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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 163 records · Page 9

High-throughput screening of tribological properties of monolayer films using molecular dynamics and machine learning

Monolayer films have shown promise as a lubricating layer to reduce friction and wear of mechanical devices with separations on the nanoscale. These films have a vast design space with many tunable properties that can affect their tribological effectiveness. For example, terminal group chemistry, film composition, and backbone chemistry can all lead to films with significantly different tribological properties. This design space, however, is very difficult to explore without a combinatorial approach and an automatable, reproducible, and extensible workflow to screen for promising candidate films. Here, using the Molecular Simulation Design Framework (MoSDeF), a combinatorial screening study was performed to explore 9747 unique monolayer films (116 964 total simulations) and a machine learning (ML) model using a random forest regressor, an ensemble learning technique, to explore the role of terminal group chemistry and its effect on tribological effectiveness. The most promising films were found to contain small terminal groups such as cyano and ethylene. The ML model was subsequently applied to screen terminal group candidates identified from the ChEMBL small molecule library. Approximately 193 131 unique film candidates were screened with approximately a five order of magnitude speed-up in analysis compared to simulation alone. The ML model was thus able to be used as a predictive tool to greatly speed up the initial screening of promising candidate films for future simulation studies, suggesting that computational screening in combination with ML can greatly increase the throughput in combinatorial approaches to generate in silico data and then train ML models in a controlled, self-consistent fashion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalyst design for small molecule activation of energy consequence

This project targets the conversion of ubiquitous small molecules (e.g. NO, CO, H 2 O) into viable precursors to synthetic fuels. Current state of the art catalyst design has not directly targeted transition metal complexes capable of mediating the multi-electron redox processes necessary to reduce the overpotential (energy loss) required achieve efficient activation of small molecule substrates. In this vein, a new strategy has been developed for the assembly of polynuclear architectures; allowing for the construction of tunable polymetallic centers that assemble easily within a pre-organized template (conferring stability, selectivity and tunability) that can effect multi-electron redox processes for reactions. Catalyst development has commenced with the following target design elements: (1) catalysts featuring multiple transition metal ions in the same reaction space to greatly expand accessible molecular redox capabilities; (2) catalysts are assembled in a polynucleating ligand framework that permits control over the cluster morphology as well as the local steric and electronic environment of the transition metal ions within the cluster. The high-tunability of the catalyst composition (metal content) and geometric flexibility has permitted a rigorous assessment of electronic-structure-to-function relationship to be developed, further guiding synthetic efforts to realize more potent catalysts. The numerous permutations possible showcase the high degree of generality to this approach with many synthetic handles to tune redox and reaction chemistry. Trinuclear complexes have been synthesized featuring homo- and hetero-trinuclear cores featuring a variety of first row transition metal ions (Cr→Ni). The molecular clusters have been shown to successfully mediate multi-electron redox processes in a cooperative fashion without requiring strong chemical reductants or oxidants. The reactive molecular complexes are being utilized to activate and breakdown the robust bonds within typical waste stream small molecules (e.g., greenhouse gases) and convert them into value-added commodity chemicals. Ultimately, the catalysts developed by this approach will be required to convert energy acquired via renewable resources (e.g., solar or wind) into synthetic fuels as an energy storage mechanism.

10 SYNTHETIC FUELS↗

Bimetallic Metal–Organic Framework Fe/Co-MIL-88(NH 2 ) Exhibiting High Peroxidase-like Activity and Its Application in Detection of Extracellular Vesicles

Metal–organic frameworks (MOFs) have many attractive features, including tunable composition, rigid structure, controllable pore size, and large specific surface area, and thus are highly applicable in molecular analysis. Depending on the MOF structure, a high number of un-saturated metal sites can be exposed to catalyze chemical reactions. In the present work, we report that by using both Co(II) and Fe(III) to prepare the MIL-88(NH 2 ) MOF, we can produce the bimetallic MOF that can catalyze the conversion of 3,3', 5,5"-tetramethylbenzidine (TMB) to a color product through reaction with H 2 O 2 at a higher reaction rate than the monometallic Fe-MIL-88(NH 2 ). The Michaelis constants (K m ) of the catalytic reaction for TMB and H 2 O 2 are 3-5 times smaller, and the catalytic constants (k cat ) are 5-10 times higher than those of the horse-radish peroxidase (HRP), supporting ultrahigh peroxidase-like activity. These values are also much more superior to those of the HRP-mimicking MOFs reported previously. Interestingly, the bimetallic MOF can be coupled with glucose oxidase (GOx) to trigger the cascade enzymatic reaction for highly sensitive detection of extracellular vesicles (EVs), a family of important biomarkers. Through conjugation to the aptamer that recognizes the marker protein on EV surface, the MOF can help isolate the EVs from biological matrices, which are subsequently labeled by GOx via antibody recognition. The cascade enzymatic reaction between MOF and GOx enables detection of EVs at a concentration as low as 7.8 × 10 4 particles/ml. Further, the assay can be applied to monitor EV secretion by cultured cells, and also can successfully detect the different EV quantities in the sera samples collected from cancer patients and healthy controls. Overall, we prove that the bimetallic Fe/Co-MIL-88(NH 2 ) MOF, with its high peroxidase-activity and high biocompatibility, is a valuable tool deployable in clinical assays to facility disease diagnosis and prognosis.

36 MATERIALS SCIENCE↗

A Sustainable Multi-Dimensional Printable Material

Polymeric materials are usually tailored for specific functionality. A single polymer exhibiting multiple simultaneous functionalities often requires intricate molecular architecture, which is difficult to manufacture at scale because of its complex synthesis routes. In this work, a facile, partly renewable composition—prepared via reactive melt processing—that induces tunable functionalities such as 3D printability, shape recovery, and self-healing while exhibiting satisfactory mechanical properties is reported. The system with a hydrogen-bonded 3D network consists of thermally reversible nano-scale agglomerates of sustainable, rigid phenolic oligomers and crystallizable flexible polymer. Local molecular mobility and temperature-dependent relaxation and recovery of the non-equilibrium networked states enable exploiting these simultaneous functionalities. Transitions involving solidification and structure stabilization at ambient temperature spanning several hours after preheating only at 70 °C directly contrast typical thermoplastic or thermoplastic elastomer behaviors. Results from this study can inform the design of future rheology modifiers and materials for soft robotics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Covalent Functionalization of Silicon with Plasma-Grown “Fuzzy” Graphene: Robust Aqueous Photoelectrodes for CO 2 Reduction by Molecular Catalysts

Carbon electrodes are ideal for electrochemistry with molecular catalysts, exhibiting facile charge transfer and good stability. Yet for solar-driven catalysis with semiconductor light absorbers, stable semiconductor/carbon interfaces can be difficult to achieve, and carbon’s high optical extinction means it can only be used in ultrathin layers. Here, we demonstrate a plasma-enhanced chemical vapor deposition process that achieves well-controlled deposition of out-of-plane “fuzzy” graphene (FG) on thermally oxidized Si substrates. The resulting Si|FG interfaces possess a silicon oxycarbide (SiOC) interfacial layer, implying covalent bonding between Si and the FG film that is consistent with the mechanical robustness observed from the films. The FG layer is uniform and tunable in thickness and optical transparency by deposition time. Using p-type Si|FG substrates, noncovalent immobilization of cobalt phthalocyanine (CoPc) molecular catalysts was employed for the photoelectrochemical reduction of CO 2 in aqueous solution. The Si|FG|CoPc photocathodes exhibited good catalytic activity, yielding a current density of ∼1 mA/cm 2 , Faradaic efficiency for CO of ∼70% (balance H 2 ), and stable photocurrent for at least 30 h at −1.5 V vs Ag/AgCl under 1-sun illumination. Furthermore, the results suggest that plasma-deposited FG is a robust carbon electrode for molecular catalysts and suitable for further development of aqueous-stable Si photocathodes for CO 2 reduction.

CO2 reduction↗

A high-resolution molecular spin-photon interface at telecommunication wavelengths

Optically addressable electronic spins in polyatomic molecules are a promising platform for quantum information science, with the potential to enable scalable qubit design and integration through atomistic tunability and nanoscale localization. However, optical state- and site-selection are an open challenge. Here, in this work, we introduce an organo-erbium spin qubit in which narrow (megahertz-scale) optical and spin transitions couple to provide high-resolution access to spin degrees of freedom with telecommunication-frequency light. This spin-photon interface enables demonstration of optical spin polarization and readout that distinguishes between spin states and magnetically inequivalent sites in a molecular crystal. Operation at frequencies compatible with mature photonic and microwave devices provides an opportunity for engineering scalable, integrated molecular spin-optical quantum technologies.

Weiss, Leah R. [University of Chicago, IL (United ↗

Proton-controlled molecular ionic ferroelectrics

Abstract Molecular ferroelectric materials consist of organic and inorganic ions held together by hydrogen bonds, electrostatic forces, and van der Waals interactions. However, ionically tailored multifunctionality in molecular ferroelectrics has been a missing component despite of their peculiar stimuli-responsive structure and building blocks. Here we report molecular ionic ferroelectrics exhibiting the coexistence of room-temperature ionic conductivity (6.1 × 10 −5 S/cm) and ferroelectricity, which triggers the ionic-coupled ferroelectric properties. Such ionic ferroelectrics with the absorbed water molecules further present the controlled tunability in polarization from 0.68 to 1.39 μC/cm 2 , thermal conductivity by 13% and electrical resistivity by 86% due to the proton transfer in an ionic lattice under external stimuli. These findings enlighten the development of molecular ionic ferroelectrics towards multifunctionality.

42 ENGINEERING↗

High-resolution vibrational predissociation spectroscopy of I - ·H 2 O by single-mode CW infrared excitation in a 3D cryogenic ion trap

We describe the integration of a tunable, single-mode, continuous wave infrared laser into a cryogenic ion spectroscopy experiment to measure the rovibrational spectrum of the I - ∙H 2 O complex in the OH stretching region. These upper levels lie about 300 cm -1 above the dissociation threshold. The measurements are carried out by loading the ions in a radiofrequency ion trap at 10 Hz and cooling them to 5 K with pulsed He buffer gas. IR photodissociation (PD) of the I - ∙H 2 O complex is monitored by recording the I - product yield by time-of-flight mass spectrometry as a function of laser wavelength. Very narrow (Δν~75 MHz) rotational lines are observed throughout the spectrum, indicating long (ca. 2 ns) lifetimes for the excited metastable rovibrational levels. Rotational analysis of the band arising from the K”=1 to K’=2 transition of the free OH stretching fundamental yields the structure of the complex for the first time. Over 50% of the trapped ion ensemble in the trap can be photodissociated upon excitation of a single rotational line. This enables very high signal-to-noise in the PD spectrum, and is traced to a mechanism in which the ground state rotational levels are rapidly equilibrated by collisions with the buffer gas.

74 ATOMIC AND MOLECULAR PHYSICS↗

2D Covalent Organic Frameworks with an Incorporated Manganese Complex for Light Driven Carbon Dioxide Reduction

Covalent organic frameworks (COFs) have emerged as a novel class of crystalline porous photocatalytic materials due to their unique properties such as large surface area, tunable porosity, and rigid structure. Here in this work, we report the direct incorporation of a manganese CO 2 molecular catalyst (MC) into COFs (Mn-TTA-COF) and the evaluation of its capability as photocatalyst for visible light driven CO 2 reduction to form CO. We found that the photocatalytic activity of Mn-TTA-COF is quite low, which mainly results from the elimination of the CO ligand in the Mn MC upon light illumination, rendering its short duration in the catalytic reaction. While this is a central concern for the further use Mn-TTA-COF as a CO 2 reduction catalyst, here we found that the stability and efficiency of Mn MC is largely enhanced after being incorporated into COFs with respect to its homogeneous version, suggesting the capability of COFs as heterogeneous platform to incorporate MC and improve the catalytic performance of MC. Moreover, transient absorption spectroscopic studies show that the intramolecular charge transfer lifetime of the Mn-incorporated COF is longer than that in the parent COF, which suggests that charge separation (CS) may occur from the parent COF to the Mn moiety. These results together suggest that COFs may show promise as a platform for creating next-generation photocatalysts with a built-in photosensitizer and MC, which can facilitate CS and enhance the stability and efficiency of the incorporated MC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithiating magneto-ionics in a rechargeable battery

Magneto-ionics, real-time ionic control of magnetism in solid-state materials, promise ultralow-power memory, computing, and ultralow-field sensor technologies. The real-time ion intercalation is also the key state-of-charge feature in rechargeable batteries. Here, we report that the reversible lithiation/delithiation in molecular magneto-ionic material, the cathode in a rechargeable lithium-ion battery, accurately monitors its real-time state of charge through a dynamic tunability of magnetic ordering. The electrochemical and magnetic studies confirm that the structural vacancy and hydrogen-bonding networks enable reversible lithiation and delithiation in the magnetic cathode. Coupling with microwave-excited spin wave at a low frequency (0.35 GHz) and a magnetic field of 100 Oe, we reveal a fast and reliable built-in magneto-ionic sensor monitoring state of charge in rechargeable batteries. The findings shown herein promise an integration of molecular magneto-ionic cathode and rechargeable batteries for real-time monitoring of state of charge.

36 MATERIALS SCIENCE↗

Microcavity-Modified Emission from Rare-Earth Ion-Based Molecular Complexes

Despite the remarkable optical properties of rare-earth ion materials, their applications as light sources and in quantum technologies are often hindered by their long lifetimes and weak emission. Leveraging the natural compatibility of rare-earth ion molecular complexes with photonic structures, here we modify their photoluminescence properties by coupling them to a flexible open Fabry-Perot cavity. The full in situ tunability of the Fabry-Perot cavity allows fine control over its cavity modes and the achievement of resonant coupling between the rare-earth ion emission and the cavity modes. This configuration allows us to achieve a maximum photoluminescence enhancement factor of 30 and accelerate the decay rate up to two orders of magnitude. Our pump-power-dependent spectroscopic studies of the emitter-cavity system suggest that the cavity-modified emission is primarily caused by amplified spontaneous emission. These results suggest that integrating rare-earth ion molecular complexes with photonic structures could be a viable approach for the effective tuning of their optical properties. This natural compatibility, together with their versatile molecular structures and the resultant electronic states, renders rare-earth ion molecular complexes a potential alternative material platform for lighting and quantum applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Review: PFAS Adsorption, Sensing, and Remediation with Engineered Nanoporous Materials

Per- and polyfluoroalkyl substances (PFAS) are among the most abundant environmental contaminant species. They are widespread due to uncontrolled industrial and commercial use and have been linked to health risks such as cancer. With rising global concerns about the public health effects of PFAS, there is an incentive to develop strategies for reliable monitoring and effective PFAS removal, particularly in drinking water. Traditional PFAS sensing techniques are inefficient due to long measurement times, high labor input, high costs, and limitations to ex situ analysis. Current commercially available sorbents for PFAS removal generally lack the ability to capture PFAS components rapidly and quantitatively. Furthermore, existing sorbents are notably inefficient in removing the more toxic, smaller PFAS chemical chains. Large-scale applications of these methods tend to be costly and resource-intensive. Pacific Northwest National Laboratory has developed unique strategies for PFAS sensing and removal with capture probe technology that has an affinity for fluorocarbons, including PFAS. For both sensing and removal, the customizable capture probes can target specific PFAS compounds since they used a metal-organic framework (MOF)-based technology that can be fine-tuned and molecularly tailored. This tailoring of the materials enables high PFAS sensitivity, selectivity, and faster uptake. PNNL’s capture probe materials have been developed into a sensing technique based on the interactions of the capture probes with PFAS at the molecular level and further transduced that to a quantifiable electrochemical response. The materials have been integrated into a sensor platform developed by New Jersey Institute of Technology (NJIT). Tunable capture probes with a range of detection sensitivities allow for faster and more sensitive PFAS detection limits as low as what appears to be 0.5 ng/L (compared to the U.S. Environmental Protection Agency health advisory level of 70 ng/L). Customization of the capture probe results in improved sorption capacities (fast kinetics and high capacities) compared to commercial granular activated carbons. This research applied various experimental and modeling tools to improve understanding the molecular level interactions between the sorbents towards PFAS adsorption properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radically Tunable n-Type Organic Semiconductor via Polymorph Control

Polymorphism has emerged as an important design consideration in organic semiconductors (OSCs). Previously, in many OSCs, even small changes in molecular stacking can cause drastic changes to the optical and electronic properties. However, investigation into n-type semiconductors has significantly lagged behind their p-type counterparts. In this work, we present the prolific polymorphism of 2-dimensional quinoidal terthiophene (2DQTT-o-B) and systematically investigate each of 5 polymorphs, 3 of which have been previously unreported. Grazing incidence X-ray diffraction provided a key method to understanding the structure of each polymorph. Via the polymorphic transitions mapped, we tuned the electron mobility by 5 orders of magnitude, from 5.63 × 10 –5 to 0.22 cm 2 V –1 s –1 . These were accompanied by modifications to the optical properties, namely we observed substantial differences in the refractive index noted by intensity differences under polarized optical microscopy and a large shift in optical band gap from 1.18 eV up to 1.40 eV. Lastly, we suggest that changes to these properties may be related to the unique quinoidal to aromatic transition observed in quinoidal molecules.

36 MATERIALS SCIENCE↗

Nematoelasticity of hybrid molecular-colloidal liquid crystals

Colloidal rods immersed in a thermotropic liquid-crystalline solvent are at the basis of so-called hybrid liquid crystals, which are characterized by tunable nematic fluidity with symmetries ranging from conventional uniaxial nematic or antinematic to orthorhombic. Here, we provide a theoretical analysis of the elastic moduli of such systems by considering interactions between the individual rods with the embedding solvent through surface-anchoring forces, as well as steric and electrostatic interactions between the rods themselves. For uniaxial systems, the presence of colloidal rods generates a marked increase of the splay elasticity, which we found to be in quantitative agreement with experimental measurements. For orthorhombic hybrid liquid crystals, we provide estimates of all 12 elastic moduli and show that only a small subset of those elastic constants play a relevant role in describing the nematoelastic properties. The complexity and possibilities related to identifying the elastic moduli in experiments are briefly discussed.

42 ENGINEERING↗

Electrolyte Engineering Stabilizes Photoanodes Decorated with Molecular Catalysts

Molecular catalysts are promising oxygen evolution promoters in conjunction with photoanodes for solar water splitting. Maintaining the stability of both photoabsorber and cocatalyst is still a prime challenge, with many efforts tackling this issue through sophisticated material designs. Such approaches often mask the importance of the electrode-electrolyte interface and overlook easily tunable system parameters, such as the electrolyte environment, to improve efficiency. We provide a systematic study on the activity-stability relationship of a prominent Fe 2 O 3 photoanode modified with Ir molecular catalysts using in situ mass spectroscopy. After gaining detailed insights into the dissolution behavior of the Ir cocatalyst, a comprehensive pH study is conducted to probe the impact of the electrolyte on the performance. An inverse trend in Fe and Ir stability is found, with the best activity-stability synergy obtained at pH 9.7. The results bring awareness to the overall photostability and electrolyte engineering when advancing catalysts for solar water splitting.

14 SOLAR ENERGY↗

Tunable Mid-Infrared Interband Emission from Tensile-Strained InGaAs Quantum Dots

We demonstrate the ability to tailor self-assembled growth of In 0.5 Ga 0.5 As quantum dots (QDs) on GaSb(111)A surfaces by molecular beam epitaxy. Spontaneous formation via the Volmer–Weber growth mode produces QDs with excellent structural and optical quality. By harnessing tensile strain to reduce their band gap energy, these QDs are characterized by light emission that extends into the midwave infrared wavelength range of 3.2–3.9 μm (0.318–0.388 eV). As we increase QD size, we can tune the band alignment from type-III to type-II, where light emission occurs due to interband recombination between quantum confined electrons in the InGaAs QDs and holes in the GaSb barriers. Of particular interest is an unusual blue-shift in emission wavelength with increasing QD size, which we attribute to the incorporation of Sb into the InGaAs QDs from the GaSb barriers. By expanding this approach to produce tensile-strained QDs from other narrow band gap semiconductors, we anticipate the development of a range of highly tunable mid-infrared light sources.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large-area nanostructured surfaces with tunable zeta potentials

Through a refined fabrication protocol based on block-copolymer self-assembly we synthesize nanostructured surfaces with conical nanopillars of different height (60, 120, and 200 nm) in hexagonal arrays with uniform spacing (~50 nm) over large areas (>cm 2 ). While the nanostructured surfaces fabricated on silicon substrates display superhydrophilic behavior, superhydrophobic properties are attained by coating with octadecyltrichlorosilane (OTS). Negative zeta potentials for all the studied surfaces are reported by electrokinetic flow measurements with aqueous KCl solutions at different concentrations (1 and 10 mM) and pH values between 4 and 8. While the surface nanostructure reduces the zeta potential magnitude, the hydrophobic OTS coating enhances it. Experimental results can be accounted for by a site-dissociation model for the surface charge density. The reported wetting properties and zeta potential tunability makes the studied surfaces particularly relevant for applications such as energy conversion and storage, membrane-based water treatment and molecular separation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Highly Stable Fe/Co-TPY-MIL-88(NH 2 ) Metal–Organic Framework (MOF) in Enzymatic Cascade Reactions for Chemiluminescence-Based Detection of Extracellular Vesicles

Metal-Organic Frameworks (MOFs) can deliver many advantages when acting as enzyme mimics to assist with signal amplification in molecular detection: they have abundant active catalytic sites per unit volume of the material; their structures and elemental compositions are highly tunable, and their high specific surface area and porous property can assist with target separation and enrichment. In the present work, we have demonstrated that, by adding the pore partition agent, 2,4,6-tris(4-pyridyl)pyridine (TPY) during synthesis of the bimetallic Fe/Co-MIL-88(NH 2 ) MOF to block the open metal sites, a highly porous MOF of Fe/Co-TPY-MIL-88(NH 2 ) can be produced. This material also exhibits high stability in basic solutions and biofluids and possesses high peroxidase-mimicking activity, which can be utilized to produce long-lasting chemiluminescence (CL) from luminol and H 2 O 2 . Moreover, acting as the peroxidase-mimic, the Fe/Co-TPY-MIL-88(NH 2 ) MOF can form the enzymatic cascade with glucose oxidase (GOx) for biomarker detection. Further, when applied to detect extracellular vesicles (EVs), the MOF material and GOx are brought to the proximity on the EVs through two surface proteins, which triggers the enzyme cascade to produce high CL from glucose and luminol. EVs within the concentration range of 5 × 10 5 - 4 ×10 7 particles/mL can be detected, and the method can be used to analyze EV contents in human serum without sample preparation and EV purification. Overall, our work demonstrates that the high versatility and tunability of the MOF structures could bring in significant benefits to biosensing and enable ultrasensitive detection of biomarkers with judicious material designs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗