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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Characterisation of nano-assemblies inside mesopores using neutron scattering

Adsorption of molecular and nanoscale matter in mesoporous materials is important in filtration and chromatography as well as membrane processes. However, the morphology and distribution of self-assembled structures of adsorbate formed within nanoconfined environments is largely unknown. Small Angle Neutron Scattering (SANS) with porous matrix matching the neutron scattering length density of the solvent has the potential to provide detailed information on the self-assemblies formed in pore spaces. However, analysis of such SANS profiles remains a challenge. In this study, we extend the SANS analysis method previously developed by Findenegg and co-workers to include interparticle correlations, providing a qualitative characterisation of the adsorption state of surfactants and nanoparticles in the cylindrical pores of silica nanomaterials. We find that the pore filling fraction and the self-assembled state of the adsorbate governs the scattering profile. We apply the model to two materials namely, triethyleneglycol monohexyl ether (C 6 E 3 ) surfactant and gold nanoparticles adsorbed in SBA-15 mesoporous silica. In contrast to the C 6 E 3 system, Bragg scattering dominates the diffuse scattering in gold nanoparticle system, which we attribute to the immobile internal structure of the nanoparticles. In conclusion, this new SANS analysis method has potential to elucidate structures of soft matter nanoassemblies inside mesopores.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Preparation of SBA-15-Supported Metals by Vapor-Phase Infiltration

A simple method is presented for incorporating various catalytic metals into the pores of SBA-15 using vapor-phase infiltration. The precursors used in Atomic Layer Deposition (ALD) for Pt, Pd, Rh, Ru, and Ni were exposed to an evacuated SBA-15, resulting in monolayer films of the adsorbed precursors inside the mesopores. The metal particles that formed after removal of the precursor ligands remained in the pores and had particle sizes ranging from 3.8 nm for Pt to 5.2 nm for Ni, as determined by Transmission Electron Microscopy (TEM), XRD, and CO chemisorption. Metal loadings for saturation exposures ranged from 5.1-wt% for Ni to 9.1-wt% for Pt; however, uniform deposition was demonstrated for lower loadings of Pd by decreasing the amount of precursor. To determine the effect of the surface composition of the mesopores, Pd particles were also added to SBA-15 that was coated with a 0.2-nm film of ZrO2.

Rh↗
DOE OSTI2024

Hierarchically porous electrospun carbon nanofiber for high-rate capacitive deionization electrodes

Capacitive deionization (CDI) is a promising technology that has gained interest for the desalination of brackish water. Hierarchically porous carbons are commonly used as electrodes for CDI due to their high surface areas and controlled pore size distributions that maximize ion adsorption capacity and rate. Electrospinning is an effective way of generating carbon nanofibers with high inter-fiber macroporosity that can be further modified to improve surface area, total pore volume, and pore size distribution. This work describes the use of sacrificial mesopore formers in tandem with a micropore etching technique to induce hierarchical porosity in electrospun fibers. Mesopores are formed via the dissolution of silica nanoparticles that are introduced into the fibers during the electrospinning step. After mesopore formation, micropores are etched into the resulting surface through KOH impregnation and thermal activation. This sequential technique creates a hierarchical network of pores from the inherent macroporosity of the fiber network, to the mesopores, and finally micropores to simultaneously maximize surface area and accessibility. Micropore formation is optimized to maximize specific surface area while maintaining physical integrity of the fibers. Further, the combination of mesopores and micropores enables fast ion adsorption rates and capacity. Carbon fiber electrodes fabricated in this method achieve specific surface areas exceeding 1400 m 2 g -1 , with pore volumes exceeding 1.0cc g -1 . The pore size distributions are highly controlled, with 80% of total pore volume coming from pores <20nm in radius. In 500 ppm constant voltage CDI tests, these fiber electrodes obtain a salt adsorption capacity of over 14 mg g -1 at a salt adsorption rate of ~4mg g -1 min -1 , showcasing the high capacity matched with high rate of these easily fabricated, inexpensive materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Two Mesoporous Domains Are Better Than One for Catalytic Deconstruction of Polyolefins

Catalytic hydrogenolysis of polyolefins into valuable liquid, oil, or wax-like hydrocarbon chains for second-life applications is typically accompanied by the hydrogen-wasting co-formation of low value volatiles, notably methane, that increase greenhouse gas emissions. Catalytic sites confined at the bottom of mesoporous wells, under conditions in which the pore exerts the greatest influence over the mechanism, are capable of producing less gases than unconfined sites. A new architecture was designed to emphasize this pore effect, with the active platinum nanoparticles embedded between linear, hexagonal mesoporous silica and gyroidal cubic MCM-48 silica (mSiO 2 /Pt/MCM-48). This catalyst deconstructs polyolefins selectively into ~C 20 –C 40 paraffins and cleaves C–C bonds at a rate (TOF = 4.2 ± 0.3 s –1 ) exceeding that of materials lacking these combined features while generating negligible volatile side products including methane. The time-independent product distribution is consistent with a processive mechanism for polymer deconstruction. In contrast to time- and polymer length-dependent products obtained from non-porous catalysts, mSiO 2 /Pt/MCM-48 yields a C 28 -centered Gaussian distribution of waxy hydrocarbons from polyolefins of varying molecular weight, composition, and physical properties, including low-density polyethylene, isotactic polypropylene, ultrahigh-molecular-weight polyethylene, and mixtures of multiple, post-industrial polyolefins. Here, coarse-grained simulation reveals that the porous-core architecture enables the paraffins to diffuse away from the active platinum site, preventing secondary reactions that produce gases.

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

Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O) 2 adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination.

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

Polyethylene in Dead-End Silica Nanopores: Forces and Mobility from Non-Equilibrium Statistical Mechanics and Exchange Spectroscopy Nuclear Magnetic Resonance

Billions of tons of plastic have been produced, and only a small fraction of this has been recycled. Tennakoon et al. [Nature Catalysis 3, 893 (2020)] developed a catalyst that repeatedly cleaves C 10 –C 30 hydrocarbons from the end of a polyethylene chain. The reaction occurs at a Pt nanoparticle at the base of a cylindrical silica mesopore with a diameter of 2 nm and a length of 110 nm. Portions of the polymer situated inside the pore can be differentiated from those outside using 13 C nuclear magnetic resonance (NMR), allowing the dynamics and extent of polymer threading to be monitored using two-dimensional (2D) exchange spectroscopy NMR. Here we construct a Fokker–Planck equation for the polymer dynamics by assuming a reptation diffusivity and a graduated adsorption free energy that depends linearly on the depth of polymer penetration in the pore. The solutions allow us to predict the intensities of the 2D NMR resonances as a function of time. We use the solutions to extract a polymer diffusivity at each temperature and estimate the per-segment desorption free energy, enthalpy, and entropy. Random and systematic errors are examined to test key assumptions in the theory and interpretation of the experiments.

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

Sorbmatech{sup R}Cs, an Innovative Highly Selective Cs Sorbent for Wastewater Decontamination - 20065

The treatment of radioactive wastewater from the operating nuclear industry (energy production, reprocessing of spent fuel, decommissioning of shut-down facilities, etc.) or in case of incidental or accidental situation (such as Fukushima Daichii NPP accident) is an important issue requiring constant improvement of the technologies and techniques used to prevent radioactive releases into the environment and/or to reduce the production of secondary waste. CEA, Orano and CTI are collaborating since 2014, with the support of the French government's program 'investments for the future', to develop Sorbmatech{sup R}Cs, an innovative and patented selective sorbent (Grandjean and Barre 2014) to deal with the removal of radioactive {sup 137}Cs, one of the most hazardous isotope to be managed in nuclear waste, highly efficient either in agitated reactor or in column process. Sorbmatech{sup R}Cs sorbent consists of mesoporous silica particles loaded with potassium-copper hexacyanoferrate nanoparticles (KCu-HCF). This peculiar structure enables much faster sorption kinetics compared to denser crystalline structures, such as Silicotitanate or Zeolite sorbents, whose drawback consists in hindering the diffusion process through the material, and whose larger sorbent particles slow down the ion exchange process. The equilibrium of Sorbmatech{sup R}Cs is reached in few minutes, even at high flow rates in a fixed-bed column process (up to 10 m.h{sup -1} Darcy velocity) with low drop pressure. Moreover, Sorbmatech{sup R}Cs can be used over a wide pH range from 2 to 10 and has a very high selectivity towards {sup 137}Cs even in brine solution (saline, mineral or sea water). This new sorbent also has a K{sub d} higher than 10{sup 5} mL.g{sup -1} depending on the salinity of the wastewater, enabling a highly efficient removal of Cs trace in radioactive wastewater compared to Cs selective sorbent such as Zeolites and Silicotitanates. Its radiological resistance enables the treatment of high, medium and low activity wastewater. The CEA-Orano-CTI/ALSYS partnership leads to the development of a simple and low-cost synthetic route, which demonstrated large-scale manufacturing of the product on a batch of 100 kg. Two products have been developed and are ready for short run market introduction so far with grain size well adapted either for column processes or agitated reactors.. Finally, the industrial implementation has been studied and largely benefits from the properties of the sorbent. Indeed, its high sorption kinetics enable high flow rates resulting in a decrease of operation times, unit sizes, and volumes of secondary waste produced. Moreover, Sorbmatech{sup R}Cs is designed to be combined into a full and integrated solution, ranging from preliminary optimization of operating conditions through numerical dimensioning model, industrial implementation and treatment of the wastewater (through cartridge or preconditioned columns systems developed thanks to Orano's extensive expertise), to long-term stabilization of generated waste (under progress). (authors)

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

Templated Mesoporous Silica Outer Shell for Controlled Silver Release of a Magnetically Recoverable and Reusable Nanocomposite for Water Disinfection

Here, we encapsulated Fe 3 O 4 @SiO 2 @Ag (MS-Ag), a bifunctional magnetic silver core–shell structure, with an outer mesoporous silica (mS) shell to form an Fe 3 O 4 @SiO 2 @ 2 Ag@mSiO 2 (MS-Ag-mS) nanocomposite using a cationic CTAB (cetyltrimethylammonium bromide) micelle templating strategy. The mS shell acts as protection to slow down the oxidation and detachment of the AgNPs and incorporates channels to control the release of antimicrobial Ag + ions. Results of TEM, STEM, HRSEM, EDS, BET, and FTIR showed the successful formation of the mS shells on MS-Ag aggregates 50–400 nm in size with highly uniform pores ~4 nm in diameter that were separated by silica walls ~2 nm thick. Additionally, the mS shell thickness was tuned to demonstrate controlled Ag + release; an increase in shell thickness resulted in an increased path length required for Ag + ions to travel out of the shell, reducing MS-Ag-mS’ ability to inhibit E. coli growth as illustrated by the inhibition zone results. Through a shaking test, the MS-Ag-mS nanocomposite was shown to eradicate 99.99+% of a suspension of E. coli at 1 × 10 6 CFU/mL with a silver release of less than 0.1 ppb, well under the EPA recommendation of 0.1 ppm. This high biocidal efficiency with minimal silver leach is ascribed to the nanocomposite’s mS shell surface characteristics, including having hydroxyl groups and possessing a high degree of structural periodicity at the nanoscale or “smoothness” that encourages association with bacteria and retains high Ag + concentration on its surface and in its close proximity. Furthermore, the nanocomposite demonstrated consistent antimicrobial performance and silver release levels over multiple repeated uses (after being recovered magnetically because of the oxidation-resistant silica-coated magnetic Fe 3 O 4 core). It also proved effective at killing all microbes from Long Island Sound surface water. The described MS-Ag-mS nanocomposite is highly synergistic, easy to prepare, and readily recoverable and reusable and offers structural tunability affecting the bioavailability of Ag + , making it excellent for water disinfection that will find wide applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Transparent silica aerogel slabs synthesized from nanoparticle colloidal suspensions at near ambient conditions on omniphobic liquid substrates

This paper presents a novel sol-gel method to synthesize large and thick silica aerogel monoliths at near ambient conditions using a commercial aqueous solution of colloidal silica nanoparticles as building blocks. To achieve slabs with high visible transmittance and low thermal conductivity, the method combines the strategies of (i) synthesizing gels on an omniphobic perfluorocarbon liquid substrate, (ii) aging at temperatures above room temperature, and (iii) performing solvent exchange with a low-surface-tension organic solvent prior to ambient drying. The omniphobic liquid substrates were used to prevent cracking and ensure an optically-smooth surface, while nanoparticle building blocks were small (<10 nm) to limit volumetric light scattering. Gels were aged at temperatures between 25 and 80 °C for up to 21 days to make them stronger and stiffer and to reduce shrinkage and cracking during ambient drying. Ambient drying was achieved by first exchanging water in the gel pores for octane, followed by drying in an octane-rich atmosphere to decrease capillary forces. The synthesized nanoparticle-based silica aerogel monoliths had thicknesses up to 5 mm, diameters up to 10 cm, porosities exceeding 80%, and thermal conductivities as low as 0.08 W m –1 K –1 . Notably, the slabs featured visible transmittance exceeding 75% even for slabs as thick as 5 mm. The as-synthesized aerogel monoliths were exposed to TMCS vapor to induce hydrophobic properties resulting in a water contact angle of 140° that prevented water infiltration into the pores and protected the aerogels from water damage. This simple synthesis route conducted at near ambient conditions produces hydrophobic aerogel monoliths with promising optically transparent and thermally insulating properties that can be adhered to glass panes for window insulation and solar-thermal energy conversion applications.

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

Pore-encapsulated catalysts for selective hydrogenolysis of plastic waste

Disclosed herein is a catalyst which comprises a silica core having an outer surface and a mesoporous silica shell having an outer surface and an inner surface with the inner surface being inside the outer surface of said mesoporous silica shell proximate to and surrounding the outer surface of said silica core. Wherein the outer surface of the mesoporous silica shell has openings leading to pores within the mesoporous silica shell which extend toward the outer surface of said silica core. The catalyst also includes catalytically active metal nanoparticles positioned within the pores proximate to said core, wherein the catalytic metal nanoparticles comprise about 0.0001 wt % to about 1.0 wt % of the catalyst. Also disclosed are methods of making the catalyst and using it to carry out a process for catalytically hydrogenolysizing a polyolefinic polymer.

Sadow, Aaron D.↗
DOE OSTI2020

Supported Pt Nanoparticles on Mesoporous Titania for Selective Hydrogenation of Phenylacetylene

Semi-hydrogenation of alkynes to alkenes is one of the most important industrial reactions. However, it remains technically challenging to obtain high alkene selectivity especially at a high alkyne conversion because of kinetically favorable over hydrogenation. In this contribution, we show that supported ultrasmall Pt nanoparticles (2.5 nm) on mesoporous TiO2 (Pt@mTiO2) remarkably improve catalytic performance toward semi-hydrogenation of phenylacetylene. Pt@mTiO2 is prepared by co-assembly of Pt and Ti precursors with silica colloidal templates via an evaporation-induced self-assembly process, followed by further calcination for thermal decomposition of Pt precursors and crystallization of mTiO2 simultaneously. As-resultant Pt@mTiO2 discloses a high hydrogenation activity of phenylacetylene, which is 2.5 times higher than that of commercial Pt/C. More interestingly, styrene selectivity over Pt@mTiO2 remains 100% in a wide phenylacetylene conversion window (20–75%). The styrene selectivity is >80% even at 100% phenylacetylene conversion while that of the commercial Pt/C is 0%. The remarkable styrene selectivity of the Pt@mTiO2 is derived from the weakened styrene adsorption strength on the atop Pt sites as observed by diffuse reflectance infrared Fourier transform spectroscopy with CO as a probe molecule (CO-DRIFTS). Our strategy provides a new avenue for promoting alkyne to alkene transformation in the kinetically unfavorable region through novel catalyst preparation.

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

Discovery of Gold Nanoparticles in Marcellus Shale

A high density of gold (Au) nanoparticles has been observed on the surfaces of the coexisting opal nanospheres in kerogen-bearing shales from the Marcellus Formation. Our analyses of the Au nanoparticles and associated minerals indicate that this represents a new formation type of colloidal gold nanoparticles. Additionally, the opal nanospheres are a new kind of natural opal-A that is characteristic of the mesoporous texture formed through oil-in-water emulsion processes. High-resolution transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectroscopy analysis directly reveals spherical gold nanoparticles and gold nanorods associated with mesoporous opal nanospheres. Our newly found textures indicate that opal nanospheres may have facilitated the co-precipitation of pure gold nanoparticles in organic-bearing, reduced environments. Furthermore, our TEM observations provide distinct images of the initial phase of colloidal gold and silica, which may contribute to the formation of Au deposits involving "invisible" gold, secondary supergene enrichments, or high-grade gold accumulations. Finally, the discovery of Au nanoparticles in hydrocarbon-rich shale formations such as Marcellus (which contains 0.6-4.1 wt % gold/opal) suggests a potential for co-production of both gas/oil and gold-two valuable commodities.

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

Superior Fischer-Tropsch Performance of Uniform Cobalt Nanoparticles Deposited into Mesoporous SiC

Electrochemically-derived well-crystalline mesoporous silicon carbide (pSiC) was used to host cobalt nanoparticles and to show superior catalytic performance during the CO hydrogenation according to Fischer-Tropsch. Colloidal metal particles (9 ± 0.4 nm) were prepared independently before depositing them into pSiC and, for comparison purposes, into commercially available silica (Davisil) and foam-like MCF-17 supports. The Co/pSiC catalyst demonstrated the highest catalytic activity of 117 ?molCO gCo-1 s-1 at 220 °C in the Fischer-Tropsch reaction, while the silica supported cobalt samples showed about one order of magnitude less activity. A significant increase in the C5+ hydrocarbons selectivity for Co/pSiC was observed. The stable performance of the catalyst is attributed to the high dispersion of the active phase and the use of silicon carbide acting as a thermally conductive and chemically inert porous support.

lablokou, V. S.↗
DOE OSTI2025

Metal–Oxide Interface Sites Created Using Atomic Layer Deposition and Tested for CO Oxidation

The performance of catalysts made out of Pt supported on TiO 2 thin films grown on SBA-15 (a silica mesoporous material) by atomic layer deposition (ALD) was characterized systematically by combining in situ infrared absorption spectroscopy (IR) with other techniques including electron microscopy and adsorption−desorption isothermal measurements. The titania films in the resulting high-surface-area catalysts were evenly distributed throughout the inner surface of the SBA-15 mesopores, and their thickness could be controlled at a submonolayer level, with 3 to 4 TiO 2 ALD cycles needed for the complete coverage of the silica sites. The titania films could be deposited either before or after adding the metal (Pt), which was dispersed in the form of small nanoparticles (NPs) approximately 4−6 nm in diameter, in order to exert some control on the density and nature of the Pt/TiO 2 interface sites. One important lesson deriving from this work is that such an order of deposition leads to significantly different catalysts in spite of the fact that most of their structural properties are similar. If the Pt is deposited on the titania films, the resulting metal NPs are slightly smaller than those grown on silica and display CO adsorption sites with lower surface Pt coordination numbers. On the other hand, when TiO 2 is deposited on the Pt/SBA-15 starting material, some titania grows on the metal and partially blocks its surface while also creating new interface sites where CO binds more weakly and displays lower C−O stretching frequencies. In terms of catalytic performance, the results from in situ IR CO site titration and kinetic measurements combined suggest a mechanism where CO first adsorbs on Pt atop sites and then migrates to Pt/TiO 2 interface sites, where oxidation takes place. Both types of sites appear to be similar in all the catalysts tested, but catalytic performance could be optimized by tuning their surface densities. Maximum catalytic activity was obtained when the TiO2 films were deposited first and with TiO 2 coverages of at least half a monolayer, that is, after at least 2 ALD cycles.

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

Heterobinuclear Molecular Precursors Direct the Formation of Supported Subnanometer Cu–M Clusters with Tunable Catalytic Behavior

Subnanometer bimetallic clusters hold great promise for catalytic applications due to their unique electronic properties and high surface-to-volume ratios. However, precise control over their composition and size remains a major challenge, particularly for immiscible metal pairs. Here, we report a surface-anchored molecular approach for synthesizing ∼0.7–0.8 nm Cu–M (M = Ru, Mo, W, Fe) bimetallic clusters on mesoporous silica supports, using heterobinuclear N-heterocyclic carbene (NHC)-based complexes as precursors. The NHC ligand functionalized with an alkoxysilane anchor enables robust grafting to the silica interface. Controlled calcination and reduction lead to subnanometer clusters with tunable composition, dictated by the metal–metal bond stability in the precursor. In situ transmission electron microscopy reveals cluster growth proceeds via sintering of adjacent surface-bound units, while elevated temperatures above 300 °C triggering diffusion and phase separation. Catalytic testing in ethylene hydrogenation demonstrates composition-dependent activity and kinetics, with CuRu and CuW clusters exhibiting lower apparent activation energy barriers compared with monometallic Cu nanoparticles. This study establishes a generalizable strategy for the interfacial synthesis of alloyed clusters from molecular precursors and provides mechanistic insight into how precursor design governs nanostructure formation and catalytic behavior.

N-heterocyclic carbene↗
DOE OSTI2022

The effect of silica oxide support on the catalytic activity of nickel-molybdenum bimetallic catalyst toward ethanol steam reforming for hydrogen production

This work investigates the effects of molybdenum promoter and silica oxide (SiO 2 ) support morphology on the ethanol steam reforming (ESR) performance of Nickel-Molybdenum (NiMo) bimetallic catalysts. Ordered mesoporous SiO 2 (SBA-15) and commercial SiO 2 supports were used as the oxide support materials. The synthesized catalysts were prepared via the wet impregnation method and characterized via XRD, H 2 -TPR, BET, FTIR, and Raman techniques. This study shows that NiMo bimetallic catalyst supported on SBA-15 has superior catalytic activity and better coking resistance at an intermediate temperature of 600 ⁰C than commercial SiO 2 supported catalysts. The presence of a uniform mesoporous structure of SBA-15 with an average pore diameter of ~ 2 nm can obstruct the carbon formation, leading to improved coking resistance. The catalytic enhancement of NiMo bimetallic catalysts toward ESR can also be linked to the ability of Mo promoter in enhancing the interaction between NiMo nanoparticles and SiO 2 support materials and restraining agglomeration of Ni nanoparticles, which results in further improvement of NiMo nanoparticle dispersion and inhibit its sintering. The NiMo bimetallic catalysts supported on SBA-15 illustrated the high H 2 yield of ~ 54% and carbon conversion of ~ 89% with the excellent stability for ESR performed at 600 ⁰C and the steam-to-carbon ratio of 2 over 65 hours.

25 ENERGY STORAGE↗
DOE OSTI2023

Molecular-Weight-Dependent Infiltration and Adsorption of Polymers into Nanochannels

The mesoporous silica shell coating hydrogenolysis nano-catalysts alters the molecular weight distributions of cleaved polymer chains compared to catalysts without a shell. The shell, composed of radially aligned narrow cylindrical nanopores, reduces the formation of low-valued gaseous products and increases the median molecular weight of the product, thus enhancing the value of the products for polymer upcycling. Here, to understand the role of the mesoporous shell, we have studied the spatial distribution of polystyrene chains, used as a model polymer, in the nanochannels in both the melt phase and solution phase. In the melt, we observed from small-angle X-ray scattering experiments that the infiltration rate of the polymer into the nanochannels is inversely proportional to the molecular weight, which is consistent with theory. In theta solution experiments using UV–vis spectroscopy, we found that the shell significantly enhances polymer adsorption compared to nanoparticles without pores. In addition, the degree of polymer adsorption is not a monotonic function of molecular weight but initially increases with the molecular weight before eventually decreasing. The molecular weight for the peak adsorption increases with the pore diameter. This adsorption behavior is rationalized as resulting from a balance between the mixing entropy gain by surface adsorption and the conformational entropy penalty incurred by chains confined in the nanochannels. The spatial distribution of polymer chains in the nanochannels is visualized by energy-dispersive X-ray spectroscopy (EDX), and inverse Abel-transformed data reveals a less uniform polymer distribution along the primary pore axis for longer chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗