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At least 91 records · Page 5

Evaluation of acidity of hierarchical zeolites using a potentiometric titration method

The method of potentiometric titration and corresponding determination of pK a of acid sites by the Gran method was applied for hierarchical zeolite materials. For hierarchical Al-, Ga- and B-silicate zeolites of MOR, BEA, MFI and MTW structural types with the morphology of aggregated nanosheets, nanorods or close to spherical nanoparticles, the distribution of acid sites by strength was determined. Furthermore, the dependence of the acidity spectrum (strength of acid sites) on the type of zeolite structure and the nature of an isomorphously substituted cation, on the one hand, and on the morphology of zeolite nanocrystals, on the other hand, was demonstrated.

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Impact of Sn Lewis Acid Sites on the Dehydration of Cyclohexanol

The impact of Sn on the concentration and strength of acid sites in Al containing zeolites with MFI topology and their catalytic activity for the dehydration of cyclohexanol in the aqueous phase has been investigated. The materials maintain constant Al concentrations and consequently Bro̷nsted acid site (BAS) concentrations, while exhibiting an increasing concentration of Sn Lewis acid sites (LAS). The presence of water alters LAS (Sn) , leading to weak BAS (Sn) that increases the concentration of water in the zeolite micropore, while leaving the rate of dehydration of cyclohexanol unchanged. The TOF increases with the concentration of BAS (Al) in close contact with framework LAS (Sn) , referred to as BAS (Pair) . The increase in the Arrhenius pre-exponential factor, without affecting the activation barrier (E a ), leads to the hypothesis that the proximity of both sites allows for a later transition state induced by the polarization of the C–O bond, leading in turn to a higher transition entropy.

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Materials Flows Through Industry Tool

As next-generation technologies gain traction and change the marketplace, they allow the U.S. manufacturing sector to steadily evolve. However, they may be more energy and emissions intensive than current technologies. That’s why the National Renewable Energy Laboratory (NREL) developed the Materials Flows through Industry (MFI) tool to help manufacturers stay efficient and sustainable.

advanced manufacturing↗

Catalytic Dehydrogenation of Ethane over Mn Oxide Supported on Zeolite Chabazite

A new class of Mn-containing zeolites prepared by incipient wetness impregnation (IWI) have been found to catalyze the ethane dehydrogenation reaction with high selectivity (98 %+). Preparation by IWI leads to the formation of Mn 2 O 3 nanoparticles on the external surface of the zeolite crystals and herein is shown that the primary active sites for the reaction are located on the surface of these particles. Propane dehydrogenation is also successfully catalyzed by this catalyst. Furthermore, other Mn-zeolites (MFI and BEA) also have high reactivity and selectivity towards light alkane dehydrogenation.

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Activity of Brønsted Acid Sites in UiO-66 for Cyclohexanol Dehydration

Brønsted-acid sites are introduced via –OSO 3 H groups on the coordinatively unsaturated ZrO 2 nodes of UiO-66 metal organic frameworks (MOF). Such groups create strong Brønsted acidic sites that are active for cyclohexanol and ethanol dehydration (in liquid organic phase and gas phase, respectively). The intrinsic activity of Brønsted acid sites at nodes increased by increasing the concentration of sulfur, which is attributed to a shift from isolated µ 3 -OSO 3 H to two groups [(µ 3 -OSO 3 H) 2 ] interacting via hy-drogen bonding. For cyclohexanol dehydration, the relatively low activation enthalpies and negative transition entropies point to an E2 elimination mechanism, similar to dehydration with MFI zeolites in organic solvents. Furthermore, our results, show that the catalytic activity can be manipulated via the functionalization of zirconia nodes of the MOF framework.

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The role of catalyst acidity and microstructure on light olefin selectivity in polyethylene deconstruction in short contact time pulse Joule-heated reactors

The growing volume of plastics waste, compounded with a low recycling rate, has led to an alarming amount of plastics ending up in landfills or being incinerated. While pyrolysis offers a route for plastic waste deconstruction, its product distribution is often broad and poorly controlled due to unselective radical chemistry at high temperatures. We recently demonstrated that rapid pulse Joule-heated catalytic cracking over HZSM-5, combined with small fractions of steam, can achieve high selectivity (>80 %) toward C 2 -C 4 olefins, while significantly reducing coking compared to continuous Joule heating. Here, we investigate how acid catalyst properties, such as silica/alumina ratio, zeolite topology, and catalyst porosity, influence light olefin selectivity during polyethylene deconstruction via rapid pulse Joule heating. We demonstrate that silica-to-alumina ratios of ∼30 yield high light olefin selectivity, and small-pore zeolites favor light olefins at the expense of increased coke formation. To mitigate coking, we synthesize HZSM-5 nanosheets and hierarchical zeolites (MFI, FAU, and CHA). Furthermore, these catalysts achieve an ethylene selectivity of approximately 35 %, a twofold increase over prior catalytic pyrolysis. Additionally, co-feeding steam and incorporating hierarchical porosity reduce coke formation and enhance catalyst stability.

Catalytic cracking↗

Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols

The varying steric environment of zeolites subtly influences the rates of hydronium-ion-catalyzed dehydration of alcohols containing a cyclohexyl group in aqueous phase. Here, the investigated primary, secondary, and tertiary alcohols show an increasing stabilization of an ionic transition state in this sequence, i.e., an increasing tendency to move from a concerted (E2 mechanism) to a stepwise dehydration (E1 mechanism). Hydronium ions confined in the micropores of MFI and BEA zeolites induced much higher catalyzed rates than those in the aqueous phase. Independent of the reaction mechanism and the environment, however, all alcohols investigated follow one compensation correlation between activation enthalpy and entropy for primary, secondary, and tertiary alcohols, respectively. For a given transition enthalpy, the rate of dehydration is the higher the larger the reaction space (translated to the reaction entropy). Surprisingly, all compensation relations intersect in one point. These dependences for the different alcohols are also reflected in the turnover rates, for which all alcohols also intersect in a common point, which appears to mark the highest reaction rate for dehydration catalyzed by hydronium ions at the investigated temperature.

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Core-shell and egg-shell zeolite catalysts for enhanced hydrocarbon processing

Developing structure-performance relationships with the underlying goal of optimizing known zeolite catalysts involves the manipulation of their physicochemical properties. Here, we systematically assessed the impact of mesoscopic gradients in acid site concentration, which has generally received little attention in the design of zeolite catalysts for hydrocarbon upgrading. A series of core–shell MEL-type zeolites were synthesized with catalytically active ZSM-11 cores and passivated silicalite-2 shells of varying thickness. Our findings revealed that ZSM-11@silicalite-2 particles with ultrathin shells (<10 nm) have enhanced mass transport, characteristic of relatively smaller particles, compared to the corresponding ZSM-11 core. Additionally, catalytic testing using the methanol-to-hydrocarbon (MTH) reaction showed that core–shell zeolites exhibit longer lifetimes, higher total turnovers, and an unexpected promotion of the aromatic cycle in the hydrocarbon pool mechanism. Time-resolved acid titration of core and core–shell catalysts confirmed that the siliceous shell introduces a hydrophobic exterior that impacts molecular diffusion. In comparison, prepared MFI core-shells (ZSM-5@silicalite-1) showed similar enhancement in catalyst performance. Moreover, we prepared egg-shell configurations of each zeolite, silicalite-2@ZSM-11 and silicalite-1@ZSM-5, comprised of an inert core and catalytically active shell. This inverse design of the egg-shell created pseudo nanosheets with total turnovers that were markedly higher than their homogeneous counterparts. Collectively, this study demonstrated that mesoscopic gradients in acid concentration via the design of core–shell and egg-shell zeolites significantly improve catalyst performance over conventional analogues for hydrocarbon upgrading.

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Pairing Ga/Al-Zeolites with tailored acidity as tandem catalysts for the conversion of alcohols to olefins

Zeolites are versatile catalysts owing to their tunable acidity where the active site(s) can be placed within the crystal framework or as extra-framework species in confined pores. A common approach to tailor Brønsted acidity is heteroatom exchange involving the replacement of framework aluminum with alternative elements. Introduction of heteroatoms often results in less acidic catalysts that can be used in tandem reactions for targeted reactive intermediates. Here, in this study, we prepare a series of three different zeolites with MWW, CHA, and MFI frameworks as aluminosilicates and gallosilicates to demonstrate their performance in alcohol dehydration reactions. The two reactions examined in this study are methanol conversion to dimethyl ether and ethanol conversion to ethylene. Our findings reveal that Ga-zeolites exhibit superior performance with Ga-MCM-22 (MWW) achieving nearly 100% alcohol conversion and selectivity to desired products at contact times that are significantly less than most dehydration catalysts reported in literature. The unique properties of Ga-zeolites are attributed to their reduced acid site strength via a direct (one-pot) synthesis that avoids conventional time-intensive, multi-step post-synthesis modifications of Al-zeolites. Here we demonstrate the use of Ga-zeolites as tandem catalysts when paired with a downstream Al-zeolite in a dual-bed reactor configuration to convert cheaper reagents (alcohols) upstream to more desired intermediates as feeds for downstream catalysts to produce light olefins. We demonstrate that dual beds using Ga-zeolite – Al-ZSM-5 (upstream–downstream) pairings outperform single bed configurations with Al-ZSM-5 or a physical mixture (Ga-/Al-zeolite) for methanol to hydrocarbons reactions, with notable improvements in catalyst lifetime and increased light olefins selectivity. Similarly, dual beds using Ga-zeolite – Al-SSZ-13 (upstream–downstream) pairings result in improved performance for ethanol to propylene reactions with significant increases in propylene selectivity (>20 %) compared to a conventional single bed configuration of Al-SSZ-13. Overall, this study offers a new perspective on the use of heteroatom-exchanged zeolite catalysts in tandem reactions as a means of capitalizing on their reduced acid site strength and suggests differences in the intrinsic acidity of zeolite crystal structures.

42 ENGINEERING↗

Mechanistic insights into nitrogen activation on atomic Ru clusters in self-pillared pentasil using operando atomistic models and experimental kinetics

Alternative catalysts to the industrial Haber Bosch process have been of significant interest in the field of heterogeneous catalysis, yet realizing ammonia synthesis under mild conditions (e.g., 300 °C and 10 bar) is challenging due to the low per-pass conversion. One strategy is to promote the associative ammonia synthesis mechanism which eschews direct N-N bond cleavage. Here, in this work, we use self-pillared pentasil, a self-pillared hierarchical zeolite built by thin MFI zeolite nanosheets, as a support for subnanometric Ru clusters to synthesize ammonia. We show that Ru remains well-dispersed during reaction and further demonstrate that ammonia synthesis rates are higher than Cs-Ru/MgO. Reaction kinetics show a positive order in H 2 providing evidence for the associative mechanism, which then becomes negative in H 2 if Ru is allowed to aggregate into nanoparticles. Operando Density Functional Theory models for Ru speciation in SPP, free energy diagrams, and microkinetic modeling were then applied to develop a reaction mechanism that involves sequential hydrogenation of N 2 from metallic Ru clusters. For this hydrogenation to occur, there are site requirements for N 2 to adopt a bridge-bound configuration that facilitates sequential hydrogenation on single sites and metal clusters. These site requirements in turn inform the design of improved zeolite-supported ammonia synthesis catalysts.

36 MATERIALS SCIENCE↗

Preactivated zeolite nanosheet plate-tiled membrane on porous PVDF film: Synthesis and study of proton-selective ion conduction

Preactivated MFI zeolite nanosheet plates (ZNPs) with large areas (~2.0 × 2.0 μm 2 ) and nanometer thicknesses (~60 nm) were prepared directly in liquid-dispersed state. The individual ZNP was a stack of 4-nm-thick single crystalline zeolite nanosheets (ZNs) interlinked by Si–O–Si bonds between neighboring ZN surfaces. The dispersed open-pore ZNPs allowed formulating suspensions for tiling ZNP membranes on polymer substrates without requiring post-coating activation. A pinhole-free ZNP-tiled (ZNPT) membrane has been achieved on macroporous PVDF film by a self-repairing vacuum-assisted filtration coating method. The resultant ZNPT layer was ~500 nm-thick consisting of about 7 ZNP layers with inter-ZNP width and inter-ZNP entrance porosity around 9 nm and 2%, respectively. The ZNPT-PVDF membrane exhibited high selectivity to proton transport over vanadyl ion and low resistances to proton conduction in aqueous solutions. The membrane also demonstrated to function as an efficient ion separator for the vanadium redox flow battery. The reported synthesis of preactivated ZNP suspension may overcome the major hurdle to realizing polymer-supported ZN membranes, which is the inefficiency of existing methods in obtaining readily dispersible open-pore ZNs. Finally, the ZNPT-PVDF membrane can be a more affordable and sustainable alternative to the Nafion-based ion separation membranes.

36 MATERIALS SCIENCE↗

Self-seeded growth of very large open-structured zeolite nanosheet assemblies with extraordinary micropore accessibility

Zeolite nanosheets (ZNs) offer improved micropore accessibilities and transport properties for enhanced molecular catalysis and separations. However, practical application of the ZN materials is hampered by the lack of efficient synthesis methods. Here, in this work, a ZN self-seeded method is demonstrated for single-step reproduction of flower-like assemblies of very large MFI ZN plates. The ZN plates are ~60 nm-thick stacks of 4-nm-thick single-crystal sheets. The ZN flower growth involves terrace nucleation on the seed surfaces and subsequent ZN epitaxial growth in [010] orientation directed by a diquaternary agent. The open architecture of the assemblies prevented collapse and agglomeration of ZNs during thermal activation that effectively preserved the interconnected intra-sheet and inter-sheet micropore system. Thus, the ZN assemblies exhibited markedly enhanced molecular adsorption capacity and transport diffusivity for the probing xylene molecules as compared to the conventional crystals. The ZN assembly and its harvestable very large-sized ZNs have the potential for developing high-performance ZN adsorbents, catalysts, and molecular-sieve membranes.

36 MATERIALS SCIENCE↗

Rapid Crystallization of Zeolites with Controllable Defects: Disentangling Fluoride Concentration and pH Using NH 4 F

Zeolite synthesis is typically conducted either under basic conditions or in neutral fluoride media using hydrofluoric acid (HF). While basic (OH − ) conditions generally result in faster zeolite crystallization, they can also increase the likelihood of framework defects and crystal intergrowths. In contrast, synthesis in neutral fluoride media tends to produce fewer defects because fluoride balances positive charges from structure-directing agents. However, this method often requires significantly longer crystallization times and involves the handling of dangerous HF. In the present study, we pursue the best of both synthesis conditions, rapid syntheses with controllable defect concentrations, by disentangling of mineralizing agent and chargebalancing agent using ammonium fluoride (NH 4 F) as an alternative to HF. We have investigated the use of NH 4 F in the syntheses of siliceous and aluminum-containing zeolite A (LTA, small pore), ZSM-5 (MFI, medium pore), and siliceous Beta(*BEA, large pore). The crystallization times of all four zeolites decreased substantially with an increasing NH 4 F concentration. Crystallization times were reduced from 24 to 4 h (Si-LTA), 96 to 36 h (Al-LTA), 240 to 6 h (ZSM-5), and 24 to 3 h (Si-*BEA). Additionally, increasing the NH 4 F concentration in the synthesis mixtures decreases the defect densities of siliceous zeolites. Raman spectroscopy, along with 29 Si MAS NMR, 19 F MAS NMR, 13 C MAS NMR, and fluorine elemental analysis of Si-LTA samples confirms that the reduction in charged defects (Si−O − ) is due to the higher incorporation of F − within the double four-membered ring (D4R) present in the LTA samples. We show that the accelerated crystallization is due to the role of F − in enhancing the silica mineralization rate (formation of silicon hexafluoride species) and stabilizing D4Rs under basic conditions. As a result, combining basic and fluoride-mediated synthesis could therefore be advantageous for faster zeolite production and improved control over structural properties for a wide variety of zeolite structures.

Anions↗

MS25: Materials Science-Focused Benchmark Data Set for Machine Learning Interatomic Potentials

Here, we present MS25, a benchmark data set for evaluating machine learning interatomic potentials (MLIPs) across diverse materials-relevant systems including MgO surfaces, liquid water, zeolites, a catalytic Pt surface reaction, high-entropy alloys (HEAs), and disordered Zr-oxides. Five MLIP architectures (MACE, NequIP, Allegro, MTP, and Torch-ANI) are trained and tested, focusing not only on traditional metrics (energies, forces, and stresses) but also explicitly validating derived physical observables such as lattice constants, volumes, and reaction barriers. We find that most models reach comparable accuracy on standard error metrics across the simple systems, although equivariant MLIPs offer 1.5–2× improvements over nonequivariant MLIPs in energy and force error for structurally complex or compositionally disordered environments such as HEAs and Zr–O systems. Our analysis highlights that low errors in energy and force predictions do not guarantee reliable observables, emphasizing the necessity of explicit validation. We demonstrate limitations in cross-framework transferability, as models trained on one zeolite framework (CHA) fail to reliably generalize to predictions of structurally distinct frameworks (e.g., MFI). Size-extensive tests show some dependence on system size for MgO, resulting from forced periodicity. The HEA and Zr–O data sets are identified as challenging tests for future benchmarks and MLIP model architecture developments as they show significant differentiation in error between MLIP architectures and are still relatively difficult at 1000 training images. Moving forward, we recommend that benchmarking efforts shift their focus from marginal accuracy improvements in energy and force errors toward identifying and understanding model failure modes, rigorously assessing transferability, and evaluating how their errors affect observable predictions. For researchers looking to choose an MLIP architecture, we suggest selecting equivariant MLIP architectures if the complexity of the system is a challenge. For simple materials problems, auxiliary features such as integration with molecular dynamics engines, trade-offs between computational data set generation cost vs MLIP inference speed, and framework integration may play a more important decision factor than small differences in error metrics that are unlikely to matter for production-level research.

chemical structure↗

First-Principles Grand-Canonical Simulations of Water Adsorption in Proton-Exchanged Zeolites

Water appears by design or as impurities in many important reactive systems. For those catalyzed by porous solid acids, such as widely used zeolites, experimentally quantifying the amount or elucidating the structure of adsorbed water clusters at reaction conditions is challenging, while computational studies (e.g., first-principles molecular dynamics simulations) often need to assume the loading to examine solvation effects. Furthermore, we perform first-principles grand-canonical simulations to predict water adsorption to H-ZSM-5 zeolites under specified experimental conditions. Presampling with inexpensive force fields and a pool-based parallelization algorithm are used to improve simulation efficiency, while molecular dynamics is used to sample configurations involving hydronium species. We observe that H + exchange dramatically increases the hydrophilicity of zeolite MFI and an appreciable amount of water is present at very low relative humidities. At all conditions examined, the zeolitic protons are found to dissociate readily from the surface basic sites and become mobile by participating in the hydrogen-bonded chains of adsorbed water molecules.

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Virgin-like High-Density Polyethylene from Recycled Mixed Polyolefins

Reported herein is the compatibilization of mixed polyolefins containing a rheology modifier (M-PO RM ) derived from municipal solid waste (MSW) by using different types of compatibilizers. One compatibilizer was produced “in situ” during reactive extrusion (REX), and the other compatibilizers were commercial styrenic block copolymer and maleated polymer-based compatibilizers. Both “in situ” and commercial compatibilizers were first used in laboratory-controlled polyolefins containing a rheology modifier (denoted as L-PO RM ) and were investigated for their mechanical properties. The study was then extended to a rheology modifier containing recycled mixed polyolefins (M-PO RM ), where the effects of both compatibilizers were evaluated. Compared to the in situ and other commercial compatibilizers, the styrenic block copolymer offered superior performance, as it enabled the synthesis of virgin-like high-density polyethylene (HDPE) from the M-PO RM . The findings suggest that M-PO RM can be transformed into blends with virgin HDPE-like properties, thus offering an industrially relevant approach for the re- and upcycling of mixed polyolefins. Finally, the M-PO RM pellets with uniform MFI and good mechanical properties can be used as injection mold feedstocks for different applications such as in the construction and automotive sectors.

compatibilization↗

Shape-Selective Synthesis of Alkylcyclopentenyl Cations in Zeolites and Spectroscopic Distinction of Constitutional Isomers

Alkylcyclopentenyl cations belong to the long-lived intermediates that make up the “hydrocarbon pool” during the catalytic conversion of methanol on zeolites, and recent works show that such cations contribute to olefin and aromatics formation. From liquid phase chemistry, two types of alkylcyclopentenyl cations are known and distinguished by the substituent at the central carbon (C-2) of the allylic system: a more stable type with a methyl group at the C-2 and a less stable type with hydrogen at the C-2. The following three linked objectives are pursued: (i) IR spectroscopic distinction of the different substitution patterns at the allylic system of alkylcyclopentenyl cations, (ii) the role of the zeolite framework in determining the substitution pattern, and (iii) identification of alkylcyclopentenyl cations from precursors relevant to methanol-to-olefins conversion. UV–vis and IR spectroscopy are applied in situ to characterize alkylcyclopentenyl cations produced by adsorption of a pentaalkylcyclopentadiene or by adsorption and thermally induced cyclization of 2,6-dimethyl-2,4,6-octatriene. Prior knowledge of electronic spectra is combined with DFT-computed and experimental IR spectra to establish the frequency of the C–H vibration of the C-2 hydrogen-substituted type, and a characteristic red shift of the asymmetric allylic stretching vibration (Δν ≈ -20 to -30 cm –1 ) after replacing hydrogen by methyl at the central carbon of the allylic system. Although DFT demonstrates that both types of ions fit into medium- and large-pore zeolites and that the C-2 methyl-substituted type is thermodynamically favored even in the pores of the considered zeolites, formation of alkylcyclopentenyl cations is found by UV–vis and IR spectra to be shape-selective. The bulkier C-2 methyl-substituted type is detected in large-pore zeolites (MOR, BEA) and in the intersections of medium-pore zeolites (MFI), whereas in channels of medium size (TON), the less bulky C-2 hydrogen-substituted type is exclusively formed. Finally, the type of ion formed and its overall size are dictated by the zeolite framework and are independent of the precursor; the same type of alkylcyclopentenyl cation as found through cyclization of dimethyloctatriene could be generated from ethene.

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