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Results for “covalent functionalization”

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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Hydrogen irradiation-driven computational surface chemistry of lithium oxide and hydroxide

We have investigated, using molecular dynamics, the surface chemistry of hydrogen incident on the amorphous and crystalline lithium oxide and lithium hydroxide surfaces upon being slowed down by a collision cascade and retained in the amorphous surface of either Li 2 O or LiOH. We looked for the bonding of H to the resident structures in the surface to understand a possible chain of chemical reactions that can lead to surface transformation upon H atom impact. Our findings, using Density-Functional Theory (DFT) trained ReaxFF force field/electronegativity equalization method potentials, stress the importance of inclusion of polarization in the dynamics of a Li–O–H system, which is also illustrated by DFT energy minimization and quantum–classical molecular dynamics using tight binding DFT. The resulting polar-covalent chemistry of the studied systems is complex and very sensitive to the instantaneous positions of all atoms as well as the ratio of concentrations of various resident atoms in the surface.

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

Imaging elliptically polarized infrared near-fields on nanoparticles by strong-field dissociation of functional surface groups

Abstract We investigate the strong-field ion emission from the surface of isolated silica nanoparticles aerosolized from an alcoholic solution, and demonstrate the applicability of the recently reported near-field imaging at 720 nm [Rupp et al., Nat. Comm., 10(1):4655, 2019] to longer wavelength (2 $$\mu $$ μ m) and polarizations with arbitrary ellipticity. Based on the experimental observations, we discuss the validity of a previously introduced semi-classical model, which is based on near-field driven charge generation by a Monte-Carlo approach and classical propagation. We furthermore clarify the role of the solvent in the surface composition of the nanoparticles in the interaction region. We find that upon injection of the nanoparticles into the vacuum, the alcoholic solvent evaporates on millisecond time scales, and that the generated ions originate predominantly from covalent bonds with the silica surface rather than from physisorbed solvent molecules. These findings have important implications for the development of future theoretical models of the strong-field ion emission from silica nanoparticles, and the application of near-field imaging and reaction dynamics of functional groups on isolated nanoparticles. Graphical abstract

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Should I stay or should I flow? An exploration of phase‐separated metallosupramolecular liquid crystal polymers

Abstract Dynamic liquid crystalline polymers (dLCPs) incorporate both liquid crystalline mesogens and dynamic bonds into a single polymeric material. These dual functionalities impart order‐dependent thermo‐responsive mechano‐optical properties and enhanced reprocessability/programmability enabling their use as soft actuators, adaptive adhesives, and damping materials. While many previous works studying dynamic LCPs utilize dynamic covalent bonds, metallosupramolecular bonds provide a modular platform where a series of materials can be accessed from a single polymeric feedstock through the variation of the metal ion used. A series of dLCPs were prepared by the addition of metal salts to a telechelic 2,6‐bisbenzimidazolylpyridine (Bip) ligand endcapped LCP to form metallosupramolecular liquid crystal polymers (MSLCPs). The resulting MSLCPs were found to phase separate into hard and soft phases which aids in their mechanical robustness. Variations of the metal salts used to access these materials allowed for control of the thermomechanical, viscoelastic, and adhesive properties with relaxations that can be tailored independently of the mesogenic transition. This work demonstrates that by accessing phase separation through the incorporation of metallosupramolecular moieties, highly processable yet robust MSLCP materials can be realized. This class of materials opens the door to LCPs with bulk flow behavior that can also be utilized as multi‐level adhesives.

Chemistry↗
DOE OSTI2024

Towards predictive control of reversible nanoparticle assembly with solid-binding proteins

Although a broad range of ligand-functionalized nanoparticles and physico-chemical triggers have been exploited to create stimuli-responsive colloidal systems, little attention has been paid to the reversible assembly of unmodified nanoparticles with non-covalently bound proteins. Previously, we reported that a derivative of green fluorescent protein engineered with oppositely located silica-binding peptides mediates the repeated assembly and disassembly of 10-nm silica nanoparticles when pH is toggled between 7.5 and 8.5. We captured the subtle interplay between interparticle electrostatic repulsion and their protein-mediated short-range attraction with a multiscale model energetically benchmarked to collective system behavior captured by scattering experiments. Here, in this work, we show that both solution conditions (pH and ionic strength) and protein engineering (sequence and position of engineered silica-binding peptides) provide pathways for reversible control over growth and fragmentation, leading to clusters ranging in size from 25 nm protein-coated particles to micrometer-size aggregate. We further find that the higher electrolyte environment associated with successive cycles of base addition eventually eliminates reversibility. Our model accurately predicts these multiple length scales phenomena. The underpinning concepts provide design principles for the dynamic control of other protein- and particle-based nanocomposites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Breaking up CO 2 through pressure-induced redox reaction with rhenium

We present results from density-functional-theory (DFT) based molecular dynamics simulations of fluid mixtures of carbon dioxide (CO 2 ) and rhenium (Re) metal at pressures up to 45 GPa and a temperature of 4000 K. Covalently-bonded carbon chains form as a result of a redox reaction between CO 2 and Re, whereas a pure CO 2 fluid is stable against decomposition at the same conditions. Furthermore, these findings have implications in reducing CO 2 by pressure-induced redox reactions with transition metals, which may play a role in CO 2 destruction and carbon storage as related to possible solutions to the current climate crisis.

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

Tuning Photoexcited Charge Transfer in Imine-Linked Two-Dimensional Covalent Organic Frameworks

The generation of a long-lived charge-separated state in versatile π-conjugated two-dimensional covalent organic frameworks (2D COFs), a process essential to extending their great potentials in advanced semiconducting applications, is yet fully elucidated. Herein, we report a systematic investigation of the photophysical properties of three highly crystalline imine-linked 2D COFs using steady-state and transient absorption spectroscopy accompanied by time-dependent density functional theory (TDDFT) calculations. The different electron affinity between 5,5',5''-(1,3,5-benzenetriyl)-tris(2-pyridinecarboxaldehyde) (BTPA) and three tunable electron-donating/accepting triamine monomers dominated the formation of the excited state, charge transfer direction and lifetime. A prominent charge transfer from electron-rich 4,4',4''-triaminotriphenylamine (TAPA) to BTPA in COFTAPA-BTPA led to the long-lived charge-separated state, which was attributed to a greater degree of delocalization compared to the two other COFs. Furthermore, these results provide fundamental insight into the importance of structure-property correlation for designing advanced photoactive 2D COF materials with the efficient charge transfer and long-lived charge-separated state.

14 SOLAR ENERGY↗
DOE OSTI2021

Crystal Structure and Properties of Layered Pnictides BaCuSi2Pn3 (Pn = P, As)

Two novel layered compounds BaCuSi 2 Pn 3 (Pn = P, As) adopting new structure types are reported. As revealed by single-crystal X-ray diffraction, both compounds are composed of unique Cu–Si–Pn layers featuring CuPn 3 and Si 2 Pn 6 structural motifs found in other archetypal pnictide materials. The stacking of the isostructural Cu–Si–Pn layers is different for phosphide and arsenide compounds. Synthesis from elements aided by in situ synchrotron powder X-ray diffraction resulted in the obtainment of bulk powders with a minimized amount of admixtures. Experimentally measured physical properties of BaCuSi 2 As 3 unexpectedly showed metal-like behavior at temperatures above 15 K, despite the fact that density functional theory calculations predict a small band gap of 0.4 eV. BaCuSi 2 As 3 exhibits ultralow thermal conductivity, which can be explained by the combination of a layered crystal structure with alternating covalent and ionic bonding, which feature rattling of Cu atoms similar to that in tetrahedrites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Harnessing the Spin-Flip Radiative Lifetimes of Optically Addressable Molecular Qubits

Optically addressable molecular qubits based on spin-flip (SF) emissive transitions are promising candidates for quantum technologies due to their sharp luminescence lines and tunable optical-spin interfaces. Yet, the microscopic mechanisms controlling the spin-flip radiative lifetime of SF emitters, a key property for efficient spin readout, remain largely unexplored. Here, we present a computational study of several Cr 4+ and Mo 4+ pseudotetrahedral molecular qubits, and we identify chemical and structural features that influence the transition dipole moment associated with the SF emission, which, in turn, governs the SF radiative lifetime. We find that the magnitude of the dipole moment is governed by the multireference character of the spin-flip excited-state wave function, which can be modulated by tuning the energy separation between the d orbitals of the metal and the spin-pairing energy. Both parameters are sensitive to molecular symmetry, metal–ligand bond covalency, and bond anisotropy and leave room for modulation via ligand and metal design, as well as applied strain, which is relevant for sensing applications. Our findings provide a mechanistic framework for understanding and tuning the spin-flip radiative behavior of molecular qubits and SF emitters that may guide future advances in quantum information science.

molecular qubits↗
DOE OSTI2023

Effects of surface acidity on the structure of organometallics supported on oxide surfaces

Well-defined organometallics supported on high surface area oxides are promising heterogeneous catalysts. An important design factor in these materials is how the metal interacts with the functionalities on an oxide support, commonly anionic X-type ligands derived from the reaction of an organometallic M–R with an –OH site on the oxide. The metal can either form a covalent M–O bond or form an electrostatic M + $\cdots$ – O ion-pair, which impacts how well-defined organometallics will interact with substrates in catalytic reactions. However, a less common reaction pathway involves the reaction of a Lewis site on the oxide with the organometallic, resulting in abstraction to form an ion-pair, which is relevant to industrial olefin polymerization catalysts. This Feature Article views the spectrum of reactivity between an organometallic and an oxide through the prism of Brønsted and/or Lewis acidity of surface sites and draws analogies to the molecular frame where Lewis and Brønsted acids are known to form reactive ion-pairs. Applications of the well-defined sites developed in this article are also discussed.

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

A Porous Crystalline Nitrone‐Linked Covalent Organic Framework**

Abstract Herein, we report the synthesis of a nitrone‐linked covalent organic framework, COF‐115, by combining N , N′ , N′ , N ′′′‐(ethene‐1, 1, 2, 2‐tetrayltetrakis(benzene‐4, 1‐diyl))tetrakis(hydroxylamine) and terephthaladehyde via a polycondensation reaction. The formation of the nitrone functionality was confirmed by solid‐state 13 C multi cross‐polarization magic angle spinning NMR spectroscopy of the 13 C‐isotope‐labeled COF‐115 and Fourier‐transform infrared spectroscopy. The permanent porosity of COF‐115 was evaluated through low‐pressure N 2 , CO 2 , and H 2 sorption experiments. Water vapor and carbon dioxide sorption analysis of COF‐115 and the isoreticular imine‐linked COF indicated a superior potential of N ‐oxide‐based porous materials for atmospheric water harvesting and CO 2 capture applications. Density functional theory calculations provided valuable insights into the difference between the adsorption properties of these COFs. Lastly, photoinduced rearrangement of COF‐115 to the associated amide‐linked material was successfully demonstrated.

Kurandina, Daria↗
DOE OSTI2021

Mixed matrix membranes for post-combustion carbon capture: From materials design to membrane engineering

Mixed matrix materials (MMMs) containing nanofillers dispersed in continuous polymer matrices have emerged as an exciting and versatile platform to develop membranes with superior CO 2 /N 2 separation performance for post-combustion carbon capture. Both polymers and nanofillers can be vertically designed and engineered to combine the advantages of excellent processability (derived from polymers) and strong size-sieving ability or/and significant permanent porosity (originated from nanofillers). However, the MMMs face major challenges, such as interfacial incompatibility, particle agglomeration, and poor thin-film formability. This report provides a comprehensive yet critical review of various polymers and nanofillers (such as metal-organic frameworks, covalent organic frameworks, and two-dimensional materials) with promising CO 2 /N 2 separation properties. We exhaustively describe strategies to improve interfacial compatibility, such as in situ syntheses of polymers and nanofillers and functionalization of both components to improve adhesion. Moreover, we highlight various approaches to engineer the MMMs into thin-film composite (TFC) membranes. The review reveals the structure/property relationship in these MMMs and outlines the challenges and opportunities to realize their potential for practical applications.

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

Small molecule microarray identifies inhibitors of tyrosyl-DNA phosphodiesterase 1 that simultaneously access the catalytic pocket and two substrate binding sites

Tyrosyl-DNA phosphodiesterase 1 (TDP1) is a member of the phospholipase D family of enzymes, which catalyzes the removal of both 3'- and 5'-DNA phosphodiester adducts. Importantly, it is capable of reducing the anticancer effects of type I topoisomerase (TOP1) inhibitors by repairing the stalled covalent complexes of TOP1 with DNA. It achieves this by promoting the hydrolysis of the phosphodiester bond between the Y723 residue of human TOP1 and the 3'-phosphate of its DNA substrate. Blocking TDP1 function is an attractive means of enhancing the efficacy of TOP1 inhibitors and overcoming drug resistance. Previously, we reported the use of an X-ray crystallographic screen of more than 600 fragments to identify small molecule variations on phthalic acid and hydroxyquinoline motifs that bind within the TDP1 catalytic pocket. Yet, the majority of these compounds showed limited (millimolar) TDP1 inhibitory potencies. We now report examining a 21 000-member library of drug-like Small Molecules in Microarray (SMM) format for their ability to bind Alexa Fluor 647 (AF647)-labeled TDP1. The screen identified structurally similar N,2-diphenylimidazo[1,2-a]pyrazin-3-amines as TDP1 binders and catalytic inhibitors. We then explored the core heterocycle skeleton using one-pot Groebke–Blackburn–Bienayme multicomponent reactions and arrived at analogs having higher inhibitory potencies. Solving TDP1 co-crystal structures of a subset of compounds showed their binding at the TDP1 catalytic site, while mimicking substrate interactions. Although our original fragment screen differed significantly from the current microarray protocol, both methods identified ligand–protein interactions containing highly similar elements. Importantly inhibitors identified through the SMM approach show competitive inhibition against TDP1 and access the catalytic phosphate-binding pocket, while simultaneously providing extensions into both the substrate DNA and peptide-binding channels. As such, they represent a platform for further elaboration of trivalent ligands, that could serve as a new genre of potent TDP1 inhibitors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Accurate Electron-Phonon Interactions from Advanced Density Functional Theory

Electron-phonon coupling (EPC) is key to understanding charge transport, band renormalization, and superconductivity in energy materials, including correlated transition-metal oxides, ferroelectric perovskites, optoelectronic semiconductors, and phonon-mediated superconductors. Although first-principles density functional theory (DFT)-based EPC calculations are used widely, their predictive power is limited by the accuracy, transferability, and efficiency of the underlying exchange-correlation functionals. These limitations become exacerbated in complex 𝑑- and 𝑓-electron materials, where beyond-DFT approaches and additional corrections, such as the Hubbard 𝑈, are commonly invoked. Here, using the examples of Co⁢O and Ni⁢O, we show how the 𝑟 2 SCAN density functional correctly captures strong EPC effects in transition-metal oxides without requiring the introduction of Hubbard 𝑈 parameters. We also find that 𝑟 2 SCAN successfully describes the subtle interplay between ionic and covalent bonding, and strong EPC effects in the low-temperature rhombohedral phase of the prototypical ferroelectric Ba⁢Ti⁢O 3 , without requiring Hubbard 𝑈 and intersite 𝑉 corrections. We further demonstrate the ability of 𝑟 2 SCAN to accurately model the EPC of the main-group semiconductor Ga⁢As and the phonon-mediated superconducting properties of Mg⁢B 2 , with reliable electronic bands and phonons. Our study establishes 𝑟 2 SCAN-based EPC as a transferable, parameter-free, and computationally efficient framework for predictive material-specific modeling of EPC in energy materials, and opens a practical route toward high-throughput screening of superconductors, thermoelectrics, optoelectronic semiconductors, and oxide electrodes and catalysts.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Self-Assembly Interactions in Magnetite-Coated Cellulose Nanocrystals: Implications for Magnetic Hyperthermia Applications

Magnetic cellulose nanocrystal (MCNC) nanocomposites are promising sustainable and biocompatible platforms for magnetic hyperthermia; however, the molecular mechanisms governing Fe 3 O 4 adsorption and deposition onto CNCs remain poorly understood. Here, sulfated (S-CNC) and TEMPO-oxidized CNCs (T-CNC) were used to prepare nanocomposites at 1:2 and 1:4 CNC:Fe 3 O 4 mass ratios, enabling a systematic evaluation of how surface chemistry and nanoparticle loading dictate interfacial interactions and magneto-colloidal behavior. Bare magnetite nanoparticles were 21 ± 5 nm by TEM but grew to 144 ± 18 in the DLS measurement at pH 7. The S-CNC nanocomposites had hydrodynamic sizes between 144 and 210 nm, not much larger than the 140 nm long CNC rods, suggesting an enhanced dispersion stability compared to Fe3O4 alone. X-ray photoelectron spectroscopy combined with density functional theory revealed that −OH and −COOH groups drive electrostatic adsorption with charge transfer from Fe 3 O 4 to the CNC surface, while T-CNCs showed more favorable adsorption energies and evidence of covalent Fe−O bonding. Vibrating sample magnetometry demonstrated superparamagnetic behavior for all samples, with S-CNC/Fe 3 O 4 1:4 and 1:2 displaying saturation magnetizations of 78 and 77 emu/g-Fe 3 O 4 , close to the 83 emu/g of bare magnetite. The T-CNC composites showed lower (60 and 66 emu/g-Fe3O4) saturation magnetizations. Zero-field-cooled/field-cooled measurements resulted in a blocking temperature of 112 K for all samples, except T-CNC/Fe 3 O 4 1:2 (100 K). Magnetic hyperthermia studies revealed that specific absorption rate (SAR) increased with field strength and Fe 3 O 4 content; however, S-CNC/Fe 3 O 4 (1:2) achieved the highest intrinsic SAR per gram of Fe 3 O 4 (649 W/g-Fe 3 O 4 ) likely due to its anisotropy and fast magnetic relaxation. Cytotoxicity assays confirmed that all nanocomposites were nontoxic toward mammalian cells. These results establish quantitative structure−property relationships between CNC surface chemistry, interfacial bonding mechanisms, and magnetic heating performance, providing a foundation for rational design of biocompatible magnetic nanocomposites for hyperthermia and related applications.

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

Electrocatalytic water oxidation performance in an extended porous organic framework with a covalent alliance of distinct Ru sites

The rational synthesis of durable, earth-abundant efficient electrocatalysts for the oxygen evolution reaction (OER) from water is one of the most important routes for storing renewable energy and minimizing fossil fuel combustion. The prime hurdles for effectively utilizing commercial RuO 2 as (OER) electrocatalysts are its very low stability, catalyst deactivation, and high cost. In this work, we explored a Ru-integrated porous organic polymer (Ru@Bpy-POP) by a facile one-pot Friedel–Crafts alkylation strategy between redox-active (Ru(demob) 3 Cl 2 ) and a carbazole unit, which is composed of unique features including an extended framework unit, isolated active sites, and tunable electrode kinetics. Ru@Bpy-POP can serve as a bridge between a Metal–Organic Framework (MOF) and POP-based catalytic systems with a balanced combination of covalent bonds (structural stability) and open metal sites (single site catalysis). Ru@Bpy-POP, deposited on a three-dimensional nickel foam electrode support, exhibits a promising electrocatalytic OER activity with an ultra-low ruthenium loading compared to a benchmark RuO 2 catalyst, providing an overpotential of about 270 mV to reach 10 mA cm –2 in an alkaline medium. Moreover, a high current density of 248 mA cm –2 was achieved for the Ru@Bpy-POP catalyst at only 1.6 V (vs. RHE), which is much higher than 91 mA cm –2 for commercial RuO 2 . The robust, albeit highly conjugated, POP framework not only triggered facile electro-kinetics but also suppressed aggregation and metallic corrosion during electrolysis. In particular, the benefits of covalent integration of distinct Ru sites into the framework can modulate intermediate adsorption and charge density, which contributes to its exceptional OER activity. All of the critical steps involved in OER are complemented by Density Functional Theory (DFT) calculations, which suggest that electrocatalytic water oxidation proceeds from a closed-shell configuration to open-shell electronic configurations with high-spin states. Finally, these open-shell configurations are more stable than their closed-shell counterparts by 1 eV, improving the overall catalytic activity.

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

Method and composition for targeted delivery of therapeutic agents

Functionalized single walled or multi-walled carbon nanotubes (f-CNTs) can be delivered into mammals to targeted organs, such as the kidney and the liver. These f-CNTs may be non-covalently linked or covalently linked to therapeutic agents. In particular, the application delivers carbon nanotube-therapeutic agent conjugates to a target organ, thereby preventing or reducing damages to the organ caused by other agents or procedure.

McDevitt, Michael R.↗
DOE OSTI2025

Electrochemical CO 2 Capture by a Quinone-Based Covalent Organic Framework

Electrochemical CO 2 capture is an emerging technology that promises to be more energy-efficient than traditional thermal or pressure-swing processes. Herein, the first evidence of electrochemical capture of CO 2 using a covalent organic framework (COF) is presented. We hypothesized that the assembly of anthraquinone units into a well-defined porous framework electrode would lead to enhanced electrochemical CO 2 capture compared to previous approaches that grafted anthraquinones on carbon supports and suffered from low CO 2 capacities and stabilities. To test this, an anthraquinone-based COF is employed, and it is found that the quinones are electrochemically accessible for reversible CO 2 capture in an ionic liquid electrolyte. The system achieves a high electrochemical CO 2 uptake capacity >2.6 mmol g –1 COF, reaching half of the theoretical CO 2 capacity of the material and surpassing the capacities of anthraquinone-functionalized carbons. The stability and CO 2 uptake rate issues encountered with the ionic liquid system are also addressed by using aqueous electrolytes where we attained stable carbon capture for 500 cycles with a 99.6% Coulombic efficiency and an electrical energy consumption of 31 kJ mol CO 2 –1 . The use of covalent organic framework electrodes can become a general strategy for understanding and enhancing the electrochemical CO 2 capture.

carbon capture and storage↗
DOE OSTI2024

Synthesis and characterization of low-dimensional N-heterocyclic carbene lattices

The covalent interaction of N-heterocyclic carbenes (NHCs) with transition metal atoms gives rise to distinctive frontier molecular orbitals (FMOs). These emergent electronic states have spurred the widespread adoption of NHC ligands in chemical catalysis and functional materials. Although formation of carbene-metal complexes in self-assembled monolayers on surfaces has been explored, design and electronic structure characterization of extended low-dimensional NHC-metal lattices remains elusive. Here, in this work, we demonstrate a modular approach to engineering one-dimensional (1D) metal-organic chains and two-dimensional (2D) Kagome lattices using the FMOs of NHC–Au–NHC junctions to create low-dimensional molecular networks exhibiting intrinsic metallicity. Scanning tunneling spectroscopy and first-principles density functional theory reveal the contribution of C–Au–C π-bonding states to dispersive bands that imbue 1D- and 2D-NHC lattices with exceptionally small work functions.

Qie, Boyu↗