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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Porous bipolar polymers as organic cathodes for sustainable sodium/potassium-ion batteries

Redox-active porous polymers are becoming promising organic electrode materials for alkali-ion batteries because of their tunable pore size, flexible chemical structure, and high thermal stability. This work presents various porous bipolar polymers as cathodes in Na-ion batteries (NIBs) and K-ion batteries (KIBs). Two structural units containing carbonyl and amine active centers, respectively, were introduced into the repeating units of the polymers by the polycondensation of N,N,N',N'-tetrakis(4-aminophenyl)-1,4-phenylenediamine (TAP) and various dianhydrides. Here, the resulting bipolar polymers undergo multi-electron redox reactions involving both cations and anions during battery charge and discharge. The impacts of extended conjugation structures and porosity on the electrochemical performances were investigated by tuning the conjugation structures in the dianhydride monomers. The bipolar polymers with extended conjugation structures and small pore size exhibit superior electrochemical performance in NIBs and KIBs in terms of high redox potentials, long cycle life, and fast-charging capability, demonstrating great promise as organic cathode materials for alkali-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2013

Improved synthesis and crystal structure of the flexible pillared layer porous coordination polymer: Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN) 4 ]

This paper reports our synthesis of flexible coordination polymer, Ni(L)[Ni(CN) 4 ], (L = 1,2-bis(4-pyridyl)ethylene (nicknamed bpene)), and its structural characterization using synchrotron single crystal X-ray diffraction. The structure of the purplish crystals has been determined to be monoclinic, space group P2 1 /m, a = 13.5941(12) Å, b = 14.3621(12) Å, c = 14.2561(12) Å, β = 96.141(2)°, V = 2767.4(4) Å 3 , Z = 4, D c = 1.46 g cm -1 . Ni(bpene)[Ni(CN) 4 ] assumes a pillared layer structure with layers defined by Ni[Ni(CN) 4 ] n nets and bpene ligands acting as pillars. With the present crystallization technique which involves the use of concentrated ammonium hydroxide solution and dimethyl sulfoxide (DMSO), disordered free bpene ligands and solvents of crystallization (DMSO and water molecules) occupy the pores, resulting in a formula of Ni(bpene)[Ni(CN) 4 ](1/2)bpene∙DMSO 2 H 2 O, or Ni 2 N 7 C 24 H 25 SO 3 . Without the inclusion of free bpene ligands and solvent molecules, the free volume is approximately 61% of the total volume; this free volume fraction is reduced to 50% with the free ligands present. Pores without the free ligands were found to have a local diameter of 5.7 Å and a main aperture of 3.5 Å. Based on the successful crystal synthesis, we also devised a new bulk synthetic technique which yielded a polycrystalline material with a significantly improved CO 2 uptake as compared to the originally reported powder material. The improved synthetic technique yielded a polycrystalline material with 40% higher CO 2 uptake compared to the previously reported powder material. An estimated 14.4 molecules of CO 2 per unit cell was obtained.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Polymeric molecular sieve membranes for gas separation

A porous polymer membrane useful in gas separation, the porous polymer membrane comprising a polymeric structure having crosslinked aromatic groups and a hierarchical porosity in which micropores having a pore size less than 2 nm are present at least in an outer layer of the porous polymer membrane, and macropores having a pore size of over 50 nm are present at least in an inner layer of the porous polymer membrane. Also described are methods for producing the porous polymer membrane in which a non-porous polymer membrane containing aromatic rings is subjected to a Friedel-Crafts crosslinking reaction in which a crosslinking molecule crosslinks the aromatic rings in the presence of a Friedel-Crafts catalyst and organic solvent under sufficiently elevated temperature, as well as methods for using the porous polymer membranes for gas or liquid separation, filtration, or purification.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Covalent integration of polymers and porous organic frameworks

Covalent integration of polymers and porous organic frameworks (POFs), including metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and hydrogen-bonded organic frameworks (HOFs), represent a promising strategy for overcoming the existing limitations of traditional porous materials. This integration allows for the combination of the advantages of polymers, i.e., flexibility, processability and chemical versatility etc., and the superiority of POFs, like the structural integrity, tunable porosity and the high surface area, creating a type of hybrid materials. These resulting polymer-POF hybrid materials exhibit enhanced mechanical strength, chemical stability and functional diversity, thus opening up new opportunities for applications across a large variety of fields, such as gas separation, catalysis, biomedical applications, environmental remediation and energy storage. In this review, an overview of synthetic routes and strategies on how to covalently integrate different polymers with various POFs is discussed, especially with a particular focus on methods like polymerization within, on and among POF structures. To investigate the unique properties and functions of these resultant hybrid materials, the characterization techniques, including nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and scanning electron microscopy (SEM), gas adsorption analysis (BET) and computational modeling and machine learning, are also presented. The ability of polymer-POFs to manipulate the pore environments at the molecular level affords these materials a wide range of applications, providing a versatile platform for future advancements in material science. Looking forward, to fully realize the potential of these hybrid materials, the authors highlight the scalability, green synthesis methods, and potential for stimuli-responsive polymer-POF materials as critical areas for future research.

Hossain, Md Amjad↗
DOE OSTI2019

Topotactic Synthesis of Phosphabenzene-Functionalized Porous Organic Polymers: Efficient Ligands in CO 2 Conversion

Progress toward the preparation of porous organic polymers (POPs) with task-specific functionalities has been exceedingly slow—especially where polymers containing low-oxidation phosphorus in the structure are concerned. In this work, a two-step topotactic pathway for the preparation of phosphabenzene-based POPs (Phos-POPs) under metal-free conditions is reported, without the use of unstable phosphorus-based monomers. The synthetic route allows additional functionalities to be introduced into the porous polymer framework with ease. As an example, partially fluorinated Phos-POPs (F-Phos-POPs) were obtained with a surface area of up to 591 m 2 g –1 . After coordination with Ru species, a Ru/F-Phos-POPs catalyst exhibited high catalytic efficiency in the formylation of amines (turnover frequency up to 204 h –1 ) using a CO 2 /H 2 mixture, in comparison with the non-fluorinated analogue (43 h –1 ) and a Au/TiO 2 heterogeneous catalysts reported previously (<44 h –1 ). This work describes a practical method for synthesis of porous organic phosphorus-based polymers with applications in transition-metal-based heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Tuning of magnetic parameters in cobalt-polystyrene nanocomposites by reduction cycling

Graphical abstract: Cobalt nanoparticles were prepared by a reduction process inside polymer pores. A porous polymer network (polystyrene) was chosen as the template for the synthesis of elementary cobalt as high surface area cobalt nanoparticles are prone to oxidation. The preliminary studies reveal that the cobalt is first formed with an oxide protective layer outside and upon repeating the reduction cycles, inner pores of the polymers are opened which enhanced the yield of metallic cobalt. These high surface area cobalt nanoparticles embedded in a polymer are ideal for the synthesis of carbon nanotubes as cobalt can act as a catalyst for the nanotube synthesis. The concentration of cobalt can be tuned in this technique by repeating the cycling process. Highlights: {yields} Elementary cobalt nanoparticles were synthesized inside polystyrene by a novel process. {yields} The self protection is achieved by the auto-shelling with the metal oxide. {yields} The magnetisation and coercivity could be tuned by repeating the cycles. {yields} Tuning of magnetic properties (both coercivity and magnetisation) could be achieved by the repetition of reduction cycles. {yields} Synthesized nanocomposite can act as a catalyst for carbon nanotube synthesis. -- Abstract: Cobalt nanoparticles were prepared by a reduction process inside polymer pores using CoSO{sub 4}.7H{sub 2}O and NaBH{sub 4}. A porous polymer network (sulphonated polystyrene) was chosen, as the template for the synthesis of elementary cobalt as high surface area cobalt nanoparticles are prone to oxidation. The preliminary studies reveal that the cobalt is first formed with an oxide protective layer outside and upon repeating the reduction cycles, inner pores of the polymers are opened which enhanced the yield of metallic cobalt. These high surface area cobalt nanoparticles embedded in a polymer are ideal for the synthesis of carbon nanotubes as cobalt can act as a catalyst for the nanotube synthesis. The concentration of cobalt can be tuned in this technique by repeating the cycling process.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Amine-functionalized porous organic polymers for carbon dioxide capture

Recent developments in CO 2 capture using porous organic polymers (POPs) have received accrescent attention due to their sorbent properties such as high CO 2 uptake capacity and selectivity, tunable chemical structure and permanent porosity. POPs are constructed using two and/or three-dimensional organic monomers (building blocks) linked to each other through covalent bonding, creating high porosity. The pore structure in POPs is exceptionally stable, which leads to their cyclable CO 2 adsorption performance. However, POPs generally suffer from low CO 2 uptake and selectivity due to their interaction with CO 2 in physisorption limits (20–40 kJ mol -1 ). Similar to that in other physisorbents, the CO 2 uptake capacity of POPs further decreases under humid conditions. Pursuant to these limitations, amine functionalization in POPs has resulted in enhanced CO 2 uptake performance with improved CO 2 selectivity over non-polar gases such as N 2 . More importantly, several types of amine-functionalized POPs showed that the CO 2 uptake could remain intact under humid conditions such as in post-combustion flue gas. This review article covers recent developments in amine-functionalized porous organic polymers. Three main categories of amine functionalization, such as direct amine synthesis, amine impregnation and amine grafting, were investigated in detail by considering the effect of amines on the sorbent properties and CO 2 capture performance of POPs. The recent findings in amine-functionalized POPs were investigated including porous polymeric networks (PPNs), covalent organic frameworks (COFs), amine linked POPs, hyper-crosslinked polymers (HCPs), conjugated microporous polymers (CMPs), benzimidazole linked polymers (BILPs), porous aromatic frameworks (PAFs) and polymers of intrinsic microporosity (PIMs).

36 MATERIALS SCIENCE↗
DOE OSTI2014

Thiazolothiazole-linked porous organic polymers

In this study, thiazolothiazole-linked porous organic polymers have been synthesized from a facile catalyst-free condensation reaction between aldehydes and dithiooxamide under solvothermal conditions. The resultant porous frameworks exhibit a highly selective uptake of CO 2 over N 2 under ambient conditions.

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

Functionalized Porous Organic Polymers as Uranium Nano-Traps for Efficient Recovery of Uranium from Seawater

The long-term use of nuclear power for energy applications relies on the secure and economical supply of nuclear fuel. Among various natural sources of uranium for use in nuclear reactors, seawater is highly appealing given that the oceans contain about 4.5 billion tons of dissolved uranium, almost 1000 times that estimated for mineral reserves. Nonetheless, the concentration of uranium in seawater is extremely low (3-3.3 mg L -1 or 3-3.3 ppb); this, coupled with the presence of a relatively high concentration of other metal ions, makes uranium recovery from seawater a challenge that requires the development of efficient and effective separation processes. Various adsorbent technologies based upon synthetic organic polymers, biopolymers, inorganic materials, mesoporous silica materials, porous carbon-based adsorbents, and ionic liquids have been widely developed for the extraction of uranium from seawater. However, these benchmark sorbent materials suffer from a number of drawbacks such as low adsorption capacity (typically 0.1~3.2 mg-U g -1 adsorbent), poor selectivity, and slow kinetics. Given the extreme complexity and vast volume of seawater, as well as the very low concentration of uranium present, to attain this ambitious task demands the design of adsorbents with high affinity and fast kinetics. The main objective of this project is to develop functional porous organic polymers (POPs) as a new type of adsorbent for mining uranium from seawater. This class of porous materials has quickly moved to the forefront of materials research due to their high internal surface areas, exceptional water/chemical stability, facile chemical tunability, and extraordinary capability to selectively adsorb large quantities of guest species The potential to deploy POPs in uranium extraction is related to the ease with which their internal surfaces can be decorated with high densities of strong binding sites. Beyond introducing postsynthetic modification, the specific functionalities also can be used as building units to be incorporated into porous frameworks. Our approach to fulfill this task involves the custom-design of POP-based uranium “nano-traps” via a “crystal engineering” guided design followed by stepwise post-synthetic modification. Furthermore, to increase the density of chelating groups and to enhance their affinity towards uranyl ions, judiciously designed chelating systems were constructed into porous organic polymers. Moreover, to improve the accessibility of the chelating groups and thereby the utilization efficiency, we assembled the chelating groups into highly crystalline materials where they are aligned in periodic arrays on the open channels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2014

Introduction of π-Complexation into Porous Aromatic Framework for Highly Selective Adsorption of Ethylene over Ethane

We report herein a strategy of incorporating air stable Ag(I) ions into water stable, high surface area porous organic polymer (POP) affording significant increase in ethylene uptake capacity and extremely high Qst for ethylene (over 100 kJ/mol at low ethylene load-ing) as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and equimolar ethylene/ethane ratio at 296 K reveal PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivi-ty (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. This alongside excellent water/air stability, high ethylene uptake capacity, and mild regeneration requirements make PAF-1-SO3Ag hold promise for adsorption-based eth-ylene/ethane separations, paving a way to develop Ag(I) ion function-alized POPs as a new platform for highly selective adsorption of eth-ylene over ethane.

Li, Baiyan↗
DOE OSTI2017

Flexible porous coordination polymer of Ni(II) for developing nanoparticles through acid formation and redox activity of the framework

Immobilization of the nanoparticles (NPs) in a two dimensional porous coordination polymer (PCP) is currently an emerging field for a number of applications. But still it is a great challenge to fabricate any specified metal NPs in a single network. Herein the synthesis of Au, Pd, Mn, Fe, Cu, Zn, Mg, Li, Fe/Cu, Zn/Mg etc, NPs in a highly flexible PCP of Ni(II); {[Ni_3(TBIB)_2(BTC)_2(H_2O)_6]·5C_2H_5OH·9H_2O}{sub n} [TBIB = 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene, H{sub 3}BTC = 1,3,5-benzenetricarboxylic acid] have been reported. This universal host is able to grow mixed metal NPs from mixed metal precursors. Monodentate carboxylate groups of BTC linker act as anchoring sites for the metal ions of the metal precursors. This is the main driving force to grow NPs within the cavities along with the high flexibility of this polymer at room temperature. Mechanism involves acid formation followed by redox reaction to synthesize metal NPs explained by EPR and FTIR. Paramagnetic properties have been shown by as-synthesized Fe NPs integrated framework at room temperature under applied magnetic field up to 17,500 Oe. - Graphical abstract: A number of nanoparticles including Au, Pd, Mn, Fe, Cu, Zn, Mg, Li as well as mixed NPs Fe/Cu, Zn/Mg have been synthesized at room temperature without use of any surfactant and reducing agent. Display Omitted - Highlights: • Different types of NPs have been synthesized in a 2D polymer at room temperature. • Surfactant and reducing agents have not been used for NPs synthesis. • Monodentate carboxylate groups of BTC linker act as anchoring sites for metal ions. • NPs were synthesized by acid formation and redox activity of the framework. • Fe NPs integrated framework shows paramagnetic properties at room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Engineering porous organic polymers for carbon dioxide capture

As atmospheric CO 2 levels rise, the development of physical or chemical adsorbents for CO 2 capture and separation is of great importance on the way towards a sustainable low-carbon future. Porous organic polymers are promising candidates for CO 2 capture materials owing to their structural flexibility, high surface area, and high stability. We highlight high-performance porous organic polymers for CO 2 capture and summarize the strategies to enhance CO 2 uptake and selectivity, such as increasing surface area, increasing interaction between porous organic polymers and CO 2 , and pore surface functionalization.

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

Highly porous organic polymers bearing tertiary amine group and their exceptionally high CO{sub 2} uptake capacities

We report a very simple and unique strategy for synthesis of a tertiary amine functionalized high surface area porous organic polymer (POP) PDVTA-1 through the co-polymerization of monomers divinylbenzene (DVB) and triallylamine (TAA) under solvothermal reaction conditions. Two different PDVTA-1 samples have been synthesized by varying the molar ratio of the monomers. The porous polymeric materials have been thoroughly characterized by solid state {sup 13}C CP MAS-NMR, FT-IR and UV–vis spectroscopy, N{sub 2} sorption, HR TEM and FE SEM to understand its chemical environment, nanostructure, bonding, morphology and related surface properties. PDVTA-1 with higher amine content (DVB/TAA=4.0) showed exceptionally high CO{sub 2} uptake capacity of 85.8 wt% (19.5 mmol g{sup −1}) at 273 K and 43.69 wt% (9.93 mmol g{sup −1}) at 298 K under 3 bar pressure, whereas relatively low amine loaded material (DVB/TAA=7.0) shows uptake capacity of 59.2 wt% (13.45 mmol g{sup −1}) at 273 K and 34.36 wt% (7.81 mmol g{sup −1}) at 298 K. Highly porous nanostructure together with very high surface area and basicity at the surface due to the presence of abundant basic tertiary amine N-sites in the framework of PDVTA-1 could be responsible for very high CO{sub 2} adsorption. - Graphical abstract: Exceptionally high CO2 uptake (85.8 wt % at 273 K) has been observed over a high surface area porous organic polymer PDVTA-1 synthesized through copolymerization of divinylbenzene and triallyl amine. - Highlights: • Designing the synthesis of a new N-rich cross-linked porous organic polymer PDVTA-1. • PDVTA-1 showed mesoporosity with very high surface area of 903 m{sup 2} g{sup −1}. • High surface area and presence of basic sites facilitates the CO{sub 2} uptake. • PDVTA-1 showed exceptionally high CO{sub 2} adsorption capacity of 85.8 wt% at 273 K, 3 bar pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis and physicochemical characterization of a porous coordination polymer of Sn-Cu xylarate: The structure of [Sn{sub 4}Cu{sub 8.5}(HL){sub 2}(L){sub 4}O{sub 2}(OH)(H{sub 2}O){sub 12.5}] {center_dot} 17.2H{sub 2}O

A porous coordination polymer of Sn-Cu xylarate [Sn{sub 4}Cu{sub 8.5}(HL){sub 2}(L){sub 4}O{sub 2}(OH)(H{sub 2}O){sub 12.5}] {center_dot} 17.2H{sub 2}O (H{sub 5}L is xylaric acid) is synthesized for the first time and characterized by chemical analysis, IR spectroscopy, and X-ray diffraction. Centrosymmetric heterometallic fragments [Sn{sub 4}Cu{sub 6}(HL){sub 2}(L){sub 4}O{sub 2}(H{sub 2}O){sub 6}] (A) including copper Cu1-3 and tin Sn1,2 atoms are distinguished in the structure. The Cu4(OH){sub 0.5}(H{sub 2}O){sub 2.5} bridges connect A units into chains running along the c axis, and the Cu5(OH)(H{sub 2}O) bridges connect A fragments into layers perpendicular to the c axis. The Cu4,5 atoms form a framework whose voids accommodate the crystallization water molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Rational Design of Porous Conjugated Polymers and Roles of Residual Palladium for Photocatalytic Hydrogen Production

Developing high efficient photocatalyts for splitting water into oxygen and hydrogen is one of the biggest chemical challenges in solar energy utilization. In this paper, we report our effort in rationally designing conjugated porous polymer (CPP) photocatalysts for photocatalytic hydrogen production (PHP) from water. A series of CPP photocatalysts with different chromophore components and bipyridyl (bpy) contents were synthesized and found to evolve hydrogen photocatalytically from water. The PHP activity of bpy-containing CPPs can be greatly enhanced due to the improved light absorption, better wettability, higher crystallinity and the improved charge separation process. Moreover, the CPP photocatalyst made of strong and fully conjugated donor chromo-phore DBD shows the highest hydrogen production rate ~ 33 μmol/h. The results indicate that copolymerization between a strong donor and weak acceptor is a useful strategy for the devel-opment of efficient photocatalysts. This study clarifies that the residual palladium in the CPP networks plays a key role for the catalytic performance. The PHP activity of CPP photocatalyst can be further enhanced to 164 μmol/h with an apparent quantum yield of 1.8% at 350 nm by loading 2 wt% of extra platinum cocat-alyst.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Precious metal recovery from electronic waste by a porous porphyrin polymer

Significance Electronic waste, also called e-waste, is rapidly becoming a major industrial hazard because of the increased use of circuits and screens. With the right technology, however, this waste could become a sustainable source for precious metals. Such a solution requires selectivity toward the precious metals, as this characteristic is even more important than capacity. A porphyrin-based porous polymer with selective binding shows remarkable selectivity and a reductive mechanism, a combination which makes for record-high recycling of precious metals––particularly gold––from e-waste.

Hong, Yeongran↗
DOE OSTI2015

Redox-active porous coordination polymer based on trinuclear pivalate: Temperature-dependent crystal rearrangement and redox-behavior

Linking of trinuclear pivalate Fe{sub 2}NiO(Piv){sub 6} (Piv=O{sub 2}CC(CH{sub 3}){sub 3}) by 2,6-bis(4-pyridyl)-4-(1-naphthyl)pyridine (L) resulted in formation of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)·Solv, which was characterized in two forms: DMSO solvate Fe{sub 2}NiO(Piv){sub 6}(L)(DMSO)·2.5DMSO (1) or water solvate Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) (2). X-ray structure of 1 was determined. Crystal lattice of 1 at 160 K contained open channels, filled by captured solvent, while temperature growth to 296 K led to the crystal lattice rearrangement and formation of closed voids. Redox-behavior of 2 was studied by cyclic voltammetry for a solid compound, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. The presence of pores in desolvated sample Fe{sub 2}NiO(Piv){sub 6}(L) was confirmed by the measurements of N{sub 2} and H{sub 2} adsorption at 77 K. Potential barriers of the different molecules diffusion through pores were estimated by the means of molecular mechanics. - Graphical abstract: Redox-behavior of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) was studied by cyclic voltammetry in thin film, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. Potential barriers of different molecules diffusion through pores were estimated by the means of molecular mechanics. - Highlights: • Porous 1D coordination polymer was synthesized. • Temperature growth led to pores closing due to crystal lattice rearrangement. • Redox-activity of ligand preserved upon incorporation into coordination polymer. • Redox-properties of solid coordination polymer were studied in thin film. • Diffusion barriers were evaluated by molecular mechanics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗