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At least 19 records

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DOE OSTI2023

Solid-state crystallization of metal organic frameworks within mesoporous materials methods and hybrid materials thereof

A method, comprising i) contacting an aqueous solution of an organic ligand salt of the formula A X (L −X ) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula A X (L −X )/MPM, ii) treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula H X (L −X )/MPM, iii) contacting an aqueous solution of a metal precursor of the formula M +y (B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M +y (B) y ][H x (L −x )]/MPM, and iv) at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M +y L −x )/MPM, wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

Minguez, Ignacio Luz↗

DOE OSTI2020

Electrochemical Behavior of Copper Ion Complexed with Nanoparticle Organic Hybrid Materials

Nanoscale Organic Hybrid Materials (NOHMs) have unique properties that show potential for their use as novel electrolytes that can interact with redox active species. In this work, we probe the effects of adding poly(ethyleneimine)-based NOHMs (NOHM-I-PEI) on copper ion electrochemical reactions. As NOHM-I-PEI is added to a solution containing Cu(II), the voltammetric peak current decreases. This is likely caused by strong complex formation between the PEI nitrogen and the copper, similar to complexation observed in solutions of the polymer with copper. Upon copper addition to a NOHM-I-PEI solution, the pH decreases from 10.1, plateauing at pH = 5.3 at ~3:1 N:Cu ratio indicating that Cu(II) displaces protons. The UV–visible spectra exhibit a Cu-PEI peak, the intensity of which levels off at ~2.8 N:Cu. Acid titration of the N-moieties of the PEI reveals three inflections corresponding to N-environments in the PEI. Upon controlling the pH of the solution by buffering, the "sequestration" of Cu(II) is found to occur when there are unprotonated nitrogens present in the NOHM-I-PEI system; this phenomenon is also supported by UV-vis results. Furthermore, this work highlights the potential of and the design of NOHMs to carry charged electroactive species in solutions along with key factors to control for optimal function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Aluminum Based Solvent-Free Organic–Inorganic Hybrid Materials

In emerging materials, molecular hybrids are especially promising, as they have molecular level mixing of the organic and inorganic components, producing homogeneous materials without interfaces that can deteriorate properties. However, the current methods of manufacturing molecular hybrids are based on solution processing, which is impractical for bulk materials such as may be used for optically clear radiation and electromagnetic shielding components or photonics. Here we examine molecular hybrids composed of aluminum isopropoxide (AIP) and epoxy resins aiming to understand the molecular scale chemistry and manufacturability of these hybrid materials. DSCmonitored cure revealed the ideal cure temperature for these materials is 160−170 °C and demonstrated that an AIP concentration of 16.7 wt % maximizes the extent of reaction. Kinetic analysis of the curing reaction showed the Sestak−Berggren autocatalytic model is effective at temperatures over 140 °C but the reaction has diffusion limitations at a temperature of 120 °C. Mechanical testing with custom resin molds revealed a decrease in properties of the bulk samples with increasing AIP content due to an increase in defects but further testing with nanoindentation demonstrated comparable or improved mechanical properties of AIP-epoxy hybrids compared to epoxy resin with a standard hardener. Ultimately, this work lays the foundation for hardener-free epoxy-aluminum inorganic/organic hybrids and presents opportunities to expand on properties for specific applications such as thermal conductivity, optical clarity, and dielectric constant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Impacts of Bond Type and Grafting Density on the Thermal, Structural, and Transport Behaviors of Nanoparticle Organic Hybrid Materials–Based Electrolytes

Nanoscale Organic Hybrid Materials (NOHMs) consist of polymers tethered to a nanoparticle surface, and NOHMs formed with an ionic bond between the polymer and nanoparticle have been proposed for electrochemical applications. NOHMs exhibit negligible vapor pressure, chemical tunability, oxidative thermal stability, and high ionic conductivity making them attractive in reactive and separation systems. In this study, NOHMs are synthesized by tethering Jeffamine M2070 (HPE) to SiO 2 nanocores via ionic (NOHM-I-HPE) and covalent (NOHM-C-HPE) bonding to investigate the effect of the bond type on the thermal, structural and transport properties of the tethered HPE. In the neat state, NOHM-C-HPE displays the highest thermal stability in a nitrogen atmosphere, while NOHM-I-HPE is the most stable under oxidative conditions. Small-angle neutron scattering (SANS) reveals the presence of multiple types of HPE polymers in aqueous solutions of NOHM-I-HPE (i.e., tethered, interacting, and free), whereas only tethered HPE is observed in NOHM-C-HPE systems. Moreover, the SANS profiles identify clustering of NOHM-C-HPE in aqueous solutions, but not in the corresponding NOHM-I-HPE solutions, suggesting that the free HPE chains stabilize the dispersion of NOHM-I-HPE. Furthermore, the results of this study elucidate how the bond type and grafting density can be used to tune the properties of NOHMs.

25 ENERGY STORAGE↗

DOE OSTI2021

Hybrid materials and nanocomposite materials, methods of making same, and uses thereof

Hybrid materials and nanocomposite materials, methods of making and using such materials. The nanoparticles of the nanocomposite are formed in situ during pyrolysis of a hybrid material comprising metal precursor compounds. The nanoparticles are uniformly distributed in the carbon matrix of the nanocomposite. The nanocomposite materials can be used in devices such as, for example, electrodes and on-chip inductors.

Archer, Lynden A.↗

DOE OSTI2021

In situ preparation of visible-light-driven carbon quantum dots/NaBiO 3 hybrid materials for the photoreduction of Cr(VI)

Here, different carbon quantum dots (CQDs)/NaBiO 3 hybrid materials were synthesized as photocatalysts to effectively utilize visible light for the photocatalytic degradation of contaminants effectively. These hybrid materials exhibit an enhanced photocatalytic reduction of hexavalent chromium (Cr(VI)) in the aqueous medium. Zero-dimensional nanoparticles of CQDs were embedded within the two-dimensional NaBiO 3 nanosheets by the hydrothermal process. Compared with that of the pure NaBiO 3 nanosheets, the photocatalytic performance of the hybrid catalysts was significantly high and 6 wt.% CQDs/NaBiO 3 catalyst exhibited better photocatalytic performance. We performed the first-principles density functional theory calculations to study the interfacial properties of pure NaBiO 3 nanosheets and hybrid photocatalysts, and confirmed the CQDs played an important role in the CQDs/NaBiO 3 composites. The experimental results indicated that the enhanced reduction of Cr(VI) was probably due to the high loading of CQDs (electron acceptor) on NaBiO 3 , which made NaBiO 3 nanomaterials to respond in visible light and significantly improved their electron-hole separation efficiency.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Controlled synthesis of hierarchically-structured hybrid materials through peptoid engineering

This disclosure concerns a method for making a hybrid organic/inorganic material having an architecture. The method includes combining a peptoid comprising a sequence of N-substituted glycine residues and an inorganic material or inorganic material precursor to form a hybrid organic/inorganic material comprising the peptoid and the inorganic material, the hybrid organic/inorganic material having an architecture based at least in part on the peptoid sequence. The hybrid organic/inorganic materials include a cluster of nanoparticles of an inorganic material and peptoids, the cluster formed by random attachment of nanoparticles to one another by peptoid-peptoid and peptoid-nanoparticle surface interactions, wherein the hybrid material has an architecture based at least in part on the peptoid sequence.

Chen, Chun-Long↗

DOE OSTI2025

Confinement-Driven Segregation Enables Glassy Polymer Hybrid Materials Featuring Disordered Hyperuniformity and Integrated Self-Healing

The blending of glassy copolymer-brush modified colloids with a viscoelastic linear copolymer featuring intrinsic self-healing enabled disordered hyperuniform hybrid materials that combined mechanical robustness with structural color, processability, environmental stability, and the ability to recover structure and properties after incurring physical damage via ‘integrated self-healing’. Symmetric linear n-butyl acrylate/methyl methacrylate (BA/MMA) were co-assembled with asymmetric glassy BA/MMA statistical copolymer brush (silica) particles. ‘Confinement-driven segregation’ resulted in a microphase-separated morphology in which the linear copolymer resided within the interstitial regions of a rigid (∼1 GPa) copolymer brush particle template with disordered hyperuniform microstructure. Diffusion of the self-healing copolymer additive into damage regions drove the recovery after damage, along with the restoration of structural color due to the materials hyperuniform microstructure. The synergistic action of intrinsic and extrinsic healing mechanisms could provide a versatile platform for the bottom-up fabrication of multifunctional hybrid materials with increased damage resistance and functional longevity.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System

Abstract Together with the synthesis and experimental characterization of 14 hybrid materials containing [UO 2 X 4 ] 2− (X=Cl − and Br − ) and organic cations, we report on novel methods for determining correlation trends in their formation enthalpy (ΔH f ) and observed vibrational signatures. Δ H f values were analyzed through isothermal acid calorimetry and a Density Functional Theory+Thermodynamics (DFT+T) approach with results showing good agreement between theory and experiment. Three factors (packing efficiency, cation protonation enthalpy, and hydrogen bonding energy [ ]) were assessed as descriptors for trends in Δ H f . Results demonstrated a strong correlation between and Δ H f , highlighting the importance of hydrogen bonding networks in determining the relative stability of solid‐state hybrid materials. Lastly, we investigate how hydrogen bonding networks affect the vibrational characteristics of uranyl solid‐state materials using experimental Raman and IR spectroscopy and theoretical bond orders and find that hydrogen bonding can red‐shift U≡O stretching modes. Overall, the tightly integrated experimental and theoretical studies presented here bridge the trends in macroscopic thermodynamic energies and spectroscopic features with molecular‐level details of the geometry and electronic structure. This modeling framework forms a basis for exploring 3D hydrogen bonding as a tunable design feature in the pursuit of supramolecular materials by rational design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System

36 MATERIALS SCIENCE↗

DOE OSTI2024

Insights into the Assembly and Conformation of Nanoparticle Organic Hybrid Materials (NOHMs) in Solution with Varying Grafting Type

Recently, nanoparticle organic hybrid materials (NOHMs) have been considered promising electrolytes for energy storage applications due to their unique combination of properties, which include high thermal stability, negligible vapor pressure, and easy synthesis. However, the structural features of NOHMs in electrochemical systems are not well understood. Hence, we investigate the impact of grafting type (ionic vs covalent) on the structure and performance of NOHMs that consist of a silica core and grafted HPE polymer (Jeffamine M2070) in aqueous solution with and without the presence of the supporting electrolyte (0.1 M KHCO 3 ) using small-angle neutron scattering. Careful analyses of the results indicate that even at low grafting density (0.8 chains nm –2 ) and concentration (1–3 wt %), ionic NOHMs solutions contain a free polymer that may interact with the grafted polymer, altering the assembly of NOHMs in solution. Our investigation also elucidates that the covalent NOHM solutions consist of both aggregated and dispersed NOHMs in the solution. Moreover, the addition of the supporting electrolyte affects the assembly and structure of the polymer in the ionic NOHMs solution significantly, whereas only a slight change in the conformation of the grafted polymer is observed for covalent NOHMs. These conformational changes alter the performance of the NOHMs solution, resulting in a dramatic change in viscosity. Careful analysis shows that this significant alteration of solution viscosity in the ionic NOHMs can be traced back to the presence of the free polymer that interacts with the grafted layer and the attenuation of this interaction between the free and grafted polymers with the addition of salt. Furthermore, these studies elucidate the impact of grafting type on the overall structure, assembly, and performance of functionalized NOHMs in aqueous solution and explicitly correlate the structure and assembly of NOHMs to their transport properties and must be considered when designing functional systems that incorporate NOHMs.

25 ENERGY STORAGE↗

DOE OSTI2021

Localized and Collective Dynamics in Liquid-like Polyethylenimine-Based Nanoparticle Organic Hybrid Materials

In this work, broadband dielectric spectroscopy, rheology, and nuclear magnetic resonance spectroscopy are employed to study molecular dynamics in a nanoparticle organic hybrid materials(NOHMs)system comprising 20 wt% silica nanoparticles ionically-bonded to a polyethylenimine canopy. By comparing the neat polymer (used as a canopy) to the derivative NOHMs, we find that timescales characterizing segmental dynamics in the NOHM are identical to those for the neat polymer. Detailed analysis of the carbon-spin lattice relaxation times yields mechanistic insights into localized and collective dynamics, in quantitative agreement with dielectric results. Interestingly, the NOHMs retain liquid-like characteristics unlike conventional polymer nanocomposites but exhibit higher viscosity due to additional contributions from tethered polymer chains, and mesoscopic structuring. These findings demonstrate the potential of achieving unique and desired material properties via NOHMs by an informed choice of the canopy material.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Encapsulation of Nanoparticle Organic Hybrid Materials within Electrospun Hydrophobic Polymer/Ceramic Fibers for Enhanced CO 2 Capture

Liquid-like nanoparticle organic hybrid materials (NOHMs) consisting of a silica core with ionically grafted branched polyethyleneimine chains (referred to as NIPEI) are encapsulated within submicron-scale polyacrylonitrile (PAN)/polymer-derived-ceramic electrospun fibers. The addition of a room-temperature curable, liquid-phase organopolysilazane (OPSZ) ceramic precursor to the PAN/NOHM solution enhances the internal dispersion of NOHMs and forms a thin ceramic sheath layer on the fiber exterior, shielding the hydrophilic NIPEI to produce near-superhydrophobic non-woven fiber mats with contact angles exceeding 140°. 60:40 loadings of NOHMs to PAN/OPSZ can be reliably achieved with low OPSZ percentages required, and up to 4:1 NOHM:polymer loadings are possible before losing hydrophobicity. These fibers demonstrate up to ≈2 mmol CO 2 g -1 fiber capture capacities in a pure CO 2 atmosphere through the nonwoven fibrous networks and the permeability of the OPSZ shell. In conclusion, the hybrid fibers additionally show enhanced capture kinetics under pure CO 2 and 400 ppm CO 2 conditions, indicating their promising application as a direct air capture platform.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Plutonium Hybrid Materials: A Platform to Explore Assembly and Metal–Ligand Bonding

In this work, we report the synthesis of five new hybrid materials containing the [PuCl 6 ] 2- anion and charge balancing, non-covalent interaction donating 4-X-pyridinium (X = H, Cl, Br, I) cations. Single crystals of the title compounds were grown and harvested from acidic, chloride-rich, aqueous media and their structures were determined via X-ray diffraction. Compounds 1-4, (4XPyH) 2 [PuCl 6 ] and 5, (4IPyH) 4 [PuCl 6 ] · 2Cl, exhibit two distinct sheet-like structure types. Structurally relevant non-covalent interactions were tabulated from crystallographic data and verified computationally using electrostatic surface potential maps and the quantum theory of atoms in molecules (QTAIM) approach. The strength of the hydrogen and halogen bonds was quantified using Kohn-Sham density functional theory and a hierarchy of acceptor-donor pairings established. In turn, the PuIV-Cl bonds were studied using the QTAIM and natural localized molecular orbital (NLMO) approaches to delineate the underlying bond mechanism and hybrid atomic orbital contributions therein. Energy decomposition (ED) and natural ED analyses were also explored to probe the bond mechanism and, more broadly, explore the efficacy of these techniques in studying these anionic systems. The results of the PuIV-Cl bond analyses were compared across composition via analogous treatments of previously reported [PuO 2 Cl 4 ] 2- and [PuCl 3 (H 2 O) 5 ] molecular units. In summary, our study indicates that the Pu-Cl bonds are predominately ionic, yet exhibit small varying degrees of covalent character that increase from [PuCl 3 (H 2 O) 5 ], [PuO 2 Cl 4 ] 2- , to [PuCl 6 ] 2- , while the participation of the Pu based s/d and f orbitals concurrently decrease and increase, respectively.

transuranic↗

DOE OSTI2021

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

An emerging area of sustainable energy and environmental research is focused on the development of novel electrolytes that can increase the solubility of target species and improve subsequent reaction performance. Electrolytes with chemical and structural tunability have allowed for significant advancements in flow batteries and CO 2 conversion integrated with CO 2 capture. Liquid-like nanoparticle organic hybrid materials (NOHMs) are nanoscale fluids that are composed of inorganic nanocores and an ionically tethered polymeric canopy. NOHMs have been shown to exhibit enhanced conductivity making them promising for electrolyte applications, though they are often challenged by high viscosity in the neat state. In this study, a series of binary mixtures of NOHM-I-HPE with five different secondary fluids, water, chloroform, toluene, acetonitrile, and ethyl acetate, were prepared to reduce the fluid viscosity and investigate the effects of secondary fluid properties (e.g., hydrogen bonding ability, polarity, and molar volume) on their transport behaviors, including viscosity and diffusivity. We report our results revealed that the molecular ratio of secondary fluid to the ether groups of Jeffamine M2070 ($λ_{\text{SF}}$) was able to describe the effect that secondary fluid has on transport properties. Our findings also suggest that in solution, the Jeffamine M2070 molecules exist in different nanoscale environments, where some are more strongly associated with the nanoparticle surface than others, and the conformation of the polymer canopy was dependent on the secondary fluid. This understanding of the polymer conformation in NOHMs can allow for the better design of an electrolyte capable of capturing and releasing small gaseous or ionic species.

25 ENERGY STORAGE↗

DOE OSTI2023

Solution-Processable Copper Halide Based Hybrid Materials Consisting of Cationic Ligands with Different Coordination Modes

Here, using cationic ligands containing both aromatic and aliphatic coordination sites, we have synthesized and structurally characterized five new CuX-based hybrid materials consisting of anionic inorganic motifs that also form coordinate bonds with the cationic organic ligands. As a result of the unique bonding nature at the inorganic/organic interfaces, these compounds demonstrate strong resistance toward heat and can be readily processed in solution. They emit light in the visible region ranging from cyan to yellow color, with the highest photoluminescence quantum yield (PLQY) reaching 71%. The influence of the different coordination modes of the ligands on their emission behavior was investigated employing both experimental and theoretical methods, which have provided insight in understanding structure–property relationships in these materials and guidelines for tuning and enhancing their chemical and physical properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2023

Techno-economic and environmental life cycle assessment of next-generation fiber-encapsulated nanoscale hybrid materials for direct air carbon capture

A techno-economic and environmental life cycle assessment was conducted for manufacturing two novel types of solid sorbents used for direct air CO 2 capture (DAC). One type of solid sorbent comprised Polyacrylonitrile (PAN)/Organopolysilizane (OPSZ)/nanoscale organic hybrid materials (NOHM)(, and the other comprised polymers of intrinsic microporosity (PIM)/NOHM. These solid sorbents were assumed to be manufactured via an unconventional route: electrospinning as fibers. Economic analyses revealed that manufacturing costs for a 0.73 MT/year capacity plant was $\$$831 and $\$$1398/kg of electrospun fiber in the case ofPAN/OPSZ/NOHM and PIM/NOHM, respectively. The costs were higher for PIM/NOHM owing to high raw material prices (Spirobisindane and tetrafluoroterephthalonitrile), that are used only in manufacturing PIM. Scaling up the plant capacity from 0.73 to 30 MT/year plant decreased the manufacturing cost by nearly half from $\$$831 to $\$$379 in the case of PAN/OPSZ/NOHM, depicting the economies of scale of effect. An LCA of both types of solid sorbent was performed using OpenLCA software, the Ecoinvent v 3.5 database, and the TRACI LCI assessment method. The Global Warming Potential (GWP) ofPAN/OPSZ/NOHM and PIM/NOHM was observed to be 151 × 10 -3 and 166 × 10 -3 kg CO 2 per kg CO 2 captured in the DAC plant, respectively. In conclusion, these GWP values were nearly five times as high as those observed for other solid sorbents existing in the literature such as PEI on silica gel, carbonate on silica, and carbonate on activated carbon owing to large amounts of electricity used in electrospinning unit operation.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Carbon Fiber and Syntactic Foam Hybrid Materials via Core–Shell Material Extrusion Additive Manufacturing

Abstract Biological materials often employ hybrid architectures, such as the core–shell (C–S) motif present in porcupine quills and plant stems, to achieve unique specific properties and performance. Drawing inspiration from these natural materials, a new method to fabricate lightweight and stiff C–S architected filaments is reported. Specifically, a C–S printhead conducive to printing highly loaded fiber‐filled inks, as well as a new low‐density syntactic foam ink, are utilized to 3D‐print C–S architectures consisting of a syntactic epoxy foam core surrounded by a stiff carbon fiber‐reinforced epoxy composite shell. Effective printing of test specimens and structures with controlled geometry, composition, and architecture is demonstrated. The new foam ink exhibits density as low as 0.68 g cm −3 and C–S structures exhibit up to 25% higher specific flexural stiffness ( E 1/3 /ρ) than either constituent alone. Finally, a new mechanical model is presented to predict this performance improvement while accounting for potential eccentricity of the core.

Pack, Robert C.↗