Unraveling the Nature of Extraframework Catalytic Ensembles in Zeolites: Flexibility and Dynamics of the Copper-Oxo Trimers in Mordenite
Ontology highlight
ABSTRACT:
SUBMITTER: Khramenkova E
PROVIDER: S-EPMC8591661 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Mesostructured pillared zeolite materials in the form of lamellar phases with a crystal structure of mordenite (MOR) and ZSM-5 (MFI) were grown using CTAB as an agent that creates mesopores, in a one-pot synthesis; then into the CTAB layers separating the 2D zeolite plates were introduced by diffusion the TEOS molecules which were further hydrolyzed, and finally the material was annealed to remove the organic phase, leaving the 2D zeolite plates separated by pillars of silicon dioxide. To monitor the successive structural changes and the state of the atoms of the zeolite framework and organic compounds at all the steps of the synthesis of pillared MOR and MFI zeolites, the nuclear magnetic resonance method (NMR) with magic angle spinning (MAS) was applied. The 27Al and 29Si MAS NMR spectra confirm the regularity of the zeolite frameworks of the as synthetized materials. Analysis of the 1H and 13C MAS NMR spectra and an experiment with variable contact time evidence a strong interaction between the charged "heads" -[N(CH3)3]+ of CTAB and the zeolite framework at the place of [AlO4]- location. According to 27Al and 29Si MAS NMR the evacuation of organic cations leads to a partial but not critical collapse of the local zeolite structure.
| S-EPMC7587376 | biostudies-literature
Project description:Aluminosilicate-based zeolite materials, such as ZSM-5 and mordenite, are well-studied as catalysts. Typical approaches to synthesize these zeolites require either templates or seeds to direct ordered crystal growth and both of these are expensive and add to the complexity of zeolite synthesis. In this paper, we describe a solvent-free and template-free method to synthesize crystalline ZSM-5 and mordenite zeolites without any added seed crystals. Key to the success of this approach is a mechanochemical precursor pre-reaction step. High-energy ball-milling is used to initiate a solid-state metathesis (exchange) reaction between Na2SiO3 and Al2(SO4)3 reagents, forming crystalline Na2SO4 and well-mixed aluminosilicate precursor. The solid precursor mixture is thermally converted to crystalline ZSM-5 or mordenite at moderate 180 °C temperatures without solvents or an organic amine structure directing template. Variations in Si/Al ratios in the precursor mixture and additions of solid NaOH to the mechanochemical reaction were found to influence the subsequent growth of either crystalline ZSM-5 or mordenite zeolites. The crystalline zeolites from this solvent-free and template free method have high ∼300 m2 g-1 surface areas directly from the synthesis without requiring high-temperature calcination. These materials are also comparably active to their commercial counterparts in cellulose and glucose biomass catalytic conversion to hydroxymethylfurfural.
| S-EPMC9418510 | biostudies-literature
Project description:The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C-H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483-498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions.
| S-EPMC4919767 | biostudies-literature
Project description:Mordenite (MOR)-type zeolites with a Si/Al molar ratio of up to 13 with crystallite sizes of ca. 60 nm were successfully synthesized from Al-rich aluminosilicates with a Si/Al ratio of 2 and additional SiO2 under seed-assisted hydrothermal conditions for 6 h or longer without any organic structure-directing agents (OSDAs). In stark contrast, under the same hydrothermal conditions for 6 h, control experiments using starting reagent(s), such as Al-poor aluminosilicate, pure SiO2, tetraethyl orthosilicate, and Al(NO3)3, all of which are typically employed for zeolite synthesis, failed to yield MOR-type zeolites. The penta-coordinated Al species, which are present in Al-rich aluminosilicates and are more reactive than the tetra- and hexa-coordinated Al species typically found in alumina and Al-poor aluminosilicates, played a decisive role in the OSDA-free synthesis of MOR-type zeolites.
| S-EPMC7931214 | biostudies-literature
Project description:Memories are assumed to be represented by groups of co-activated neurons, called neural ensembles. Describing ensembles is a challenge: complexity of the underlying micro-circuitry is immense. Current approaches use a piecemeal fashion, focusing on single neurons and employing local measures like pairwise correlations. We introduce an alternative approach that identifies ensembles and describes the effective connectivity between them in a holistic fashion. It also links the oscillatory frequencies observed in ensembles with the spatial scales at which activity is expressed. Using unsupervised learning, biophysical modeling and graph theory, we analyze multi-electrode LFPs from frontal cortex during a spatial delayed response task. We find distinct ensembles for different cues and more parsimonious connectivity for cues on the horizontal axis, which may explain the oblique effect in psychophysics. Our approach paves the way for biophysical models with learned parameters that can guide future Brain Computer Interface development.
| S-EPMC5600840 | biostudies-literature
Project description:Noninvasive and ultra-accurate optical manipulation of nanometer objects has recently gained interest as a powerful tool in nanotechnology and biophysics. Self-induced back-action (SIBA) trapping in nano-optical cavities has the unique potential for trapping and manipulating nanometer-sized objects under low optical intensities. However, thus far, the existence of the SIBA effect has been shown only indirectly via its enhanced trapping performances. In this article, we present the first time direct experimental evidence of the self-reconfiguration of the optical potential that is experienced by a nanoparticle trapped in a plasmonic nanocavity. Our observations enable us to gain further understanding of the SIBA mechanism and to determine the optimal conditions for boosting the performances of SIBA-based nano-optical tweezers.
| S-EPMC6059943 | biostudies-literature
Project description:Catalytic ozonation process (COP) is considered as a cost-efficient technology for the treatment of refractory chemical wastewaters. The catalyst performance plays an important role for the treatment efficiency. The present study investigated efficiencies and mechanisms of manganese (Mn)-based Y zeolites in COPs for removing nitrobenzene from water. The catalysts of Mn/NaY and Mn/USY were prepared by incipient wetness impregnation, while Mn-USY was obtained by hydrothermal synthesis. Mn-USY contained a greater ratio of Mn2+ than Mn/NaY, and Mn/USY. Mn oxides loaded on Y zeolites promoted the COP efficiencies. Mn/NaY increased total organic carbon removal in COP by 7.3% compared to NaY, while Mn/USY and Mn-USY increased 11.5 and 15.8%, respectively, relative to USY in COP. Multivalent Mn oxides (Mn2+, Mn3+, and Mn4+) were highly dispersed on the surface of NaY or USY, and function as catalytic active sites, increasing mineralization. Mn-USY showed the highest total organic carbon removal (44.3%) in COP among the three catalysts, because Mn-USY had a higher ratio of Mn2+ to the total Mn oxides on the surface than Mn/NaY and Mn/USY and the catalytic effects from intercorrelations between Mn oxides and mesoporous surface structures. The hydroxyl radicals and superoxide radicals governed oxidations in COP using Mn-USY. Nitrobenzene was oxidized to polyhydroxy phenol, polyhydroxy nitrophenol, and p-benzoquinone. The intermediates were then oxidized to small organic acids and ultimately carbon dioxide and water. This study demonstrates the potential of Y zeolites used in COP for the treatment of refractory chemical wastewaters.
| S-EPMC7028746 | biostudies-literature
Project description:We have developed a suite of protein redesign algorithms that improves realistic in silico modeling of proteins. These algorithms are based on three characteristics that make them unique: (1) improved flexibility of the protein backbone, protein side-chains, and ligand to accurately capture the conformational changes that are induced by mutations to the protein sequence; (2) modeling of proteins and ligands as ensembles of low-energy structures to better approximate binding affinity; and (3) a globally optimal protein design search, guaranteeing that the computational predictions are optimal with respect to the input model. Here, we illustrate the importance of these three characteristics. We then describe OSPREY, a protein redesign suite that implements our protein design algorithms. OSPREY has been used prospectively, with experimental validation, in several biomedically relevant settings. We show in detail how OSPREY has been used to predict resistance mutations and explain why improved flexibility, ensembles, and provability are essential for this application.OSPREY is free and open source under a Lesser GPL license. The latest version is OSPREY 2.0. The program, user manual, and source code are available at www.cs.duke.edu/donaldlab/software.php.osprey@cs.duke.edu.
| S-EPMC3692370 | biostudies-literature
Project description:Dealuminated zeolites are widely used acid catalysts in research and the chemical industry. Bulk-level studies have revealed that the improved catalytic performance results from an enhanced molecular transport as well as from changes in the active sites. However, fully exploiting this information in rational catalyst design still requires insight in the intricate interplay between both. Here we introduce fluorescence and stimulated Raman scattering microscopy to quantify subcrystal reactivity as well as acid site distribution and to probe site accessibility in the set of individual mordenite zeolites. Dealumination effectively introduces significant heterogeneities between different particles and even within individual crystals. Besides enabling direct rationalization of the nanoscale catalytic performance, these observations reveal valuable information on the industrial dealumination process itself.
| S-EPMC4278416 | biostudies-literature
Project description:Incorporation of germanium in zeolites is well known to confer static flexibility to their framework, by stabilizing the formation of small rings. In this work, we show that the flexibility associated to Ge atoms in zeolites goes beyond this static effect, manifesting also a clear dynamic nature, in the sense that it leads to enhanced molecular diffusion. Our study combines experimental and theoretical methods providing evidence for this effect, which has not been described previously, as well as a rationalization for it, based on atomistic grounds. We have used both pure-silica and silico-germanate ITQ-29 (LTA topology) zeolites as a case study. Based on our simulations, we identify the flexibility associated to the pore breathing-like behavior induced by the Ge atoms, as the key factor leading to the enhanced diffusion observed experimentally in Ge-containing zeolites.
| S-EPMC6680141 | biostudies-literature