Search NASA⌕ Search

SEARCH · Search NASA

Results for “Hybrid material”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 163 records · Page 9

Biomimetic Rebuilding of Multifunctional Red Blood Cells: Modular Design Using Functional Components

The design and synthesis of artificial materials that mimic the structures, mechanical properties, and ultimately functionalities of biological cells remains a current holy grail of materials science. Here based on a silica cell bio-replication approach, we report the design and construction of synthetic rebuilt red blood cells (RRBCs) that fully mimic the broad properties of native RBCs: size, biconcave shape, deformability, oxygen carrying capacity, long circulation time. Four successive nano-scale processing steps: RBC bioreplication, layer-by-layer polymer deposition, and precision silica etching, followed by RBC ghost membrane vesicles fusion are employed for RRBC construction. A panel of physicochemical analyses including zeta potential measurement, fluorescence microscopy, and antibody-mediated agglutination assay proved the recapitulation of RBC shape, size, and membrane structure. Flow-based deformation studies carried out in a microfluidic blood capillary model confirrned the ability of RRBCs to deform and pass through small slits and reconstitute themselves in a manner comparable to native RBCs. Circulation studies of RRBCs conducted ex-ovo in a chick embryo and in vivo in a mouse model demonstrated the requirement of both deformability and native cell membrane surface to achieve long-term circulation. To confer additional non-native functionalities to RRBCs, we developed modular procedures in which to load functional cargos such as hemoglobin, drugs, magnetic nanoparticles, and ATP biosensors within the RRBC interior to enable various functions, including oxygen delivery, therapeutic drug delivery, magnetic manipulation, and toxin biosensing and detection. Taken together, RRBCs represent a class of long circulating RBC-inspired artificial hybrid materials with a broad range of potential applications.

59 BASIC BIOLOGICAL SCIENCES↗

Ligand‐Mediated Quantum Yield Enhancement in 1‐D Silver Organothiolate Metal–Organic Chalcogenolates

X-ray free electron laser (XFEL) microcrystallography and synchrotron single-crystal crystallography are used to evaluate the role of organic substituent position on the optoelectronic properties of metal–organic chalcogenolates (MOChas). MOChas are crystalline 1D and 2D semiconducting hybrid materials that have varying optoelectronic properties depending on composition, topology, and structure. While MOChas have attracted much interest, small crystal sizes impede routine crystal structure determination. A series of constitutional isomers where the aryl thiol is functionalized by either methoxy or methyl ester are solved by small molecule serial femtosecond X-ray crystallography (smSFX) and single crystal rotational crystallography. While all the methoxy examples have a low quantum yield (0-1%), the methyl ester in the ortho position yields a high quantum yield of 22%. Here, the proximity of the oxygen atoms to the silver inorganic core correlates to a considerable enhancement of quantum yield. Four crystal structures are solved at a resolution range of 0.8–1.0 Å revealing a collapse of the 2D topology for functional groups in the 2- and 3- positions, resulting in needle-like crystals. Further analysis using density functional theory (DFT) and many-body perturbation theory (MBPT) enables the exploration of complex excitonic phenomena within easily prepared material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying Dense NiSe 2 /CoSe 2 Heterointerfaces Coupled with Surface High-Valence Bimetallic Sites for Synergistically Enhanced Oxygen Electrocatalysis

Constructing heterostructures with abundant interfaces is essential for integrating the multiple functionalities in single entities. Herein, the synthesis of NiSe 2 /CoSe 2 heterostructures with different interfacial densities via an innovative strategy of successive ion injection is reported. The resulting hybrid electrocatalyst with dense heterointerfaces exhibits superior electrocatalytic properties in an alkaline electrolyte, superior to other benchmarks and precious metal catalysts. Advanced synchrotron techniques, post structural characterizations, and density functional theory (DFT) simulations reveal that the introduction of atomic-level interfaces can lower the oxidation overpotential of bimetallic Ni and Co active sites (whereas Ni$^{2+}$ can be more easily activated than Co$^{2+}$) and induce the electronic interaction between the core selenides and surface in situ generated oxides/hydroxides, which play a critical role in synergistically reducing energetic barriers and accelerating reaction kinetics for catalyzing the oxygen evolution. Hence, the heterointerface structure facilitates the catalytic performance enhancement via increasing the intrinsic reactivity of metallic atoms and enhancing the synergistic effect between the inner selenides and surface oxidation species. This work not only complements the understanding on the origins of the activity of electrocatalysts based on metal selenides, but also sheds light on further surface and interfacial engineering of advanced hybrid materials.

36 MATERIALS SCIENCE↗

Tunable Photocatalytic Production of Syngas Using Co@C 3 N 4 and Black Phosphorus

Photocatalytic syngas production is an attractive option to efficiently generate a feedstock for the Fischer-Tropsch processes that can produce liquid fuels and other chemicals. Here, one-pot photocatalytic production of syngas (H 2 +CO) with specific and controllable ratios of H 2 /CO has proven to be a significant challenge to date. In this work, single Co 2+ sites loaded onto carbon nitride (Co@C 3 N 4 ) is combined with black phosphorus (BP) to form a hybrid material, which is capable of simultaneous photocatalytic evolution of H 2 and CO. H 2 /CO syngas ratios can be controlled in the range from 0.30 to 5.16 by changing the % weight of BP in this system or by the addition of CoCl 2 in the reaction solution. Maximum total gas evolution of 70 μmol g –1 h –1 was achieved with 20 wt % BP (BP 20% /Co@C 3 N 4 ) at a H 2 /CO ratio of 2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interactions involved in the adsorption of ethylene glycol and 2-hydroxyethoxide on the Au(111) surface: a Density Functional Theory study

Abstract Context:The monolayers of ethylene glycol and 2-hydroxyethoxide on gold surfaces have been used in hybrid materials as biosensors. In this article, the adsorption of ethylene glycol and 2-hydroxyethoxide on the Au(111) surface was analyzed. For the first system, ethylene glycol on Au(111), there are Au$$\cdot \cdot \cdot $$ · · · O and Au$$\cdot \cdot \cdot $$ · · · H interactions. To the best of our knowledge, the Au$$\cdot \cdot \cdot $$ · · · H interaction has been overlooked until now. However, in this work, there is strong evidence that this interaction is important to stabilize the system. For the second system, the atomic interactions mentioned previously are also predicted, although there is an additional interaction between 2-hydroxyethoxide molecules. Such an interaction induces the link -O-H-O-, with high values of the electron density at the critical points of the corresponding bond path of the O-H interaction. These links suggest the forming of ethylene glycol chains.Methods:The calculations were performed using two exchange-correlation functionals: BEEF-vdW and C09$$_{x}$$ x -vdW; both functionals incorporate dispersion effects within the Kohn-Sham approach in Density Functional Theory as implemented in GPAW code and ASE computational packages. The contacts between the molecules considered in this article and the Au(111) surface were analyzed through the Quantum Theory of Atoms in Molecules implemented in GPUAM code.

Biochemistry & Molecular Biology↗

Novel self-assembled two-dimensional layered oxide structure incorporated with Au nanoinclusions towards multifunctionalities

Two-dimensional (2D) layered oxides have recently attracted wide attention owing to the strong coupling among charges, spins, lattice, and strain, which allows great flexibility and opportunities in structure designs as well as multifunctionality exploration. In parallel, plasmonic hybrid nanostructures exhibit exotic localized surface plasmon resonance (LSPR) providing a broad range of applications in nanophotonic devices and sensors. A hybrid material platform combining the unique multifunctional 2D layered oxides and plasmonic nanostructures brings optical tuning into the new level. Here, a novel self-assembled Bi 2 MoO 6 (BMO) 2D layered oxide incorporated with plasmonic Au nanoinclusions has been demonstrated via one-step pulsed laser deposition (PLD) technique. Comprehensive microstructural characterizations, including scanning transmission electron microscopy (STEM), differential phase contrast imaging (DPC), and STEM tomography, have demonstrated the high epitaxial quality and particle-in-matrix morphology of the BMO-Au nanocomposite film. DPC-STEM imaging clarifies the magnetic domain structures of BMO matrix. Three different BMO structures including layered supercell (LSC) and superlattices have been revealed which is attributed to the variable strain states throughout the BMO-Au film. Owing to the combination of plasmonic Au and layered structure of BMO, the nanocomposite film exhibits a typical LSPR in visible wavelength region and strong anisotropy in terms of its optical and ferromagnetic properties. This study opens a new avenue for developing novel 2D layered complex oxides incorporated with plasmonic metal or semiconductor phases showing great potential for applications in multifunctional nanoelectronics devices.

36 MATERIALS SCIENCE↗

Carbon nanotube coated metal mesh: Bridging nanoscale and macroscale

A novel hybrid structure has been developed by growing carbon nanotubes (CNTs) on a metal mesh that functions as a literally unlimitedly extendable backbone. This hybrid material structure provides a new approach of extending CNTs’ advantageous properties such as ultrahigh thermal and electrical conductivities, high sensitivity to gases, and distinctive wettability for different liquids with chemical inertness to macroscale—otherwise available only in nano- and microscales. In this feasibility work, CNTs were grown on a Type 316 stainless steel (SS) mesh by self-catalytical chemical vapor deposition (CVD) without the need of an externally added catalyst or catalyst support. For the radially aligned and entangled CNT forest on the SS mesh, the average CNT diameter is around 50 nm, while the length varies from 20 to 25 µm. High-resolution transmission electron microscopy analysis revealed the multiwall structure of the CNTs with >30 rolled-up graphitic sheets. Raman spectra of the CNTs showed a dominant G band, indicating a well-ordered graphitic nanostructure. Being highly hydrophobic with a water contact angle of ∼145° and oleophilic, the CNT-coated SS mesh could be used in fluid separation and organic contaminant removal from water. Moreover, CNTs are recognized for their exceptional thermal conductivity and the CNT-coated mesh offers a supportive structure with directly connected CNTs for efficient heat transfer. Proof of concept has been achieved for the CNT-coated mesh’s potentials as a liquid filter and an thermal interface material (TIM). Specifically, the CNT-coated mesh demonstrated the capability of capturing water from a water-organic mixture with a 100 % efficiency while allowing organic liquids to pass through the filter. Furthermore, when used as a TIM, the CNT-coated mesh reduced the interfacial thermal impedance by >30 %.

Carbon nanotubes (CNTS)↗

Precisely modulate interfacial Bi-O bridge bond in Co-TCPP/Bi 3 O 4 Br to trigger long-lasting charge separation for boosting CO 2 photoreduction

Insufficient charge separation and feeble CO 2 activation limit the CO 2 photoreduction efficiency. It is highly desirable to consciously construct organic–inorganic hybrid composites to simultaneously accelerate charge separation and provide favorable active sites. Herein, a defect-induced interfacial Bi-O bridge bond is constructed by grafting terminal O of cobalt porphyrin (Co-TCPP) with Bi 3 O4Br. Systematic investigations reveal that the Bi-O bridge bond as the charge migration bridge accelerates the extraction and transfer of electron from the external [Bi 3 O 4 ] layers to Co-TCPP, and the millisecond separation lifetime of electrons on Co-TCPP can be achieved. Co atoms as the active sites optimized the CO 2 adsorption and activation, thus promoting the formation of COOH*. As a result, the CO 2 photoreduction rate of 0.5% Co-TCPP/Bi 3 O4Br reaches 71.3 μmol g -1 h -1 in pure water, 2.53-fold of that on the pristine Bi 3 O4Br. This work provides atomistic insights and strategies for the construction of new organic–inorganic hybrid materials for artificial photosynthesis and CO 2 photoreduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Core-shell metallic alloy nanopillars-in-dielectric hybrid metamaterials with magneto-plasmonic coupling

Combining plasmonic and magnetic properties, namely magneto-plasmonic coupling, inspires great research interest and the search for magneto-plasmonic nanostructure becomes considerably critical. In this work, we designed a nanopillar-in-matrix structure with core–shell alloyed nanopillars for both BaTiO 3 (BTO)-Au 0.5 Co 0.5 (AuCo) and BTO-Au 0.25 Cu 0.25 Co 0.25 Ni 0.25 (AuCuCoNi) hybrid systems, i.e., ferromagnetic alloy cores (e.g., Co or CoNi) with plasmonic shells (e.g., Au or Au/Cu). These core–shell alloy nanopillars are uniformly embedded into a dielectric BTO matrix to form a vertically aligned nanocomposite (VAN) structure. Both hybrid systems present excellent epitaxial quality and interesting multi-functionality, e.g., high magnetic anisotropy, magneto-optical coupling response, tailorable plasmonic resonance wavelength, tunable hyperbolic properties and strong optical anisotropy. These alloyed nanopillars-in-matrix designs provide enormous potential for complex hybrid material designs with multi-functionality and demonstrate strong interface enabled magneto-plasmonic coupling along with plasmonic and magnetic performance.

36 MATERIALS SCIENCE↗

Sequential Infiltration Synthesis of Multinary Metal Oxides: The Role of Precursor Diffusion and Reactivity

Understanding volatile metal–organic precursor transport in polymer matrices during sequential infiltration synthesis (SIS) is critical to the design of hybrid materials of tailored composition and uniform structure. Here, we investigate the diffusion and reaction behavior of diethylzinc (DEZ) in poly(methyl methacrylate) (PMMA) matrices with variable indium and zinc incorporation. Unlike conventional SIS where precursors adduct or react directly with the polymer backbone, DEZ shows minimal interaction with PMMA. However, DEZ may interact strongly with In–OH or Zn–OH moieties that are previously incorporated into a PMMA thick film. Using spectroscopic ellipsometry, X-ray photoelectron spectroscopy depth profiling, and EDX line scans, we quantify Zn incorporation as a function of exposure time, polymer thickness, and previous infiltration steps. The Zn distribution evolves from surface-localized to deep within the ∼1 μm thick film with increasing DEZ exposures up to 30 min. A reaction-diffusion model incorporating a hindering factor to capture diffusivity decay due to product accumulation reproduces the Zn depth profile and yields physically meaningful parameters to guide future growth. Furthermore, this study provides a framework for interpreting metal–organic precursor infiltration behavior and highlights the utility of model-guided SIS process design.

diethylzinc↗

Pressure-Driven Helium Insertion for Structural Stability of CH 3 NH 3 PbBr 3 Hybrid Perovskites

Organic−inorganic metal halide perovskites (MHPs) have garnered significant attention due to their outstanding performance in optoelectronic devices, but they are prone to degradation through a variety of pathways. High-pressure studies are being used to understand the mechanical and structural stability of MHPs and investigate new methods for improving these. In this study, we map the high-pressure, low-temperature structural phase diagram of CH 3 NH 3 PbBr 3 (MAPbBr 3 ) between 15−300 K and up to 1.5 GPa. We first compare the temperature and pressure effects on the global and local structures of MAPbBr 3 using synchrotron X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS), respectively, and find evidence of PbBr 6 octahedral distortion. Our results also suggest that He inserts into the MAPbBr 3 structure. The thermodynamics of He insertion into MAPBHe x are calculated to be plausible at room temperature for x ≤ 1 and P = 1−3 GPa and shown to stabilize higher-symmetry phases. This phenomenon increases the fitted bulk modulus of MAPbBr 3 . Structural stabilization by inert atom insertion is proposed as a method to improve the mechanical robustness of MHPs and other soft hybrid materials.

Diffraction↗

Regioselective Hydrosilylation Catalysis with Supported Well-Defined Pt(0) Complexes: Effects of Surface Anions and Phosphenium Ligands

Achieving stable, selective single-atom catalysts is challenging because localsurface-site structures are difficult to control. Surface organometallic chemistry and organic−inorganic hybrid materials offer partial solutions, but applications to supporting zero-valent metals are limited. We demonstrate that well-defined, ionically bound N-heterocyclic phosphenium ([NHP] + ) ligands can be generated on silylium-functionalized sulfated zirconia ([ i Pr 3 Si][SZO]). These surface-bound [NHP][SZO] ligands coordinate Pt(0) centers, forming [(NHP)Pt(0)L][SZO] precatalysts that are highly active for alkyne hydrosilylation. Systematic studies reveal that sterically bulky aromatic ligands enhance regioselectivity, achieving performances comparable to molecular Pt catalysts. Further, more-coordinating anions support more-regioselective precatalysts; therefore, SZO supports more-selective species than weaker-coordinating Al(OC(CF 3 ) 3 ) 3 - functionalized silica, a trend confirmed by molecular analogues. These results demonstrate that both the ligand and support control catalytic behavior and enable solid-state structure− activity relationships.

Catalysts↗

Effects of Strain Rate and Temperature on the Mechanical Properties of Simulated Silica Ionogels

Ionogels are hybrid materials formed by impregnating the pore space of a solid matrix with a conducting ionic liquid. By combining the properties of both component materials, ionogels can act as self-supporting electrolytes in Li batteries. In this study, molecular dynamics simulations are used to investigate the dependence of mechanical properties of silica ionogels on solid fraction, temperature, and pore width. Comparisons are made with corresponding aerogels. We find that the solid matrix fraction increases the moduli and strength of the ionogel. This varies nonlinearly with temperature and strain rate, according to the contribution of the viscous ionic liquid to resisting deformation. Additionally, owing to the temperature and strain sensitivity of the ionic liquid viscosity, the mechanical properties approach a linear mixing law at high temperature and low strain rates. The median pore width of the solid matrix plays a complex role, with its influence varying qualitatively with deformation mode. Narrower pores increase the relevant elastic modulus under shear and uniaxial compression but reduce the modulus obtained under uniaxial tension. Conversely, shear and tensile strength are increased by narrowing the pore width. All of these pore size effects become more pronounced as the silica fraction increases. Pore size effects, similar to the effects of temperature and strain rate, are linked to the ease of fluid redistribution within the pore space during deformation-induced changes in the geometry of the pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Light-Emitting Organic Semiconductor-Incorporated Perovskites: Fundamental Properties and Device Applications

Recently, organic semiconductor-incorporated perovskites (OSiPs) have emerged as a new subclass of next-generation organic–inorganic hybrid materials. OSiPs combine the advantages of organic semiconductors, such as large design windows and tunable optoelectronic functionalities, with the excellent charge-transport properties of the inorganic metal-halide counterparts. OSiPs provide a new materials platform for the exploitation of charge and lattice dynamics at the organic–inorganic interfaces for various applications. This Perspective reviews recent achievements in OSiPs highlighting the benefits from organic semiconductor incorporation and elucidates the fundamental light-emitting mechanism, energy transfer, as well as band alignment structures at the organic–inorganic interface. Finally, insights on the emission tunability lead toward a discussion of the potential of OSiPs in light-emitting applications, such as perovskite light-emitting diodes or lasing systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microscopic Dynamics Controls Coupling and Cluster Formation in Brush Particle Solids

Thermodynamics-based models predict the structure of polymer-grafted nanoparticles (PGNs) as well as their assembly behavior based on geometric parameters such as particle size, degree of polymerization, and density of grafted chains. The role of microscopic polymer dynamics, such as the mobility of repeat units in the melt state, in the evolution of the structure and properties remains unknown. Brillouin light spectroscopy (BLS), due to its capability to concurrently discern the local and global elastic properties of PGN assemblies, enables the probing of microscopic processes, such as brush interdigitation, sensitive to the annealing of the assembly. For poly(methyl methacrylate) (PMMA)-grafted silica (SiO 2 ) PGNs in the dry powder state and annealed above the glass transition temperature, BLS revealed fully reversible local elasticity, indicative of limited interdigitation between adjacent PGNs. This contrasts with polystyrene (PS)−SiO 2 analogs that displayed ready (and irreversible) fusion of brush layers during annealing. The retardation of brush interdigitation in PMMA-grafted systems is surprising, given the similar thermomechanical properties of both polymers, and is rationalized as the consequence of higher friction between PMMA repeats compared to PS. Microscopic dynamics thus has a profound impact on the kinetic path of structure (and property) evolution and thus should be considered during the processing of PGNs into functional hybrid materials.

chemical structure↗

Effect of Initiator Density, Catalyst Concentration, and Surface Curvature on the Uniformity of Polymers Grafted from Spherical Nanoparticles

Polymer-grafted nanoparticles (PGNPs) are versatile hybrid materials whose properties critically depend on brush dimensions, uniformity, and grafting density. Herein, we systematically investigated how initiator density, catalyst concentration, and nanoparticle curvature govern the growth of poly(methyl methacrylate) (PMMA) brushes grafted from spherical SiO 2 nanoparticles via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). By tuning the initiator density through a combination of “active” and “dummy” silane initiators anchored on the nanoparticles’ surface and controlling the catalyst concentration, we reveal that increased initiator crowding and smaller surface curvature amplify steric hindrance, leading to decreased initiation efficiency and broader molecular weight distributions. Correlation with the corresponding unattached chains by ARGET ATRP suggests the presence of permanently inaccessible (“buried”) initiation sites, which are a characteristic of surface-grafted systems. At sufficient Cu catalyst concentrations, uniform brush growth is attained across different initiator densities, whereas decreased catalyst concentrations accentuate nonconcurrent initiation and propagation. These findings provide mechanistic insights into the interplay of initiator density, catalyst concentration, and surface curvature, offering design principles for tailoring the PGNP architecture. These results can guide the structural engineering of densely grafted surfaces, including nanoparticles and flat substrates, for applications in nanocomposites, photonics, and functional coatings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanomolar Sensitivity Chirality Transfer from Designed Helical Repeat Proteins to Achiral CdS Nanorods

Bridging chirality across length scales with inorganic− organic hybrid materials is a rapidly expanding area of research. Here, we establish asymmetry at CdS nanorod (NR) interfaces using a designed helical repeat protein bearing four cysteine residues (DHR- 4Cys). Hydrophobic NRs are transferred into water with glycine, and then glycine is displaced by DHR-4Cys, leveraging the thiophilicity of cadmium. Circular dichroism (CD) in the visible, coincident with CdS electronic transitions, reveals a chiral DHR-4Cys:CdS interface. Here, the dissymmetry factor [g-factor = 4.5 × 10 −4 (short NRs) and 5.0 × 10 −4 (long NRs)] is weakly dependent on the NR length, and CD persists at nanomolar protein loadings. Additionally, control experiments demonstrate that DHR-4Cys:CdS NR chirality is dictated by the local coordination of Cys with no significant contribution from the chiral secondary structure of the protein (g-factors of short and long Cys:CdS NRs are 4.8 × 10 −4 and 4.0 × 10 −4 , respectively). Together with far-UV CD and transmission electron microscopy, which provide evidence of preserved protein structure, these results provide the first demonstration that a structurally defined protein can induce chirality in CdS nanocrystals while maintaining protein structure at biologically relevant concentrations.

Cadmium sulfide↗

Role of Transition Metals in Metal–Organic Frameworks as Nanoporous Ion Emitters for Thermal Ionization Mass Spectrometry

Thermal ionization mass spectroscopy (TIMS) is a powerful analytical technique that allows for precise determination of isotopic ratios. Analysis on low abundance samples, however, can be limited by the ionization efficiency. Following an investigation into a new type of metal-organic hybrid material devised to promote the emission of analyte ions (nano-PIES) and reduce traditional sample loading problems, this work probes the impact that changing the metal in the material has on the ionization of Uranium-238. Being derived from metal-organic frameworks (MOFs), nano-PIEs inherit the tunability of the parent MOFs; the MOF-74 series has been well studied for probing the impact various framework metals (i.e., Mg, Mn, Co, Ni, Cu, Zn, and Cd) have on material properties, and thus, a series of nano-PIEs with different metals were derived from an isoreticular MOF-74 series. In conclusion, trends in ionization efficiency were studied as a function of ionization potential, volatility, and work function of the framework metals as well as the mechanism of ionization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗