Zeolite Cluster Research Articles

Regioselective encapsulation of Pd clusters in hollow polycrystalline shell

Zeolite catalysts have been widely applied in petroleum and chemical industries. Nano/hierarchical structure could improve the utilization efficiency of active sites, especially for metal species encapsulated in zeolites. However, the uniformity of zeolite surface and crystallinity would decrease, leading to low stabilization effect. Herein, we developed a seed-directed method to prepare Pd clusters (∼1.3 nm) regioselectively encapsulated in hollow polycrystalline shell of Silicalite-1 zeolite. In nitrobenzene hydrogenation reaction, the optimized Pd@S-1-hp showed a high conversion of 92.2 % at 110 °C, which is 40 % higher than that of Pd clusters in bulk zeolite. Sub-nano Pd species in polycrystalline shell could significantly shorten the diffusion length on the basis of strong microporous confinement effect. Catalytic hydrogenation activity remained stable after six cycles. This structure could be extended to heterogeneous reactions suffering from diffusion limitation.

Encapsulation of Ru nanoparticles within NaY zeolite for ammonia decomposition

Uniform and minuscule Ru particles confined in NaY zeolite (Ru@NaY) are prepared via a simple in situ synthesis technique. Transmission electron microscopy studies indicate that the Ru particles are encapsulated within the micropores of NaY zeolite and form a uniform size of 1.5–3.5 nm. Thanks to the effective confinement of Ru particles within the NaY zeolite, as well as the high concentration of B-5 sites and basic sites, the prepared Ru@NaY catalysts show excellent NH3 decomposition activity and highly efficient H2 formation. Notably, the 0.1Ru@NaY catalyst achieves a 92.7% NH3 conversion and a H2 formation rate of 690 mmol min−1·gRu−1 at 500 °C and GHSV = 9000 mLNH3·gcat−1·h−1 and shows outstanding stability throughout a 95-h lifetime test. The encapsulation synthesis of Ru clusters in zeolites endows the catalysts with exceptional catalytic activities and excellent stability, thus providing new prospects for the production of H2 from NH3 decomposition.

Subnanometric bimetallic Pt–Pd clusters in zeolites for efficient hydrogen production and selective tandem hydrogenation of nitroarenes

Subnanometric bimetallic Pt–Pd clusters in zeolites for efficient hydrogen production and selective tandem hydrogenation of nitroarenes

Confining platinum clusters in indium-modified ZSM-5 zeolite to promote propane dehydrogenation

Designing highly active and stable catalytic sites is often challenging due to the complex synthesis procedure and the agglomeration of active sites during high-temperature reactions. Here, we report a facile two-step method to synthesize Pt clusters confined by In-modified ZSM-5 zeolite. In-situ characterization confirms that In is located at the extra-framework position of ZSM-5 as In+, and the Pt clusters are stabilized by the In-ZSM-5 zeolite. The resulting Pt clusters confined in In-ZSM-5 show excellent propane conversion, propylene selectivity, and catalytic stability, outperforming monometallic Pt, In, and bimetallic PtIn alloys. The incorporation of In+ in ZSM-5 neutralizes Brønsted acid sites to inhibit side reactions, as well as tunes the electronic properties of Pt clusters to facilitate propane activation and propylene desorption. The strategy of combining precious metal clusters with metal cation-exchanged zeolites opens the avenue to develop stable heterogeneous catalysts for other reaction systems.

Subnanometer palladium-manganese clusters in hydrophilic amino-functionalized zeolites for efficient formic acid dehydrogenation

Formic acid (FA) has emerged as a promising candidate for hydrogen storage, due to its excellent stability, low cost, and renewability. The rational design of catalysts for FA dehydrogenation is crucial for integrating FA into the hydrogen economy system. Herein, subnanometric bimetallic Pd-Mn clusters were encapsulated within hydrophilic amino-functionalized silicalite-1 (S-1) zeolite via an in-situ ligand-protection direct H2 reduction method. The graft of amino groups within zeolites not only endowed the zeolites with alkaline sites, but also significantly improved the hydrophilicity of zeolites, and enhanced the interaction between zeolite supports and encapsulated metal species, forming highly active electron-enriched Pd species. Thanks to the high dispersion of metal species and synergy between Pd and Mn species as well as the additive alkaline sites and hydrophilicity of zeolites, the optimized PdMn0.25@S-1-NH2 catalyst exhibited a superhigh H2 evolution rate from FA decomposition, with a turnover frequency value of 11,401 molH2·molPd−1·h−1 at 333 K without any additives, overcoming almost all of the state-of-the-art heterogeneous catalysts under the similar catalytic condition. This study highlights the effective synergistic effect between metal species and supports for improving catalytic efficiency in FA dehydrogenation reactions, and also opens a new paradigm for the design of functionalized zeolite-encapsulated metal catalysts for other important catalytic reactions.

Structural insight into palladium-nickel clusters over mordenite zeolite for carbene-insertion reaction

The advancement of heterogeneous catalysts incorporating metal clusters in the nanometric size range has garnered significant attention due to their extraordinary catalytic activity and selectivity. The detailed characterization and understanding of the atomic structure of these metal clusters within catalysts is crucial for elucidating the underlying reaction mechanisms. In the present study, a distinctive three-atom PdNi cluster, characterized by two Pd atoms at terminal positions and a central Ni atom, was synthesized over mordenite zeolite. The presence of atomic PdNi clusters within the eight-membered ring side pocket area was confirmed by multiple advanced analytical techniques, including magic-angle spinning nuclear magnetic resonance spectroscopy, synchrotron X-ray powder diffraction, extended X-ray absorption fine structure spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy. The catalytic activity of the confined active species was examined by the carbene-mediated reactions of ethyl-2-diazoacetate to ethyl-2-methoxyacetate as a model reaction. Compared to the Pd-mordenite and Ni-mordenite, the PdNi-mordenite catalyst incorporates a PdNi cluster, which demonstrates a superior performance, achieving 100% conversion and high selectivity under the same reaction conditions. Our study elucidates the potential of constructing bimetallic clusters in zeolites, providing valuable insights for developing new heterogeneous catalysts applicable to a wide range of catalytic processes.

Regioselective hydroformylation with subnanometre Rh clusters in MFI zeolite

Regioselective hydroformylation with subnanometre Rh clusters in MFI zeolite

Solvent-Free Synthesis Enables Encapsulation of Subnanometric FeOx Clusters in Pure Siliceous Zeolites for Efficient Catalytic Oxidation Reactions.

Metal/metal oxide clusters possess a higher count of unsaturated coordination sites than nanoparticles, providing multiatomic sites that single atoms do not. Encapsulating metal/metal oxide clusters within zeolites is a promising approach for synthesizing and stabilizing these clusters. The unique feature endows the metal clusters with an exceptional catalytic performance in a broad range of catalytic reactions. However, the encapsulation of stable FeOx clusters in zeolite is still challenging, which limits the application of zeolite-encapsulated FeOx clusters in catalysis. Herein, we design a modified solvent-free method to encapsulate FeOx clusters in pure siliceous MFI zeolites (Fe@MFI). It is revealed that the 0.3-0.4 nm subnanometric FeOx clusters are stably encapsulated in the 5/6-membered rings intersectional voids of the pure siliceous MFI zeolites. The encapsulated Fe@MFI catalyst with a Fe loading of 1.4 wt % demonstrates remarkable catalytic activity and recycle stability in the direct oxidation of methane, while also promoting the direct oxidation of cyclohexane, surpassing the performance of conventional zeolite-supported Fe catalysts.

Oxygenic iron clusters in ZSM-5 zeolite promote quantum sieving of gaseous hydrogen isotopes

Oxygenic iron clusters in ZSM-5 zeolite promote quantum sieving of gaseous hydrogen isotopes

An alternative catalytic cycle for selective methane oxidation to methanol with Cu clusters in zeolites.

The partial oxidation of methane to methanol catalyzed by Cu-exchanged zeolites involves at present a three-step procedure that requires changing reaction conditions along the catalytic cycle. In this work we present an alternative catalytic cycle for selective methane conversion to methanol using as active species small Cu5 clusters supported on CHA zeolite. Periodic DFT calculations show that molecular O2 is easily activated on Cu5 clusters producing bi-coordinated O atoms able to dissociate homolytically a CH bond from CH4 and to react with the radical-like non-adsorbed methyl intermediate formed producing methanol, while competitive overoxidation to CO2 is energetically disfavored. The present mechanistic study opens a new avenue to design catalytic materials based on their ability to stabilize radical species.

In Situ Incorporation of Atomically Precise Au Nanoclusters within Zeolites for Ambient Temperature CO Oxidation.

Preserving ultrasmall sizes of metal particles is a key challenge in the study of heterogeneous metal-based catalysis. Confining the ultrasmall metal clusters in a well-defined crystalline porous zeolite has emerged as a promising approach to stabilize these metal species. Successful encapsulation can be achieved by the addition of ligated metal complexes to zeolite synthesis gel before hydrothermal synthesis. However, controlling the metal particle size during post-reduction treatment remains a major challenge in this approach. Herein, an in situ incorporation strategy of pre-made atomically precise gold clusters within Na-LTA zeolite was established for the first time. With the assistance of mercaptosilane ligands, the gold clusters were successfully incorporated within the Na-LTA without premature precipitation and metal aggregation during the synthesis. We have demonstrated that the confinement of gold clusters within the zeolite framework offers high stability against sintering, leading to superior CO oxidation catalytic performance (up to 12 h at 30 °C, with a space velocity of 3000 mL g-1 h-1).

Ultrasmall Pd Clusters in FER Zeolite Alleviate CO Poisoning for Effective Low-Temperature Carbon Monoxide Oxidation.

Ultrasmall Pd4 clusters form in the micropores of FER zeolite during low-temperature treatment (100 °C) in the presence of humid CO gas. They effectively catalyze CO oxidation below 100 °C, whereas Pd nanoparticles are not active as they are poisoned by CO. Using catalytic measurements, infrared (IR) spectroscopy, X-ray absorption spectroscopy (EXAFS), microscopy, and density functional theory calculations, we provide the molecular-level insight into this previously unreported phenomenon. Pd nanoparticles get covered with CO at low temperatures, which effectively blocks O2 activation until CO desorption occurs. Small Pd clusters in zeolites, in contrast, demonstrate fluxional behavior in the presence of CO, which significantly increases the affinity for binding O2. Our study provides a pathway to achieve low-temperature CO oxidation activity on the basis of a well-defined Pd/zeolite system.

First‐Principles Study of Optical Properties of Linde‐Type A Zeolite

Within the framework of density functional theory, electronic structures of Linde‐type A (LTA) zeolite membranes are calculated, and based on the electronic structures, several key optical properties of LTA zeolite membranes can be conveniently determined, with the method of the full‐potential linearized augmented plane wave under the random phase approximation for the boundaries and the generalized gradient approximation for the exchange–correlation potentials. The calculated optical properties as a function of frequency include the real and imaginary parts of the dielectric function ε(ω), the refraction index n(ω), the extinction coefficient k(ω), the reflectivity R(ω), the energy loss function L(ω), the absorption coefficient α(ω), and finally the optical conductivity σ(ω), along with specific directions of the primitive cell. It is demonstrated that the optical properties of the sodium LTA zeolite cluster appear anisotropic within the range of UV. The nature of anisotropy implies that all the functions are 3 × 3 tensors with nonzero off‐diagonal elements. Three diagonal and three off‐diagonal elements are simultaneously presented.

From Basic Research on Supported-Metal Catalysts to their Practical Applications for Reduction of Food Waste

Abstract Supported metal catalysts are one of the most important heterogeneous catalysts, and they are widely used in chemical processes such as naphtha reforming, purification of exhaust gas from automobiles and so on. However, rational design of supported metal catalysts is still a target in heterogeneous catalysis. The author had a hypothesis that metal nanoparticles in ordered pores of zeolite or mesoporous silica may exhibit novel catalytic properties. Based on this idea, we used micropores of zeolites to accommodate metal carbonyl clusters, and then mesoporous silica to prepare metal nanoparticles. First, we studied ship-in-bottle synthesis of Rh carbonyl clusters in zeolite and its reactivity. Rh6(CO)16 was synthesized in NaY zeolite accompanied with formation of a mononuclear Rh(CO)2, which acted as a carrier of 13CO in 12CO-13CO exchange reaction. Then we worked on synthesis of platinum nanoparticles in mesoporous silica, and found that high activity in preferential oxidation of CO in hydrogen and in low-temperature oxidation of ethylene. The high catalytic performance in ethylene oxidation has led to practical application of platinum/silica catalysts for preservation of fruits and vegetables, resulting in reduction of food waste. This article describes the development process of this research.

Insights into adsorption of various gases on extra-framework cations of zeolite: A dispersion corrected DFT study on zeolite cluster models with Li[formula omitted], Na[formula omitted] and K[formula omitted] charge compensating ions

Design of an economical and sustainable gas separation material is relevant in several industrial processes. Zeolites with tunable pore sizes are ideal molecular sieves of many gases. The adsorption centers of these molecular sieves are extra-framework Lewis acid centers. In this study, we attempt to delineate the electronic properties of such centers (Li+, Na+ and K+) and their sorption properties towards N2, O2, CO, CO2 and H2. Negative framework of zeolites are modeled using different cluster models that present distinct electronic environment and role of this environment on the Lewis acidity of the cation. The sorption property towards different gases is evaluated using dispersion corrected DFT studies. The results obtained are benchmarked for one of the studied model using CCSD calculations. The results indicate that while the local environment modulates the adsorption properties, the relative adsorption properties between different ions follow the same order irrespective of the type of negative framework modeled. This reveals that intrinsic atomic properties of the charge compensating cations drive the sorption properties of the zeolites. Adsorption energies compounded with the analysis of IR stretching frequencies of the adsorbed gases reveals that Li centers shows molecular adsorption (charge donation to the cationic centers) towards N2 as compared to O2 and towards CO2/CO as compared to H2, demonstrating the applicability of Li-Zeolites as ideal membranes for oxygen concentrators and syngas separation. These adsorption studies are ratified by the BOMD simulations at 300 K, where H2 and O2 desorbs while N2, CO and CO2 remains adsorbed to the cationic site.

An automated reaction route mapping for the reaction of NO and active species on Ag4 clusters in zeolites.

A computational investigation of the catalytic reaction on multinuclear sites is very challenging. Here, using an automated reaction route mapping method, the single-component artificial force induced reaction (SC-AFIR) algorithm, the catalytic reaction of NO and OH/OOH species over the Ag42+ cluster in a zeolite is investigated. The results of the reaction route mapping for H2 + O2 reveal that OH and OOH species are formed over the Ag42+ cluster via an activation barrier lower than that of OH formation from H2O dissociation. Then, reaction route mapping is performed to examine the reactivity of the OH and OOH species with NO molecules over the Ag42+ cluster, resulting in the facile reaction path of HONO formation. With the aid of the automated reaction route mapping, the promotion effect of H2 addition on the SCR reaction was computationally proposed (boosting the formation of OH and OOH species). In addition, the present study emphasizes that automated reaction route mapping is a powerful tool to elucidate the complicated reaction pathway on multi-nuclear clusters.

DFT calculations for adsorption of H2S and other natural gas compounds on (Fe, Co, Ni, Cu and Zn)–Y zeolite clusters

The acid compounds removal from natural gas by adsorption on zeolites is an environmentally friendly alternative technology for its purification and commercialization. However, despite numerous theoretical studies determining the adsorption energies for gases on zeolites are found, for important natural gas compounds adsorption on Y zeolite they are poorly reported, especially with respect to long range van der Waals interactions, the description of their nature and related thermodynamic properties. Thus, this work aims to pre-select transition metal-exchanged Y zeolite for selective removal of H2S and other acid compounds from natural gas streams by DFT calculations for H2S, COS, CO2 and CH4 adsorption on Fe–Y, Co–Y, Ni–Y, Cu–Y and Zn–Y zeolite clusters. Adsorption energies, thermodynamic properties, chemical hardness, electronegativity, Natural Bond Orbital (NBO) and Energy Decomposition Analysis (EDA) were determined using B3LYP hybrid functional and Grimme's D3 empirical dispersion correction. Comparison between H2S and other compounds adsorption energies indicates that Ni–Y zeolite has potential for selective removal of H2S, despite Co–Y zeolite presents stronger adsorption energy for all compounds. Moreover, the NBO and EDA analyzes reveal that there is a transfer of d electrons from H2S molecule to unoccupied orbitals of the cation. Charge transfer and polarization phenomena contribute mainly to the adsorption energy of H2S, COS and CO2 in transition metal-exchanged Y zeolite clusters, showing the presence of surface chemisorption.

Template Guiding for the Encapsulation of Uniformly Subnanometric Platinum Clusters in Beta-Zeolites Enabling High Catalytic Activity and Stability.

Subnanometric metal clusters have attracted extensive attention because of their unique properties as heterogeneous catalysts. However, it is challenging to obtain uniformly distributed metal clusters under synthesis and reaction conditions. Herein, we report a template-guidance protocol to synthesize subnanometric metal clusters uniformly encapsulated in beta-zeolite, with the metal ions anchored to the internal channels of the zeolite template via electrostatic interactions. Pt metal clusters with a narrow size range of 0.89 to 1.22 nm have been obtained on the intersectional sites of beta-zeolite (Pt@beta) with a broad range of Si/Al molar ratios (15-200). The uniformly distributed Pt clusters in Pt@H-beta are subject to strong electron withdrawal by the zeolite, which promotes transfer of active hydrogen, providing excellent activity and stability in hydrodeoxygenation reactions. A general strategy is thus proposed for the encapsulation of subnanometric metal clusters in zeolites with high thermal stability.

Template Guiding for the Encapsulation of Uniformly Subnanometric Platinum Clusters in Beta‐Zeolites Enabling High Catalytic Activity and Stability

AbstractSubnanometric metal clusters have attracted extensive attention because of their unique properties as heterogeneous catalysts. However, it is challenging to obtain uniformly distributed metal clusters under synthesis and reaction conditions. Herein, we report a template‐guidance protocol to synthesize subnanometric metal clusters uniformly encapsulated in beta‐zeolite, with the metal ions anchored to the internal channels of the zeolite template via electrostatic interactions. Pt metal clusters with a narrow size range of 0.89 to 1.22 nm have been obtained on the intersectional sites of beta‐zeolite (Pt@beta) with a broad range of Si/Al molar ratios (15–200). The uniformly distributed Pt clusters in Pt@H‐beta are subject to strong electron withdrawal by the zeolite, which promotes transfer of active hydrogen, providing excellent activity and stability in hydrodeoxygenation reactions. A general strategy is thus proposed for the encapsulation of subnanometric metal clusters in zeolites with high thermal stability.

Facile synthesis of sub-nanometer Cd4S6+ and Cd2S2+ cluster in zeolite Y and its structural characterization

Facile synthesis of sub-nanometer Cd4S6+ and Cd2S2+ cluster in zeolite Y and its structural characterization