/NF-OH electrode exhibits excellent OER performance with a low overpotential of 239 mV at 10 mA cm –2 under alkaline condition. The OER charge transfer process and bimetallic coupling effect in ionic NiFe-btz are probed by density functional theory calculations and confirmed via X-ray photoelectron spectroscopy and in situ Raman measurements. The partial density of states of NiFe-btz indicates that the main contribution for electron density around the Fermi level is from Cl ions clarifying the profitable impact of ionic MOF framework. This work systematically demonstrates the relationship of electronic structure and OER activity in ionic, bimetallic MOFs and expands the scope of 3D MOF films for efficient OER.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Cu-, Co-, and Zn-Based Metal–Organic Framework-Derived Nanoporous Ion Emitters for Picogram Level Analysis of Actinides

Thermal ionization mass spectrometry (TIMS) is often regarded as the preferred technique for trace-level isotopic analysis of actinides owing to its high sensitivity and absence of carry-over effects. However, actinide sample utilization efficiency (SUE) is typically low (<0.05%) without the use of activators or specialized loading approaches which can yield SUEs of >5%. To this effect, we investigate a series of metal–organic framework (MOF)-based nanoporous ion emitters (nano-PIEs) that show enhanced ionization of actinides when used in TIMS loading. We study the impact of physical and chemical properties of MOFs on TIMS SUEs using two families of MOFs that can be synthesized under similar reaction conditions. The structural and chemical properties of these MOFs can be systematically modified one at a time while keeping other features the same. This allows us to strategically investigate their impact on SUEs. The first family of MOFs considered in this study is Zeolitic Imidazole Frameworks (ZIFs) which are made using 2 methyl-imidazole as an organic linker with zinc (ZIF-8) and cobalt (ZIF-67) as metal centers. Additionally, the effect of morphology was also studied using Zn-based ZIF-L with a 2-dimensional structure. The second family of MOFs was synthesized using benzene-1,3,5-tricarboxylate (BTC) with copper (Cu-BTC) and zinc (Zn-BTC) as the metal center. Among the MOFs tested, Cu-BTC showed the highest SUE with an average SUE of 0.27 ± 0.15%, followed closely by Zn-BTC (0.24 ± 0.10%), ZIF-8 (0.17 ± 0.10%), and trailed by the other MOFs. When the MOFs were pyrolyzed in N 2 before loading, an apparent increase in the SUE was observed with ZIF-8 and Cu-BTC showing average SUEs of 0.25 ± 0.08% and 0.34 ± 0.13%, respectively, with the highest measured SUE of 0.53% for pyrolyzed Cu-BTC. In conclusion, this observed increase in SUE by up to an order of magnitude compared to bare filaments demonstrates the efficacy and potential of MOF-derived nano-PIEs for TIMS application.

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

Metal–Carbodithioate-Based 3D Semiconducting Metal–Organic Framework: Porous Optoelectronic Material for Energy Conversion

Solar energy conversion requires the working compositions to generate photoinduced charges with high potential and the ability to deliver charges to the catalytic sites and/or external electrode. These two properties are typically at odds with each other and call for new molecular materials with sufficient conjugation to improve charge conductivity but not as much conjugation as to overly compromise the optical band gap. In this work, we developed a semiconducting metal-organic framework (MOF) prepared explicitly through metal-carbodithioate"(-CS 2 ) n M" linkage chemistry, entailing augmented metal-linker electronic communication. The stronger ligand field and higher covalent character of metal-carbodithioate linkages-when combined with spirofluorene-derived organic struts and nickel-(II) ion-based nodes-provided a stable, semiconducting 3D-porous MOF, Spiro-CS 2 Ni. This MOF lacks long-range ordering and is defined by a flexible structure with non-aggregated building units, as suggested by reverse Monte Carlo simulations of the pair distribution function obtained from total scattering experiments. The solvent-removed "closed pore"material recorded a Brunauer-Emmett-Teller area of similar to 400m 2 /g, where the "open pore" form possesses90 wt % solvent-accessible porosity. Electrochemical measurements suggest that Spiro-CS 2 Ni possesses a band gap of 1.57 eV(sigma = 10 -7 S/cm at -1.3 V bias potential),which can be further improved by manipulating the d-electron configuration through an axial coordination (ligand/substrate), the latter of which indicates usefulness as an electrocatalyst and/or a photoelectrocatalyst(upon substrate binding). Transient-absorption spectroscopy reveals a long-lived photo-generated charge-transfer state (τ CR = 6.5 mu s) capable of chemical transformation under a biased voltage. Spiro-CS 2 Ni can endure a compelling range of pH(1-12 for weeks) and hours of electrochemical and photoelectrochemical conditions in the presence of water and organic acids. We believe this work provides crucial design principles for low-density, porous,light-energy-conversion materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Review of the adsorbents/catalysts for the removal of sulfur compounds from natural gas

Here this paper aims to provide a compilation of studies on adsorptive removal of H2S and organic sulfur compounds from natural gas at relatively low temperatures and pressures. The manuscript compares sulfur uptakes among different materials, including zeolites, activated carbons, metallic organic frameworks (MOFs), and metal oxides, and the impact of modifications to these materials. Best sulfur uptakes were achieved by adding metallic or nitrogen species to the adsorbent surfaces. This contribution to the peer-reviewed literature could provide a better understanding of the improvements necessary to achieve greater sulfur capacities and the mechanisms of sulfur interactions with adsorbents' surfaces.

03 NATURAL GAS↗