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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Viscosity-temperature relation based on the evolution of medium-range structures of silica

The viscosity of glass is the most important technological property to glass manufactures and various applications. Practically, finding an accurate equation to express the glass viscosity behavior in the entire glass transition temperature range is tremendously challenge because it spans more than ten orders of magnitude. After a brief review of existing empirical viscosity equations, this work focuses on the correlating silica viscosity behavior with the evolution of glass medium-range structure, based on the recently proposed nanoflake model. From this new model, a new equation is constructed, which correctly describes the Arrhenius-type behavior of silica viscosity η above the melting temperature Tm, and non-Arrhenius-type behavior from Tm to a critical temperature Tc. At temperature lower than Tc, the equation predicts Arrhenius-type behavior again for the viscous flow with increased activation energy. The new equation agrees with experimental data in the entire temperature spanned from extremely high to extremely low. Furthermore, the application of the new equation is shown to extend to sodium silicate glasses as well.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Radiation-induced negative optical nonlinearities in fused silica, sapphire, and borosilicate glass

Here, negative nonlinear absorption is reported in neutron- and gamma-irradiated high-OH content fused silica, low-OH content fused silica, sapphire, borosilicate glass, and radiation-resistant borosilicate glass irradiated to total neutron fluences of 3.4 × 10 16 n ∙ cm –2 (42 Mrad γ), 1.7 × 10 17 n ∙ cm –2 (211 Mrad γ), and 3.6 × 10 17 n ∙ cm –2 (433 Mrad γ). Nonlinear absorption coefficients were measured via Z-scan and are on the order of – (10 –14 –10 –10 ) m∙W –1 . The Z-scan also reveals a negative nonlinear index of refraction in neutron- and gamma-irradiated radiation-resistant borosilicate glass on the order of –10 –19 m 2 ∙ W –1 . Thermal annealing at temperatures up to 800 °C is shown to restore these nonlinearities to their positive unirradiated values in all four materials. All Z-scan measurements were performed at 532 nm with a nanosecond pulsed laser. The occurrence of negative nonlinearities may be attributed to the presence of metallic impurities and the resulting saturable absorption. A limited effect of photobleaching is observed in measurements and is quantified in multiple Z-scans.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Measurements of scattering and absorption properties of submillimeter bauxite and silica particles

Submillimeter solid particles have been considered as thermal storage media for concentrated solar power applications. Knowledge of the scattering and absorption properties of individual particles is crucial for modeling the radiative heat transfer of the particle bed. In this work, a laser scatterometer is used to measure the single-particle scattering properties at a wavelength of 635 nm by using two configurations: (1) a falling particle curtain and (2) a taped particle layer. Because a one-particle nominal thickness is formed with area fractions of 5-55% depending on the configuration, multiple scattering is minimized and hence the single scattering phase function, averaged over all illuminated particles, is directly measured. Bauxite-based ceramic particles that are strongly absorbing in the solar spectrum and silica particles that are nonabsorbing in the visible and near-infrared are investigated. The directional-hemispherical reflectance and transmittance of the taped particles are also measured to deduce the forward and backward scattering efficiency factors and the absorption efficiency factors. Only weak wavelength dependence is observed in the measured region from 380 nm to 1020 nm. Furthermore, the scattering phase functions of all bauxite-based particles with varying sizes and compositions are very similar and can be fitted to a Henyey-Greenstein phase function with an asymmetry factor g = -0.20. For the silica particles, forward scattering dominates and g = 0.45 yields the best fit. A Monte Carlo method is developed to model the particle scattering characteristics, and reasonable agreements between the modeling and experimental results are observed by introducing a specularity parameter.

42 ENGINEERING↗
DOE OSTI2021

Flow reduction of hydrocarbon liquid in silica nanochannel: Insight from many-body dissipative particle dynamics simulations

A modified many-body dissipative particle dynamics (mDPD) model recently developed for realistic mesoscale multiphase flow simulations is rigorously parameterized, calibrated, and applied for elucidating the flow mechanisms of hydrocarbon liquids (i.e., heptane in this work) in amorphous silica cylindrical nanochannels with inner diameters ranging from 4.5 to 22.5 nm. The simulation results suggest the presence of a strong threshold of pressure gradient under which heptane cannot be driven to flow. The threshold for the 4.5 nm diameter pore is 10 to 100 times as high as for the 9–22.5 nm diameter pore, highlighting a remarkable nanoconfinement effect. Fluid viscosity is found to exhibit a shear-thinning phenomenon with intensity to weaken with increasing channel diameter — a phenomenon not observed in nanochannel flow of liquid water and gas in literature. Most remarkably, the radial profiles of average longitudinal flow velocity fitted by the modified Hagen-Poiseuille equation showed a negative slip length (–2.5% to –0.5% relative to the diameter) and a reduction of apparent permeability by 16% to 23%. Furthermore, this finding suggests silica nanochannels tend to deter hydrocarbon flow, a phenomenon that is opposed to the flow enhancement reported in most of the prior nanochannel flow studies in literature.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Langmuir adsorption model to assess the impact of silane coupling on nano-dispersion of silica in SBR

Surface active agents are often used to improve dispersion of nanoparticles. Quantitative correlation between these surface-active molecules and nanoscale dispersion is absent from the literature partly because a quantitative measure of nanoscale dispersion does not exist. Recently, we have developed the Virial-van der Waals method to quantify dispersion in nanocomposites using virial coefficients. In this paper, the Langmuir adsorption model is used to quantify the influence of surface-active agents on nano-scale dispersion in terms of the effective second virial coefficient B 2 *. The impact of silane coupling agent on the nano-dispersion and silica aggregate structure in precipitated silica/SBR nanocomposites is demonstrated. It is shown that the higher viscosity SBR matrix led to a greater silica aggregate structural breakup, while lower viscosity matrix improved surface silanization. The isomeric content of the SBR, which impacts the dielectric behavior, impacted whether the system could be modeled through a mean-field or specific interactions. We earlier showed that larger aggregates improve dispersion, and this is reaffirmed in these results. After account is made for aggregate size, nano-scale dispersion improves with the addition of silane coupling agent. The behavior is well modeled using Langmuir monolayer adsorption.

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

Metallic Cation-Mediated Entrapment of Nucleic Acids on Mesoporous Silica Surface: Application in Castration-Resistant Prostate Cancer

The use of exogenous nucleic acid technologies to modulate aberrant protein expression resulting from genetic mutations is a promising therapeutic approach for the treatment of diseases such as advanced prostate cancer (PC). The promise of nucleic-based therapeutics is dependent on the development of platforms that effectively protect nucleic acids from nuclease degradation and deliver the nucleic acids to the cytosol of target cells. In this work, we present the development of a divalent metal-mediated nucleic acid entrapment strategy with a porous silica matrix. This simple strategy results in efficient loading percentages of both siRNA (>60%) and mRNA (>80%) as well as their release within relevant biological environments (80%). Additionally, our data supports that the current method reduces endosomal entrapment and supports the lipid coating of mesoporous silica nanoparticles (LC-MSNs). Finally, the metal-enhanced nanosystem is assessed for biocompatibility, stability, and circulation within in vitro, ex ovo, and in vivo models of PC.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Perovskite-Derived Cs 2 SnCl 6 –Silica Composites as Advanced Waste Forms for Chloride Salt Wastes

Advanced materials and processes are required to separate halides and fission products from complex salt waste streams associated with the chemical reprocessing of used nuclear fuels and molten salt reactor technologies for immobilization into chemically durable waste forms. Here, in this work, we explore an innovative concept using metal-halide perovskites as advanced host phases to incorporate Cs and Cl with very high waste loadings. Wet chemistry-synthesized Cs 2 SnCl 6 powders from CsCl salt solutions are successfully encapsulated into a silica matrix to form a composite using low-temperature spark plasma sintering with tunable Cs and Cl loadings up to 31 wt.% and 26 wt.%, respectively. Chemical durability testing of the composite waste forms by semi-dynamic leaching experiments demonstrates that incongruent leaching mechanism dominated. The metal-halide perovskite-silica composite waste forms display exceptional chemical durability with the long-term release rates of Cs and Cl comparable to or outperforming the state-of-the-art waste form materials but with significantly higher waste loadings. The scalable synthesis of the metal-halide perovskite from wet-chemistry processes opens up new opportunities in designing perovskite-glass composite waste forms for salt wastes with very high waste loadings and exceptional chemical durability for the sustainable development of advanced fuel cycles and next-generation reactor technologies.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Determining the Three-Dimensional Structures of Silica-Supported Metal Complexes from the Ground Up

The immobilization of molecularly precise metal complexes to substrates, such as silica, provides an attractive platform for the design of active sites in heterogeneous catalysts. Specific steric and electronic variations of the ligand environment enable the development of structure–activity relationships and the knowledge-driven design of catalysts. At present, however, the three-dimensional environment of the precatalyst, much less the active site, is generally not known for heterogeneous single-site catalysts. We explored the degree to which NMR-based surface-to-complex interatomic distances could be used to solve the three-dimensional structures of three silica-supported metal complexes. Furthermore, the structure solution revealed unexpected features related to the environment around the metal that would be difficult to discern otherwise. This approach appears to be highly robust and, due to its simplicity, is readily applied to most single-site catalysts with little extra effort.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Water Uptake by Silica Nanopores: Impacts of Surface Hydrophilicity and Pore Size

Water uptake at 298 K by two mesoporous silicas with different pore sizes was studied using volumetric vapor sorption. Here, through variation of sample pretreatment temperature and time, the number of surface hydroxyl groups was varied, leading to marked changes in the water sorption behavior. With increasing surface hydroxyl density, the adsorption of water to the pore surfaces increases, leading to formation of a thicker and denser water sorption layer. The BET model was used to measure surface hydroxyl density from low pressure parts of water adsorption isotherms. Adsorption of water molecules scales with the number density of surface hydroxyl groups, and monolayer coverage is reached at reduced pressure of ca. 0.3. The onset of adsorption pore condensation of water shifts to lower reduced pressure with increasing surface hydroxyl density, indicating growing thickness of adsorption layers. However, the water pore condensation step of the desorption branch shifts to smaller reduced pressure with increasing surface hydroxylation, reducing the adsorption-desorption hysteresis width. An adsorbed phase model is utilized to calculate the distribution of pore water molecules between adsorbed and pore condensation phases, and characterize the density and thickness of the water sorption phase. In the smaller pores, the adsorbed phase forms a sparse monolayer, while approximately a bilayer is formed in the wider pores. The previously reported silica nanopore underfilling by water is confirmed and rationalized by a significantly reduced water density in the adsorbed phase with respect to bulk, while the pore core is filled with water of approximately bulk density.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Extremely Slow Diffusion of Gold Nanoparticles under Confinement in Mesoporous Silica

Here, we report an X-ray photon correlation spectroscopy (XPCS) study of the mobility of colloidal gold nanoparticles with a diameter of approximately 4 nm in glycerol under confinement within the channels of SBA-15 mesoporous silica with pore diameters of approximately 6 and 12 nm. The XPCS correlation functions result from an effective heterodyne signal due to the mixing of the coherent scattering from the nanoparticles and the mesoporous silica. Over the range of wave vectors and hence length scales probed, the nanoparticle dynamics are well described by one-dimensional diffusion. The nanoparticle diffusivity varies with temperature in a manner expected based on the temperature-dependent viscosity of glycerol; however, the magnitudes of the diffusion coefficients are several orders of magnitude smaller than those of the nanoparticles in bulk glycerol. We consider mechanisms that might contribute to this reduction in diffusivity including enhancement in hydrodynamic drag under confinement, effects of nanoparticle adsorption to the pore walls, and slowing structural dynamics in glycerol due to the combination of the nanometer-scale confinement and the presence of the nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Probing the Morphology and Mobility of Amines in Porous Silica CO 2 Sorbents by 1 H T 1 – T 2 Relaxation Correlation NMR

Molecular and oligomeric amines supported in porous oxide supports are a promising class of CO 2 sorbent materials studied for CO 2 removal from diverse streams such as flue gas and ambient air. Among the various amines investigated, low molecular weight, hyperbranched poly(ethyleneimine) (PEI), and tetraethylenepentamine (TEPA) are among the most extensively studied. While macroscopic structure–performance relationships relating the support structure, amine loading, and other factors affecting CO 2 sorption capacities and kinetics have been developed, structural and dynamic information about the organic amine phase in the porous support is less plentiful. The structure and mobility of amines impregnated in the pores of porous supports directly impact gas sorption, as the accessibility of amine sites in the pores directly relates to amine distribution in the pores and overall pore filling as well as the dynamics of the amine chains. Here, we prepare a family of mesoporous silica SBA-15 materials containing varying loadings of oligomeric (PEI) and molecular (TEPA) amines. 1 H T 1 –T 2 relaxation correlation solid-state NMR experiments are used to characterize the structural and dynamic properties of the confined amines. Both TEPA and PEI are shown to form multiple different domains in the pores, each with distinguishable dynamic properties. TEPA and PEI form more rigid layers around the silica support walls at lower organic loading fractions, characterized by lower mobilities, followed by the formation of more mobile domains less engaged in pore wall interactions at higher loadings. TEPA shows faster mobilities than PEI because of its lower molecular weight. TEPA also appears to more easily transfer between domains within the pores, leading to generally faster CO 2 uptake rates with higher sorption capacities, while PEI located closer to the pore walls remained much less mobile and is thus less engaged in CO 2 capture.

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

pH-Mediated Colorimetric and Luminescent Sensing of Aqueous Nitrate Anions by a Platinum(II) Luminophore@Mesoporous Silica Composite

Increased levels of nitrate (NO 3 – ) in the environment can be detrimental to human health. Herein, we report a robust, cost-effective, and scalable, hybrid material-based colorimetric/luminescent sensor technology for rapid, selective, sensitive, and interference-free in situ NO 3 – detection. These hybrid materials are based on a square-planar platinum(II) salt [Pt(tpy)Cl]PF6 (tpy = 2,2';6',2''-terpyridine) supported on mesoporous silica. The platinum salt undergoes a vivid change in color and luminescence upon exposure to aqueous NO 3 – anions at pH ≤ 0 caused by substitution of the PF6– anions by aqueous NO 3 – . This change in photophysics of the platinum salt is induced by a rearrangement of its crystal lattice that leads to an extended Pt···Pt···Pt interaction, along with a concomitant change in its electronic structure. Furthermore, incorporating the material into mesoporous silica enhances the surface area and increases the detection sensitivity. A NO 3 – detection limit of 0.05 mM (3.1 ppm) is achieved, which is sufficiently lower than the ambient water quality limit of 0.16 mM (10 ppm) set by the United States Environmental Protection Agency. The colorimetric/luminescence of the hybrid material is highly selective to aqueous NO 3 – anions in the presence of other interfering anions, suggesting that this material is a promising candidate for the rapid NO 3 – detection and quantification in practical samples without separation, concentration, or other pretreatment steps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH 3 -TPD), and DFT calculations revealed that the supported ZnO x phase was present as isolated surface ZnO x sites on SiO 2 , with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO) 2 Zn 2+ O 2 Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO x sites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH) + Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH) + Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO) 2 Zn 2+ O 2 Si= sites were inactive. Greater heterogeneity among all surface ZnO x sites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnO x sites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO x sites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO) 2 Zn 2+ O 2 Si= sites on the silica support caused a greater number of active surface ZnO x sites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH) + Si) sites. Such findings suggested that inactive surface ZnO x sites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

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

Leveraging Hydration Forces for Size-Specific Nanoparticle Enrichment with a Redox-Responsive Silica-Binding Elastin-Like Polypeptide

Elastin-like polypeptides (ELPs) are low-complexity proteins that coacervate above a characteristic lower critical solution temperature (LCST). While the thermoresponsiveness of ELPs has been widely exploited in the biomedical and biomaterials fields, their ability to mediate nanoparticle assembly below their transition temperature remains largely unexplored. Here, we show that unmodified ELPs induce the reversible flocculation of silica nanoparticles (SiNPs) by forming backbone hydrogen bonds with surface silanols. Interparticle bridging is modulated by ELP length and concentration and by the presence of N- and C-terminal anchoring groups such as a cysteine residue and a Car9 silica-binding peptide. Using a redox-responsive fusion protein consisting of disulfide-bonded ELP domains terminated by Car9 segments, we stabilize 20 nm SiNPs under oxidizing conditions while triggering particle flocculation upon addition of reductant. We find that SiNP sedimentation under reducing conditions exhibits a sharp dependency on particle size that arises from the curvature-dependent structure of surface silanols. While the isolated silanols of SiNPs smaller than 30 nm are efficiently engaged by the ELP domains of Car9-anchored proteins, repulsion forces associated with the presence of a layer of molecular water together with increased electrostatic repulsion preclude efficient engagement of H-bonded silanols displayed on the surface of SiNPs larger than 60 nm. We harness these findings to selectively enrich SiNPs based on size and expand the concept to titania (TiO2) by demonstrating that rutile nanoparticles can be stabilized or sedimented with solid-binding ELPs by adjusting the solution pH to promote or discourage the formation of a hydration layer. These strategies should prove broadly useful for the separation of other oxides and their polymorphs and provide a tunable strategy for nanoparticle assembly and bioinspired colloidal design.

ELP↗
DOE OSTI2023

Silica Supported Organometallic Ir I Complexes Enable Efficient Catalytic Methane Borylation

Catalytic C–H borylation is an attractive method for the conversion of the most abundant hydrocarbon, methane (CH 4 ), to a mild nucleophilic building block. However, existing CH 4 borylation catalysts often suffer from low turnover numbers and conversions, which is hypothesized to result from inactive metal hydride agglomerates. Herein we report that the heterogenization of a bisphosphine molecular precatalyst, [(dmpe)Ir(cod)CH 3 ], onto amorphous silica dramatically enhances its performance, yielding a catalyst that is 12-times more efficient than the current standard for CH 4 borylation. The catalyst affords over 2000 turnovers at 150 °C in 16 h with a selectivity of 91.5% for mono- vs diborylation. Higher catalyst loadings improve yield and selectivity for the monoborylated product (H 3 CBpin) with 82.8% yield and >99% selectivity being achieved with 1255 turnovers. X-ray absorption and dynamic nuclear polarization-enhanced solid-state NMR spectroscopic studies identify the supported precatalyst as an Ir I species, and indicate that upon completion of catalysis, multinuclear Ir polyhydrides are not formed. This is consistent with the hypothesis that immobilization of the organometallic Ir species on a surface prevents bimolecular decomposition pathways. Importantly, immobilization of the homogeneous Ir I fragment onto amorphous silica represents a unique and simple strategy to improve the TON and longevity of a CH 4 borylation catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Silica accelerates the selective hydrogenation of CO 2 to methanol on cobalt catalysts

The reaction pathways on supported catalysts can be tuned by optimizing the catalyst structures, which helps the development of efficient catalysts. Such design is particularly desired for CO 2 hydrogenation, which is characterized by complex pathways and multiple products. Here, we report an investigation of supported cobalt, which is known for its hydrocarbon production and ability to turn into a selective catalyst for methanol synthesis in CO 2 hydrogenation which exhibits good activity and stability. The crucial technique is to use the silica, acting as a support and ligand, to modify the cobalt species via Co-O-SiOn linkages, which favor the reactivity of spectroscopically identified *CH 3 O intermediates, that more readily undergo hydrogenation to methanol than the C-O dissociation associated with hydrocarbon formation. Cobalt catalysts in this class offer appealing opportunities for optimizing selectivity in CO 2 hydrogenation and producing high-grade methanol. By identifying this function of silica, we provide support for rationally controlling these reaction pathways.

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

Monte carlo simulations and experiments of all-silica zeolite LTA assembly combining structure directing agents that match cage sizes

In this work, we investigated the influence of organic structure-directing agents (OSDAs) on the formation rates of all-silica zeolite LTA using both simulations and experiments, to shed light on the crystallization process. We compared syntheses using one OSDA with a diameter close to the size of the large cavity in LTA, and two OSDAs of diameters matching the sizes of both the small and large LTA cavities. Reaction-ensemble Monte Carlo (RxMC) simulations predict a speed up of LTA formation using two OSDAs matching the LTA pore sizes; this qualitative result is confirmed by experimental studies of crystallization kinetics, which find a speedup in all-silica LTA crystallization of a factor of 3. Analyses of simulated rings and their Si–O–Si angular energies during RxMC crystallizations show that all ring sizes in the faster crystallization exhibit lower angular energies, on average, than in the slower crystallization, explaining the origin of the speedup through packing effects.

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

Are the Brønsted acid sites in amorphous silica-alumina bridging?

Competing models exist to explain the differences in the activity of zeolites and amorphous silica–aluminas. Some postulate that silica–alumina contains dilute zeolitic bridging acid sites, while others favor a pseudo-bridging silanol model. Here, we employed a selective isotope labeling strategy to assess the existence of Si–O(H)–Al bonds using NMR-based distance measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗