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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Nanoporous weakly coordinating anionic frameworks (Final Technical Report)

Under this award, we synthesized and characterized new weakly coordinating, anionic covalent organic frameworks. The motivation was to expand the class of covalent organic frameworks though the introduction of the first weakly coordinating anionic ones. The significance of the weakly coordinating anionic character of these frameworks is associated with the character of the counter (metal) cations in their pores. Those counter-cations, due to the inability to effectively coordinate to the pore walls, have a “naked”, and thus highly electrophilic, Lewis acidic character. Such properties are expected to translate to a number of interesting physical properties that can be potentially used for a range of energy-relevant applications. One of these applications is gas adsorption, separation, and storage. The electrophilic, Lewis acidic character of the counter-cations are expected to strongly bind to gas molecules entering the pores leading to higher gas sorption capacities. Other applications include heterogeneous catalysis, ion exchange, and solid state ion conduction. Within the project we explored a range of chemical blocks, and tested synthesis conditions to polymerize these building blocks to form the target materials. In particular, we focused on materials with group 15 elements like phosphorus in the oxidation state +5 and the coordination number 6, that have a formal -1 charge. The synthesis of such materials is challenging because its success depends on the absence of residual monomeric and oligomeric side-products in the pores, and the absence of significant framework interpenetration. Crystalline forms of these materials require sufficient reversibility of the polymerization reaction (which is difficult to achieve because group 15 elements like P tend to make strong covalent bonds with neighbored elements), as well as suitable polymerization rates that prevent the formation of kinetically controlled products. We had success with the preparation of anionic porous organic frameworks with anionic building blocks containing P(V)O6 octahedra synthesized through Yamamoto coupling reactions. These materials are non-crystalline because of the irreversible nature of the Yamamoto coupling reaction, but show porosity. The porosity and surface area can be significantly increased by co-reaction with electrostatically neutral co-reactants. Very high porosity and surface areas can be achieved when the materials are washed with hydrochloric acid. This method is commonly used to free products from Yamamoto coupling reactions from by-products. Indeed, this method removed by products from the pores of our materials, however it also led to the hydrolysis of the PO6 octahedra to form pending phosphonic acid groups (-PO3H)-groups in the frameworks (PA-POFs) which was actually not desired. Nonetheless, these materials showed high CO2 sorption capacities. In addition, they show extremely high (actually record) sorption capacities for the removal of a range of common micropollutants such as bisphenol A (BPA) and 4-nitrophenol in water. BPA is a wide-spread organic pollutant and a known endocrine disruptor. The maximum adsorption capacity of BPA at equilibrium is found to be as high as 3,366 mg g-1 by Langmuir adsorption model, which is more than 10 times greater than peer materials. The polymer also rapidly removes various other organic micropollutants with more than 90% removal efficiencies. In addition, the PA-POF material can be regenerated at least five times by mild washing using methanol without significant loss in removal efficiency. This is significant advantage over commonly used activated carbon materials (that are in Brita water faucet filters, for example). Comparison studies showed that only materials with the phosphonate groups show extreme sorption although the number of PA group is actually small according to solid state NMR and EDX data. More research would be needed to investigate why this is (a possibility is that the phosphonate groups have a multiplying effect in which a PA-induced initial adsorption leads to the adsorption of much more adsorbate). The extreme sorption capabilities can also be visually seen when colored adsorbates such as 4-nitrophenol are used, as the adsorption of the nitrobenzene leads to the decoloration of the solution. We have produced three short videos that illustrate the sorption capabilities compared to two peer materials (activated carbon from dismantled Brita water filters, and a electrostatically neutral, chemically related, porous organic polymer, respectively).

36 MATERIALS SCIENCE↗
DOE OSTI2023

Evaluating energy justice metrics in early-stage science and technology research using the JUST-R metrics framework

Embedding principles of energy justice throughout all aspects of clean energy technology research and development (R&D) can facilitate a more just energy transition; yet gaps remain in our understanding of how to best integrate energy justice from the earliest R&D stages. The Justice Underpinning Science and Technology Research (JUST-R) metrics framework has been developed to enable early-stage energy researchers to assess and address justice considerations associated with their research, but the impacts of the framework, and others like it, have yet to be evaluated. This study seeks to evaluate the JUST-R metrics framework in terms of its effectiveness and appeal to researchers engaged in early-stage technical R&D using qualitative analyses of documents and workshop transcripts. We find that the metrics framework helps researchers identify problems and potential solutions surrounding the energy justice implications of their work and spurs a change in perspective for researchers, but, simultaneously, there is no evidence of solution follow-through within the evaluation timeframe. Greater institutional support, specialization to research areas, knowledge of energy justice fundamentals, and earlier incorporation of energy justice considerations in research projects arise as factors needed to aid continued use of the framework and pursuit of identified solutions. This evaluation protocol and these findings can serve as a guide for improving other frameworks with similar goals of encouraging sociotechnical engagement in early-stage energy R&D.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2018

Tunable Crystallinity and Charge Transfer in Two‐Dimensional G‐Quadruplex Organic Frameworks

Abstract DNA G‐quadruplex structures were recently discovered to provide reliable scaffolding for two‐dimensional organic frameworks due to the strong hydrogen‐bonding ability of guanine. Herein, 2,7‐diaryl pyrene building blocks with high HOMO energies and large optical gaps are incorporated into G‐quadruplex organic frameworks. The adjustable substitution on the aryl groups provides an opportunity to elucidate the framework formation mechanism; molecular non‐planarity is found to be beneficial for restricting interlayer slippage, and the framework crystallinity is highest when intermolecular interaction and non‐planarity strike a fine balance. When guanine‐functionalized pyrenes are co‐crystallized with naphthalene diimide, charge‐transfer (CT) complexes are obtained. The photophysical properties of the pyrene‐only and CT frameworks are characterized by UV/Vis and steady‐state and time‐resolved photoluminescence spectroscopies, and by EPR spectroscopy for the CT complex frameworks.

Wu, Yi‐Lin↗
DOE OSTI2015

A framework for selecting indicators of bioenergy sustainability

A framework for selecting and evaluating indicators of bioenergy sustainability is presented. This framework is designed to facilitate decision-making about which indicators are useful for assessing sustainability of bioenergy systems and supporting their deployment. Efforts to develop sustainability indicators in the United States and Europe are reviewed. The first steps of the framework for indicator selection are defining the sustainability goals and other goals for a bioenergy project or program, gaining an understanding of the context, and identifying the values of stakeholders. From the goals, context, and stakeholders, the objectives for analysis and criteria for indicator selection can be developed. The user of the framework identifies and ranks indicators, applies them in an assessment, and then evaluates their effectiveness, while identifying gaps that prevent goals from being met, assessing lessons learned, and moving toward best practices. The framework approach emphasizes that the selection of appropriate criteria and indicators is driven by the specific purpose of an analysis. Realistic goals and measures of bioenergy sustainability can be developed systematically with the help of the framework presented here.

09 BIOMASS FUELS↗
DOE OSTI2025

Optimal sizing of battery energy storage systems for peak shaving and demand response using a degradation-aware Bayesian Optimization-Mixed-Integer Linear Programming framework

The increasing integration of renewable energy and rising electricity demand highlight the importance of battery energy storage systems for peak shaving and demand response. Unlike prior approaches that overlook operational impacts on degradation, this study proposes a Bayesian Optimization–Mixed Integer Linear Programming framework for optimal battery energy storage system sizing. In this framework, Mixed Integer Linear Programming determines short-term scheduling while a calibrated electrochemical model iteratively evaluates degradation. The central hypothesis is that the framework can efficiently identify optimal sizes that yield realistic and economically robust outcomes. The method is tested across three scenarios: peak shaving, peak shaving with energy-reduction demand response, and peak shaving with power-reduction demand response. Results show that the framework converge to the optimum within 20 iterations out of 150 possible sizes. Under baseline conditions, the framework consistently selects the smallest feasible system, minimizing unnecessary degradation costs from oversized storage. Sensitivity analyses reveal that larger systems are favored as demand rates or incentives increase. Comparisons of demand response programs indicate that power-reduction demand response offers greater economic benefits than energy-reduction demand response, although demand savings from peak shaving remain the dominant contributor to overall performance. This study demonstrates that the proposed framework balances computational tractability with degradation fidelity, identifies critical economic thresholds for investment, and offers a practical, flexible tool to guide industrial stakeholders in cost-effective battery energy storage system deployment.

Batteries↗
DOE OSTI2026

Optimizing district energy systems by integrating Borehole Thermal Energy Storage Using a Mixed-Integer Linear Programming g-function framework with a Multi-Timescale Rolling Horizon method

Shallow geothermal has gained increasing attention in recent years; however, a reliable framework for its accurate incorporation into large-scale energy system optimization remains lacking. This study proposes a Mixed-Integer Linear Programming (MILP) framework combined with the g-function approach to integrate Borehole Thermal Energy Storage (BTES) technology into energy system optimization. Validation against a Modelica-based reservoir network simulation demonstrates that the proposed framework effectively captures the ground thermal response under varying energy loads and accurately estimates the borefield energy supply. To enhance scalability, a Rolling Horizon with Multi-Timescale (RH-MTS) method is further introduced, reducing computational time by 73 % for the 1-year optimization model with only minor loss of optimality. The framework is demonstrated through the case study of the UC Berkeley campus. Results indicate that BTES is a cost-effective and low-carbon solution: two borefields comprising 382 boreholes can meet 8.0 % and 6.6 % of the total campus heating and cooling demand, respectively, at an average energy rate of 0.70–0.77 USD/kWh and carbon intensity of 0.54 kg-CO2/kWh. Short-term analysis reveals a 35%–65% decline in BTES energy flow after 3–6 months of continuous heating/cooling operation, while long-term simulation shows that annual energy production of BTES can vary by up to 12.0 % after four years before stabilizing. Overall, this study develops a novel optimization framework that couples physics-based g-function method with MILP optimization framework, thereby advancing methodological development for shallow-geothermal integration and providing actionable guidance for BTES deployment in district-energy systems.

Yang, Jiahui↗
DOE OSTI2020

Cybersecurity Vulnerability Mitigation Framework through Empirical Paradigm: Enhanced Prioritized Gap Analysis

Existing cybersecurity vulnerability assessment tools were designed based on the policies and standards defined by organizations such as the U.S. Department of Energy and the National Institute of Standards and Technology (NIST). Frameworks such as the cybersecurity capability maturity model (C2M2) and the NIST Cybersecurity Framework (CSF) are often used by the critical infrastructure owners and operators to determine the cybersecurity maturity of their facility. Although these frameworks are exceptional at performing qualitative cybersecurity analysis and identifying vulnerabilities, they do not provide a means to perform prioritized mitigation of those vulnerabilities in order to achieve a desired cybersecurity maturity. To address that challenge, we developed a framework and software application called the cybersecurity vulnerability mitigation framework through empirical paradigm (CyFEr). This paper presents the detailed architecture of CyFEr’s enhanced prioritized gap analysis (EPGA) methodology and its application to CSF. The efficacy of the presented framework is demonstrated by comparing against existing similar models and testing against the cyber injects from a real-world cyber-attack that targeted industrial control systems (ICS) in critical infrastructures.

Gourisetti, Sri Nikhil G.↗
DOE OSTI2015

Synthesis, characterizations and catalytic studies of a new two-dimensional metal−organic framework based on Co–carboxylate secondary building units

A metal–organic framework [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}] was synthesized and structurally characterized. X-ray single crystal analysis revealed that the framework contains a 2D polymeric chain through coordination of 1,4-benzenedicarboxylic acid linker ligand to cobalt centers. The polymer crystallize in monoclinic P2{sub 1}/n space group with a=13.989(3) Å, b=9.6728(17) Å, c=16.707(3) Å, and Z=2. The polymer features a framework based on the perfect octahedral Co–O6 secondary building units. The catalytic activities of [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}]{sub n} for olefins oxidation was conducted. The heterogeneous catalyst could be facilely separated from the reaction mixture, and reused three times without significant degradation in catalytic activity. Furthermore, no contribution from homogeneous catalysis of active species leaching into reaction solution was detected. - Graphical abstract: A metal–organic framework of [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}] was synthesized by hydrothermal method. This 2D-periodic framework is constructed from the infinite Co–O–C secondary building units and crystallizes in the monoclinic P2{sub 1}/n space group based on Co(II)–carboxylate units. The catalytic oxidation of various olefins was effectively carried out with [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}]{sub n} catalyst by TBHP as oxidant. - Highlights: • A metal–organic framework of [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}] is prepared by hydrothermal method. • The [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}]{sub n} is constructed from Co–carboxylate secondary building units. • This coordination polymer displayed high catalytic activity for olefin oxidation reactions. • The catalytic reaction is heterogeneous and catalyst can be simply separated. • The heterogeneous catalyst can be reused several times without significant loss of catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Selective adsorption in two porous triazolate–oxalate-bridged antiferromagnetic metal-azolate frameworks obtained via in situ decarboxylation of 3-amino-1,2,4-triazole-5-carboxylic acid

Solvothermal reactions of metal salts, 3-amino-1,2,4-triazole-5-carboxylic acid (H{sub 2}atzc) and ammonium oxalate in different temperature produced two metal azolate frameworks, namely, [Cu{sub 3}(atzc){sub 2}(atz)(ox)]·1.5H{sub 2}O (1) and [Co{sub 5}(atz){sub 4}(ox){sub 3}(HCOO){sub 2}]·DMF (2) (H{sub 2}atzc=3-amino-1,2,4-triazole-5-carboxylic acid, Hatz=3-amino-1,2,4-triazole, and ox=oxalate), in which the atzc precusor was in situ decarboxylated. Structural determination reveals that 1 contains [Cu{sub 3}(atzc){sub 2}(atz)]{sup 2−} layers of mixed μ{sub 4}-atzc and μ{sub 3}-atz ligands, which are pillared by ox{sup 2−} groups to form a 3D porous framework. Compound 2 contains 2D layers with basic spindle-shaped decanuclear units, which extended by ox{sup 2−} and formates to form 3D porous framework. Gas adsorption investigation revealed that two kinds of frameworks exhibited selective CO{sub 2} over N{sub 2} sorption. Moreover, activated 2 shows H{sub 2} storage capacity. Additionally, magnetic properties of both the compounds have been investigated. - Graphical abstract: Solvothermal reactions of metal salts, 3-amino-1,2,4-triazole-5-carboxylate and oxalate produced two metal azolate frameworks, which could store gas molecules, especially H{sub 2} due to small pores. in situ decarboxylation of precursor was observed. - Highlights: • Two MAFs were synthesized via in situ decarboxylation of H{sub 2}atzc. • Both activated frameworks exhibited selective CO{sub 2} over N{sub 2} sorption. • Activated 2 could adsorb H{sub 2}, which makes it promising candidates for gas storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Pore surface engineering in a zirconium metal–organic framework via thiol-ene reaction

A porous olefin-functionalized Zr(IV)-based metal–organic framework, denoted as UiO-68-allyl, has been constructed. Our results clearly demonstrated that the surface of UiO-68-allyl could be decorated with organic molecule (ethanethiol) via thiol-ene reaction. More importantly, the crystallinity of the framework were maintained during the post-synthetic modification process. However, the microporosity of the framework is retained but the surface area decreased, due to the grafting of ethylthio groups into the pores. From our studies, we can conclude that the strategy of post-synthetic modification of UiO-68-allyl via thiol-ene reaction may be general. Furthermore, we may anchor other desired functional group onto the pore walls in Zr-MOFs via thiol-ene reaction, enabling more potential applications. - graphical abstract: In this manuscript, we reported the post-synthetic modification of an olefin-functionalized Zr(IV)-based metal–organic framework via thiol-ene reaction. - Highlights: • A porous olefin-functionalized Zr(IV)-based metal–organic framework has been constructed. • The surface of olefin-functionalized Zr-MOF could be decorated with organic molecules via thiol-ene reaction. • The crystallinity and permanent porosity of the framework were maintained during the post-synthetic modification process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

How the guest molecules in nanoporous Zn(II) metal-organic framework can prevent agglomeration of ZnO nanoparticles

The host and the apohost framework of [Zn{sub 2}(BDC){sub 2}(H{sub 2}O){sub 2}·(DMF){sub 2}]{sub n} (1·2H{sub 2}O·2DMF), (BDC{sup 2−}=benzene-1,4-dicarboxylate and DMF=N,N-Dimethylformamide), were synthesized and subsequently used for preparation of ZnO nanomaterials. With calcination of the host framework of 1·2H{sub 2}O·2DMF, ZnO nanoparticles were obtained. By the same process on the apohost framework of 1, agglomerated nanoparticles of ZnO were formed. These nano-structures were characterized by X-ray powder diffraction (XRD) and Scanning electron microscopy (SEM). These results indicate that with removal of the guest DMF and coordinated H{sub 2}O molecules from the one-dimensional channels of 1·2H{sub 2}O·2DMF, the tendency of nanoparticles to agglomerate increases and the role of this MOF in preparation of ZnO nanoparticles from this precursor was reduced. - Graphical abstract: Nano-porous zinc(II) MOF with guest DMF and coordinated H{sub 2}O molecules has been synthesized and characterized. The host and the apohost framework of it were used for preparation of ZnO nanomaterials. The role of these species in preparation of ZnO nanoparticles from the host framework is probably similar to the role of polymeric stabilizers in formation of nanoparticles. - Highlights: • Nanoparticles of ZnO were fabricated from nanoporous metal-organic framework. • The effect of guest DMF and coordinated H{sub 2}O molecules on this process was studied. • The effect of them in formation nanoparticle is similar to polymeric stabilizers.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

M(II)-dipyridylamide-based coordination frameworks (M=Mn, Co, Ni): Structural transformation

A series of 1-D double-zigzag (([M(papx){sub 2}(H{sub 2}O){sub 2}](ClO{sub 4}){sub 2}){sub n}; M=Mn, x=s (1), x=o (3); M=Co, x=s (4), x=o (5); M=Ni, x=s (6), x=o (7)) and 2-D polyrotaxane ([Mn(paps){sub 2}(ClO{sub 4}){sub 2}]{sub n} (2)) frameworks were synthesized by reactions of M(ClO{sub 4}){sub 2} (M=Mn, Co, and Ni) with papx (paps, N,N’-bis(pyridylcarbonyl)-4,4’-diaminodiphenylthioether; papo, N,N’-bis(pyridylcarbonyl)-4,4’-diaminodiphenyl ether), which have been isolated and structurally characterized by X-ray diffraction. Based on powder X-ray diffraction (PXRD) experiments, heating the double-zigzag frameworks underwent structural transformation to give the respective polyrotaxane ones. Moreover, grinding the solid samples of the respective polyrotaxanes in the presence of moisture also resulted in the total conversion to the original double-zigzag frameworks. In this study, we have successfully extended studies to Mn{sup II}, Co{sup II}, and Ni{sup II} frameworks from the previous Zn{sup II}, Cd{sup II}, and Cu{sup II} ones, and interestingly such structural transformation is able to be proven experimentally by powder and single-crystal X-ray diffraction studies as well. - Graphical abstract: 1-D double-zigzag and 2-D polyrotaxane frameworks of M(II)-papx (x=s, o; M=Mn, Co, Ni) frameworks can be interconverted by heating and grinding in the presence of moiture, and such structural transformation has be proven experimentally by powder and single-crystal X-ray diffraction studies.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The ADAQ framework: An integrated toolkit for data acquisition and analysis with real and simulated radiation detectors

Here, the ADAQ framework is a collection of software tools that is designed to streamline the acquisition and analysis of radiation detector data produced in modern digital data acquisition (DAQ) systems and in Monte Carlo detector simulations. The purpose of the framework is to maximize user scientific pro-ductivity by minimizing the effort and expertise required to fully utilize radiation detectors in a variety of scientific and engineering disciplines. By using a single set of tools to span the real and simulation domains, the framework eliminates redundancy and provides an integrated workflow for high-fidelity comparison between experimental and simulated detector performance. Built on the ROOT data analysis framework, the core of the ADAQ framework is a set of Cþþ and Python libraries that enable high-level control of digital DAQ systems and detector simulations with data stored into standardized binary ROOT files for further analysis. Two graphical user interface programs utilize the libraries to create powerful tools: ADAQAcquisition handles control and readout of real-world DAQ systems and ADAQAnalysis provides data analysis and visualization methods for experimental and simulated data. At present, the ADAQ framework supports digital DAQ hardware from CAEN S.p.A. and detector simulations performed in Geant4; however, the modular design will facilitate future extension to other manufacturers and simulation platforms.

detector simulation↗
DOE OSTI2017

Exploring New Assembly Modes of Uranyl Terephthalate: Templated Syntheses and Structural Regulation of a Series of Rare 2D → 3D Polycatenated Frameworks

In this paper, the reaction of uranyl nitrate with terephthalic acid (H 2 TP) under hydrothermal conditions in the presence of an organic base, 1,3-(4,4'-bispyridyl)propane (BPP) or 4,4'-bipyridine (BPY), provided four uranyl terephthalate compounds with different entangled structures by a pH-tuning method. [UO 2 (TP) 1.5 ](H 2 BPP) 0.5 ·2H 2 O (1) obtained in a relatively acidic solution (final aqueous pH, 4.28) crystallizes in the form of a noninterpenetrated honeycomb-like two-dimensional network structure. An elevation of the solution pH (final pH, 5.21) promotes the formation of a dimeric uranyl-mediated polycatenated framework, [(UO 2 ) 2 (μ-OH) 2 (TP) 2 ] 2 (H 2 BPP) 2 ·4.5H 2 O (2). Another new polycatenated framework with a monomeric uranyl unit, [(UO 2 ) 2 (TP) 3 ](H 2 BPP) (3), begins to emerge as a minor accompanying product of 2 when the pH is increased up to 6.61, and turns out to be a significant product at pH 7.00. When more rigid but small-size BPY molecules replace BPP molecules, [UO 2 (TP) 1.5 ](H 2 BPP) 0.5 (4) with a polycatenated framework similar to 3 was obtained in a relatively acidic solution (final pH, 4.81). The successful preparation of 2–4 represents the first report of uranyl–organic polycatenated frameworks derived from a simple H 2 TP linker. Finally, a direct comparison between these polycatenated frameworks and previously reported uranyl terephthalate compounds suggests that the template and cavity-filling effects of organic bases (such as BPP or BPY), in combination with specific hydrothermal conditions, promote the formation of uranyl terephthalate polycatenated frameworks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Accelerated Computational Analysis of Metal–Organic Frameworks for Oxidation Catalysis

High-spin iron(IV)–oxo compounds are known to activate strong C–H bonds. Stabilizing the high-spin S = 2 electronic configuration is difficult in molecular species for homogeneous catalysis, but recent experimental and computational results suggest this can be achieved in the metal–organic framework Fe 2 (dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogues. With a novel computational screening approach, we have identified three additional frameworks that are predicted to form high-spin iron(IV)–oxo species upon dissociative adsorption of nitrous oxide. The computational work is supported by follow-up experiments which show that, among these three materials, Fe-BTT (BTT 3– = 1,3,5-benzenetristetrazolate) selectively oxidizes ethane to ethanol at 120 °C. Subsequent spectroscopic and cycling studies suggest that framework defects, rather than the bulk framework or extraframework sites, are likely responsible for the observed reactivity. Furthermore, this work shows how computational methods can be used to rapidly identify promising candidate frameworks, and highlights the need for new methods that allow defect sites in metal–organic frameworks to be better understood and exploited for catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Confined Ionic Liquid in an Ionic Porous Aromatic Framework for Gas Separation

Ionic liquids (ILs) and porous frameworks are commonly employed in gas separation, but rarely together. To leverage their combined advantages, we designed a novel system comprising an ionic liquid inside a charged porous-polymer framework. A positively charged ionic porous aromatic framework was impregnated with an ionic liquid to confine the cations and anions inside the polymeric framework via electrostatic interactions. Molecular dynamics and free energy simulations were performed to determine the solubility, diffusivity, and hence permeability of CO 2 and CH 4 through the composite material. We found that the polymeric framework introduces nanoscale space in the confined IL, improving gas solubility, while the IL promotes gas transport in the porous structure. Here, the confinement impacts CO 2 and CH 4 very differently regarding their solubility and diffusivity. Through tuning of the ionic-liquid loading, both high CO 2 permeability and high CO 2 /CH 4 selectivity could be achieved, overcoming the Robeson upper bound. This work highlights the advantages of confined ionic liquids in an ionic porous-polymer framework in enhancing selective gas separation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Liquid and Glass Phases of an Alkylguanidinium Sulfonate Hydrogen-Bonded Organic Framework

Glassy phases of framework materials feature unique and tunable properties that are advantageous for gas separation membranes, solid electrolytes, and phase-change memory applications. However, the structural and chemical diversity of porous frameworks that can be liquified and quenched into a glass has been limited by thermal decomposition at-or below-the high temperatures required to induce a melting transition. Utilizing a desymmetrization strategy, in this work we report a new guanidinium organosulfonate hydrogen-bonded organic framework (HOF) that melts and vitrifies below 100 °C. In this low-temperature regime, non-covalent interactions between guest molecules and the porous framework become a dominant contributor to the overall stability of the structure, resulting in unusual phase behavior such as guest dependent melting, glass, and recrystallization transitions. Through molecular dynamics simulations and pair distribution function analysis, we show that the local structure of the amorphous liquid and glass phase resembles that of the parent crystalline framework. Access to molten phases of framework materials at moderate temperatures should permit the use of more thermally sensitive functional groups and enhance the structural control and tunability that can be realized in network-forming glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Structural and electronic switching of a single crystal 2D metal-organic framework prepared by chemical vapor deposition

The incorporation of metal-organic frameworks into advanced devices remains a desirable goal, but progress is hindered by difficulties in preparing large crystalline metal-organic framework films with suitable electronic performance. We demonstrate the direct growth of large-area, high quality, and phase pure single metal-organic framework crystals through chemical vapor deposition of a dimolybdenum paddlewheel precursor, Mo 2 (INA) 4 . These exceptionally uniform, high quality crystals cover areas up to 8600 µm 2 and can be grown down to thicknesses of 30 nm. Moreover, scanning tunneling microscopy indicates that the Mo 2 (INA) 4 clusters assemble into a two-dimensional, single-layer framework. Devices are readily fabricated from single vapor-phase grown crystals and exhibit reversible 8-fold changes in conductivity upon illumination at modest powers. Moreover, we identify vapor-induced single crystal transitions that are reversible and responsible for 30-fold changes in conductivity of the metal-organic framework as monitored by in situ device measurements. Gas-phase methods, including chemical vapor deposition, show broader promise for the preparation of high-quality molecular frameworks, and may enable their integration into devices, including detectors and actuators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗