Beyond Creation of Mesoporosity: The Advantages of Polymer‐Based Dual‐Function Templates for Fabricating Hierarchical Zeolites

Direct synthesis of hierarchical zeolites currently relies on the use of surfactant‐based templates to produce mesoporosity by the random stacking of 2D zeolite sheets or the agglomeration of tiny zeolite grains. The benefits of using nonsurfactant polymers as dual‐function templates in the fabrication of hierarchical zeolites are demonstrated. First, the minimal intermolecular interactions of nonsurfactant polymers impose little interference on the crystallization of zeolites, favoring the formation of 3D continuous zeolite frameworks with a long‐range order. Second, the mutual interpenetration of the polymer and the zeolite networks renders disordered but highly interconnected mesopores in zeolite crystals. These two factors allow for the synthesis of single‐crystalline, mesoporous zeolites of varied compositions and framework types. A representative example, hierarchial aluminosilicate (meso‐ZSM‐5), has been carefully characterized. It has a unique branched fibrous structure, and far outperforms bulk aluminosilicate (ZSM‐5) as a catalyst in two model reactions: conversion of methanol to aromatics and catalytic cracking of canola oil. Third, extra functional groups in the polymer template can be utilized to incorporate desired functionalities into hierarchical zeolites. Last and most importantly, polymer‐based templates permit heterogeneous nucleation and growth of mesoporous zeolites on existing surfaces, forming a continuous zeolitic layer. In a proof‐of‐concept experiment, unprecedented core–shell‐structured hierarchical zeolites are synthesized by coating mesoporous zeolites on the surfaces of bulk zeolites.     

Shape Selectivity in Adsorption of n‐ and Iso‐alkanes on a Zeotile‐2 Microporous/Mesoporous Hybrid and Mesoporous MCM‐48

The adsorption of linear and branched C5–C9 alkanes in the temperature range 50–250 °C on mesoporous MCM‐48 material and its microporous/mesoporous variant Zeotile‐2 at low surface coverage is investigated using the pulse chromatographic technique. On MCM‐48, the differences in adsorption between linear and branched alkanes are merely a result of differences in volatility, indicating that the MCM‐48 material does not present shape‐selective adsorption sites. On Zeotile‐2, there is a preferential adsorption of linear over branched alkanes. The difference arises from a difference in adsorption entropy rather than enthalpy. Upon their adsorption on Zeotile‐2 branched alkanes lose relatively more entropy than their linear isomers do. Zeolitic molecular pockets embedded in the walls of the mesoporous Zeotile‐2 impose steric constraints on the bulky isoalkanes. Zeotile‐2 combines adsorption properties from microporous and mesoporous materials. Compared to the nitrogen molecule, linear and branched C5–C9 alkanes are superior probes for investigating micropores and micropockets in hierarchical materials.     

Synthesis of ZSM‐5 Films and Monoliths with Bimodal Micro/Mesoscopic Structures

A route to synthesize ZSM‐5 crystals with a bimodal micro/mesoscopic pore system has been developed in this study; the successful incorporation of the mesopores within the ZSM‐5 structure was performed using tetrapropylammonium hydroxide (TPAOH)‐impregnated mesoporous materials containing carbon nanotubes in the pores, which were encapsulated in the ZSM‐5 crystals during a solid rearrangement process within the framework. Such mesoporous ZSM‐5 zeolites can be readily obtained as powders, thin films, or monoliths.     

Zeolite Catalysts with Tunable Hierarchy Factor by Pore‐Growth Moderators

The design of hierarchical zeolite catalysts is attempted through the maximization of the hierarchy factor (HF); that is, by enhancing the mesopore surface area without severe penalization of the micropore volume. For this purpose, a novel desilication variant involving NaOH treatment of ZSM‐5 in the presence of quaternary ammonium cations is developed. The organic cation (TPA⁺ or TBA⁺) acts as a pore‐growth moderator in the crystal by OH^?‐assisted silicon extraction, largely protecting the zeolite crystal during the demetallation process. The protective effect is not seen when using cations that are able to enter the micropores, such as TMA⁺ Engineering the pore structure at the micro‐ and mesolevel is essential to optimize transport properties and catalytic performance, as demonstrated in the benzene alkylation with ethylene, a representative mass‐transfer limited reaction. The hierarchy factor is an appropriate tool to classify hierarchically structured materials. The latter point is of wide interest to the scientific community as it not only embraces mesoporous zeolites obtained by desilication methods but it also enables to quantitatively compare and correlate various materials obtained by different synthetic methodologies.     

Interplay of Properties and Functions upon Introduction of Mesoporosity in ITQ‐4 Zeolite

The introduction of mesoporosity in zeolites is often directly coupled to changes in their overall catalytic performance without the detailed assessment of other key functions required for the rational design of the catalytic process such as accessibility, adsorption, and transport. This study presents an integrated approach to study property–function relationships in hierarchical zeolites. Accordingly, desilication of the 1D ITQ‐4 zeolite in alkaline medium is applied to develop different degrees of mesoporosity. Along with porosity modification, significant changes in composition, structure, and acidity occur. Relationships are established between the physicochemical properties of the zeolites and their characteristics in the adsorption and elution of light hydrocarbons (C₂ to C₅, alkanes and alkenes) as well as in the catalytic activity in low‐density polyethylene (LDPE) pyrolysis. The recently introduced hierarchy factor can appropriately relate porosity changes to catalytic performance.     

Hierarchical FAU‐ and LTA‐Type Zeolites by Post‐Synthetic Design: A New Generation of Highly Efficient Base Catalysts

Hierarchical FAU‐ and LTA‐type catalysts are prepared by post‐synthetic modifications and evaluated in the base‐catalyzed Knoevenagel condensation of benzaldehyde with malononitrile. A novel route to attain mesoporous Al‐rich zeolites (A and X) is demonstrated, while mesoporous Y and USY zeolites are prepared using recently developed methods. Base functionality is introduced by alkali ion exchange (Cs, Na) or by high‐temperature nitridation in ammonia. A thorough characterization of the zeolites' structure, composition, porosity, morphology, and basicity demonstrates that the presence of a secondary mesopore network enhances the ion‐exchange efficiency and the structural incorporation of nitrogen. The modified USY zeolites display twice the conversion, while the hierarchical A, X, and Y are up to 10 times more active based on the enhanced accessibility. These results demonstrate that the Knoevenagel condensation takes place predominately at the external surface, highlighting secondary porosity as a key criterion in the design of basic zeolite catalysts.     

Direct Synthesis of Highly Stable Mesoporous Molecular Sieves Containing Zeolite Building Units

A novel, one‐step synthesis of a highly stable mesoporous molecular sieve (MMS‐H), which has a structure analogous to MCM‐48 but which contains zeolite building units, is reported. A variety of experimental techniques—X‐ray diffraction (XRD), N₂ adsorption/desorption, transmission electron microscopy (TEM), Fourier‐transform infrared (FTIR) spectroscopy, hyperpolarized ¹²⁹Xe NMR, and solid‐state ²⁷Al and ³¹P magic‐angle spinning (MAS) NMR spectroscopies—have been used to characterize the framework structure, porosity, and acidity of this novel mesoporous/microporous composite material, which is also found to possess superior thermal, hydrothermal, steam, and mechanical stabilities.     

Preparation of Hollow Zeolite Spheres and Three‐Dimensionally Ordered Macroporous Zeolite Monoliths with Functionalized Interiors

A novel and flexible strategy involving hydrothermal transformation of guest‐incorporated zeolite‐seeded mesoporous silica spheres was proposed to prepare guest‐encapsulated hollow zeolite spheres and three‐dimensionally (3D) ordered macroporous zeolite monoliths. The guest species that were pre‐incorporated into the mesopores of silica spheres could be spontaneously encapsulated inside the formed hollow zeolite shells by consuming silica nutrition of the original mesoporous silica cores during the hydrothermal process. A wide range of guest materials with a size ranging from nanometers to micrometers, e.g., Ag and PdO nanoparticles, and mesoporous spheres of carbon and polymer of micrometer size were successfully encapsulated into both discrete hollow zeolite spheres and 3D ordered macroporous zeolite monoliths. Such materials are expected to find a variety of applications such as catalysis, adsorption, and novel microreactors for their special structures with active species inside and zeolitic porous shell outside.     

CoFe2O4 Nanocrystals Mediated Crystallization Strategy for Magnetic Functioned ZSM‐5 Catalysts

Zeolites have many applications in the petrochemical and fine chemical industry and their functionalization does expand the spectrum of potentials. However, the integration of functional nanocrystals into zeolite frameworks with controlled size, dispersion, and crystallization behavior still remains a significant challenge. Here, a new synthesis of magnetic functioned ZSM‐5 zeolite catalysts via a CoFe₂O₄ nanocrystal mediated crystallization strategy is reported. It is found that high crystallinity of CoFe₂O₄ nanocrystals results in a well‐dispersed encapsulation of them into a single‐crystal of ZSM‐5 due to non‐further‐grown nanocrystals during the fast ZSM‐5 growth. On the contrary, low crystallinity of CoFe₂O₄ nanocrystals leads to the polycrystalline zeolite growth due to the secondary growth of nanocrystals accompanied by the zeolite crystallization and large lattice mismatch between them. The successful encapsulation of small CoFe₂O₄ nanocrystals (≈4 nm) into single crystals lies on the preattachment of them into solid silica gel. During the growth of ZSM‐5 crystals, no secondary growth of nanocrystals happens and its motion is restricted. The encapsulation of magnetic CoFe₂O₄ nanocrystals not only endows magnetic function into zeolites for the first time, but also does not impact catalytic performance of ZSM‐5 in acetalization of cyclohexanone with methanol, which is highly promising in catalytic industries.     

Hydrophilic and Antimicrobial Zeolite Coatings for Gravity‐Independent Water Separation

Condensing heat exchangers onboard manned spacecraft require hydrophilic fin surfaces to facilitate wetting and wicking of condensate to achieve gravity‐independent water separation in the zero‐ or micro‐gravity environment of space. In order to prevent the proliferation of microbes, the coating must also be biocidal. Here we show for the first time that zeolite A and ZSM‐5 coatings deposited via in‐situ crystallization on stainless steel and aluminum alloys have excellent hydrophilicity, biocidal properties, and adhesion. Water contact angles below 5° were obtained on most substrates tested. When silver‐ion exchange is carried out on the zeolite A coating, it becomes highly antibacterial. This biocidal capability of zeolite A is regenerative by repeated ion exchange. All coatings exhibit the highest rating of 5B as determined by adhesion test ASTM D‐3359‐02 (American Society for Testing and Materials). These properties, in addition to zeolite coating's low‐temperature crystallization process and demonstrated corrosion resistance, make zeolite coatings advantageous over the current sol–gel coatings and well suited for use in condensing heat exchangers onboard manned spacecraft.     

“Brain‐Coral‐Like” Mesoporous Hollow CoS2@N‐Doped Graphitic Carbon Nanoshells as Efficient Sulfur Reservoirs for Lithium–Sulfur Batteries

Hollow carbon materials are considered promising sulfur reservoirs for lithium–sulfur batteries owing to their internal void space and porous conductive shell, providing high loading and utilization of sulfur. Since the pores in carbon materials play a critical role in the infusion of sulfur, access of the electrolyte, and the passage of lithium polysulfides (LPSs), the creation and tuning of hierarchical pore structures is strongly required to improve the electrochemical properties of sulfur/porous carbon composites, but remains a major challenge. Herein, a “brain‐coral‐like” mesoporous hollow carbon nanostructure consisting of an in situ‐grown N‐doped graphitic carbon nanoshell (NGCNs) matrix and embedded CoS₂ nanoparticles as an efficient sulfur host is presented. The rational synthetic design based on metal–organic framework chemistry furnishes unusual multiple porosity in a carbon scaffold with a macrohollow in the core and microhollows and mesopores in the shell, without the use of any surfactant or template. The CoS₂@NGCNs/S composite electrode facilitates high sulfur loading (75 wt%), strong adsorption of LPSs, efficient reaction kinetics, and stable cycle performance (903 mAh g^?1 at 0.1 C after 100 cycles), derived from the synergetic effects of the dual hollow features, chemically active CoS₂, and the conductive and mesoporous N‐doped carbon matrix.     

Transparent Mesoporous Nanocomposite Films for Self‐Cleaning Applications

A versatile approach is studied for the elaboration of TiO₂ based photocatalytic coatings for self‐cleaning applications on transparent substrates. The basic principle of the synthesis relies on the use of preformed TiO₂ colloidal particles that are further dispersed within a transparent silica binder with a mesoporous structure. Film porosity in the nanometer range is controlled by achieving the sol–gel silica condensation around self‐organized micellar assemblies of a templating copolymer surfactant. The latter also acts as a stabilizer for the TiO₂ particles, thus preserving their high dispersion within the film so that excellent optical properties are maintained even for high TiO₂ loading (up to 50 %). Studies of photodegradation kinetics show that such mesoporous films are at least 15 times more active than films synthesized with a usual microporous silica binder. Moreover, the measured quantum‐yield efficiency (1.1 %) is found to be among the highest reported up to now. Improved photoactivity of the films is discussed as resulting from the closer proximity between the organic molecules and the surface of the TiO₂ crystallites as well as the improved diffusion rate of water and oxygen through the interconnected pore network.     

Pure‐Silica‐Zeolite MFI and MEL Low‐Dielectric‐Constant Films with Fluoro‐Organic Functionalization

The synthesis of organic‐functionalized pure‐silica‐zeolites (PSZs) with MFI‐ and MEL‐type structures for low‐k applications prepared through a direct‐synthesis method by adding a fluorinated silane to the synthesis solution is reported. The added fluorine functionality increases the hydrophobicity of the zeolites, which are characterized by scanning electron microscopy, X‐ray diffraction, ²⁹Si and ¹⁹F solid‐state NMR spectroscopy, nitrogen adsorption, and thermogravimetric analysis. The functionalized zeolite powders have low water content and calcined spin‐on films prepared from the functionalized nanoparticle suspensions exhibit higher water contact angles and lower k values (2.1 and 1.8 for the functionalized MFI‐ and MEL‐type zeolites, respectively) than PSZ films. The use of a direct‐synthesis method to decrease the moisture adsorption in the films eliminates the extra post‐spin‐on silylation steps that are traditionally used to render the zeolite films hydrophobic.     

Hierarchical Porosity in Self‐Assembled Polymers: Post‐Modification of Block Copolymer–Phenolic Resin Complexes by Pyrolysis Allows the Control of Micro‐ and Mesoporosity

It is shown that self‐assembled hierarchical porosity in organic polymers can be obtained in a facile manner based on pyrolyzed block‐copolymer–phenolic resin nanocomposites and that a given starting composition can be post‐modified in a wide range from monomodal mesoporous materials to hierarchical micro‐mesoporous materials with a high density of pores and large surface area per volume unit (up to 500–600 m² g^–1). For that purpose, self‐assembled cured composites are used where phenolic resin is templated by a diblock copolymer poly(4‐vinylpyridine)‐block‐polystyrene (P4VP‐b‐PS). Mild pyrolysis conditions lead only to monomodal mesoscale porosity, as essentially only the PS block is removed (length scale of tens of nanometers), whereas during more severe conditions under prolonged isothermal pyrolysis at 420 °C the P4VP chains within the phenolic matrix are also removed, leading to additional microporosity (sub‐nanometer length scale). The porosity is analyzed using transmission electron microscopy (TEM), small‐angle X‐ray scattering, electron microscopy tomography (3D‐TEM), positron annihilation lifetime spectroscopy (PALS), and surface‐area Brunauer–Emmett–Teller (BET) measurements. Furthermore, the relative amount of micro‐ and mesopores can be tuned in situ by post modification. As controlled pyrolysis leaves phenolic hydroxyl groups at the pore walls and the thermoset resin‐based materials can be easily molded into a desired shape, it is expected that such materials could be useful for sensors, separation materials, filters, and templates for catalysis.     

Novel Three Dimensional Cubic Fm3m Mesoporous Aluminosilicates with Tailored Cage Type Pore Structure and High Aluminum Content

Novel three dimensional cubic Fm3m mesoporous aluminosilicates (AlKIT‐5) with very high structural order and unprecedented loadings of Al in the silica framework have been successfully prepared for the first time by using non ionic surfactant as a template in a highly acidic medium. The obtained materials have been unambiguously characterized in detail by several sophisticated techniques such as XRD, N₂ adsorption, HRTEM, HRSEM, EDS, elemental mapping, ²⁷Al MAS NMR, and NH₃‐TPD. We also demonstrate that the nature, and the amount of Al incorporation in the silica framework can easily be controlled by simply varying the n_H2O/n_HCl and the n_Si/n_Al ratios, and the Al sources in the synthesis gel. Among the Al sources examined, the Al isopropoxide (AiPr) is superior over other Al sources. ²⁷Al MAS NMR results reveal that the amount of tetrahedral Al in the framework can be controlled by simply adjusting the n_Si/n_Al ratio in the synthesis gel, which increases with increasing the Al incorporation. One of the interesting findings in the work is the increase of the specific surface area, specific pore volume and the pore diameter of AlKIT‐5 with increasing the Al incorporation in the silica framework (up to n_Si/n_Al ratio of 10) while retaining the well‐ordered three dimensional cage type porous structure, and the mechanism for the unusual behavior has been discussed in detail. Finally, the acidity and the catalytic activity in the acetylation of veratrole of the AlKIT‐5 catalysts have been studied and the results have been compared with the several zeolites catalysts. Among the catalysts examined, AlKIT‐5(10) is found to be superior over the zeolites catalysts such as mordenite, zeolite H‐Y, zeolite H‐β, and ZSM‐5.     

General Synthesis of Dual Carbon‐Confined Metal Sulfides Quantum Dots Toward High‐Performance Anodes for Sodium‐Ion Batteries

Sponge‐like composites assembled by cobalt sulfides quantum dots (Co₉S₈ QD), mesoporous hollow carbon polyhedral (HCP) matrix, and a reduced graphene oxide (rGO) wrapping sheets are synthesized by a simultaneous thermal reduction, carbonization, and sulfidation of zeolitic imidazolate frameworks@GO precursors. Specifically, Co₉S₈ QD with size less than 4 nm are homogenously embedded within HCP matrix, which is encapsulated in macroporous rGO, thereby leading to the double carbon‐confined hierarchical composites with strong coupling effect. Experimental data combined with density functional theory calculations reveal that the presence of coupled rGO not only prevents the aggregation and excessive growth of particles, but also expands the lattice parameters of Co₉S₈ crystals, enhancing the reactivity for sodium storage. Benefiting from the hierarchical porosity, conductive network, structural integrity, and a synergistic effect of the components, the sponge‐like composites used as binder‐free anodes manifest outstanding sodium‐storage performance in terms of excellent stable capacity (628 mAh g^?1 after 500 cycles at 300 mA g^?1) and exceptional rate capability (529, 448, and 330 mAh g^?1 at 1600, 3200, and 6400 mA g^?1). More importantly, the synthetic method is very versatile and can be easily extended to fabricate other transition‐metal‐sulfides‐based sponge‐like composites with excellent electrochemical performances.     

Template‐Free Fabrication and Enhanced Photocatalytic Activity of Hierarchical Macro‐/Mesoporous Titania

Hierarchical macro‐/mesoporous titania is prepared without the addition of templates or auxiliary additives at room temperature by the simple dropwise addition of tetrabutyl titanate to pure water, and then calcined at various temperatures. The products are characterized by X‐ray diffraction, N₂‐adsorption–desorption analysis, scanning electron microscopy, and the corresponding photocatalytic activity is evaluated by measuring the photocatalytic oxidation of acetone in air. The results reveal that hierarchical macro‐/mesoporous structures of titania can spontaneously form by self‐assembly in alkoxide–water solutions in the absence of organic templates or auxiliary additives. The calcination temperature has a strong effect on the structures and photocatalytic activity of the prepared titania. At 300 °C, the calcined sample shows the highest photocatalytic activity. At 400 and 500 °C, the photocatalytic activity slightly decreases. When the calcination temperature is higher than 500 °C, the photocatalytic activity greatly decreases because of the destruction of the hierarchical macro‐/mesoporous structure of the titania and the drastic decrease of specific surface area. The hierarchically macro‐/mesostructured titania network with open and accessible pores is well‐preserved after calcination at 500 °C, indicating especially high thermal stability. The macroporous channel structures are even preserved after calcination at 800 °C. This hierarchical macro‐/mesostructured titania is significant because of its potential applications in photocatalysis, catalysis, solar‐cell, separation, and purification processes.     

Hollow ZSM‐5 with Silicon‐Rich Surface,Double Shells,and Functionalized Interior with Metallic Nanoparticles and Carbon Nanotubes

Hollow ZSM‐5 single crystals with silicon‐rich exterior surface are prepared by a “dissolution–recrystallization” strategy in tetrapropylammonium hydroxide solution. Selective dissolution and exterior recrystallization cause the silicon components to migrate from the inside to outside, resulting in a regular void in the interior of the crystal, increased Brönsted acid sites and a silicon‐rich external surface. The as‐prepared hollow ZSM‐5 exhibits excellent acid catalysis with enhanced shape selectivity, as shown in biphenyl methylation as a probe reaction, which is attributed to the silicon‐rich external surface and thus the inhibition of isomerization on external surface. More interestingly, hollow ZSM‐5 single crystals with double shells are successfully prepared by layer‐by‐layer technique followed with dissolution–recrystallization strategy. Furthermore, hollow ZSM‐5 encapsulating iron and carbon nanotubes are successfully synthesized. Furthermore, hollow ZSM‐5 nanosized crystals with the interior functionalized as bimetallic (oxide) nanoparticles such as CuO‐Pd are also successfully synthesized.     

CaO‐Templated Growth of Hierarchical Porous Graphene for High‐Power Lithium–Sulfur Battery Applications

Structural hierarchy plays an important role in the biological world and for functional materials with optimized properties and high efficiency. As promising candidates for various energy storage systems, hierarchical porous carbon/graphene materials have been intensively investigated over the past decades, while the favorable regulation of their hierarchical porosity remains a challenge. Herein, porous CaO serves as both the catalyst and template for a versatile chemical vapor deposition (CVD) of hierarchical porous graphene. The gas atmosphere during CVD and nanostructure of adopted catalysts impact significantly on the graphitization degree and hierarchical porosity of resultant materials. The as‐fabricated material exhibits abundant microsized in‐plane vacancies, mesosized wrinkled pores, and macrosized strutted cavities, thereby contributing to a strong surface entrapment, short ion diffusion pathways, rapid mass transport, low interfacial resistance, and robust framework. It is demonstrated as a favorable scaffold for lithium–sulfur battery cathodes with superior rate capability, high coulombic efficiency, and excellent stability. A high capacity of 357 (656 ) is manifested at the current rate of 5.0 C, exhibiting a 74% retention of the capacity at 0.1 C. The first use of CaO‐templated CVD growth of graphene reported herein opens up new perspectives on the effective fabrication of hierarchical porous graphene materials on metal oxide catalysts with promising applications in energy storage, catalysis, adsorption, drug delivery, and so on.     

Hierarchical Y and USY Zeolites Designed by Post‐Synthetic Strategies

Strategic combinations of affordable and scalable post‐synthetic modifications enabled to design a broad family of hierarchical Y and USY zeolites (FAU topology) independent on the Si/Al ratio. Pristine (Y, Si/Al = 2.4), steamed (USY, Si/Al = 2.6), and steamed and dealuminated (USY, Si/Al = 15 and 30) zeolites were exposed to a variety of acid (H₄EDTA and Na₂H₂EDTA) and base (NaOH) treatments, which led to the introduction of mesopore surfaces up to 500 m² g^?1, while preserving the intrinsic zeolite properties. Pristine Y and USY zeolites (Si/Al ～ 2.5) required mild dealumination (to Si/Al > 4 in the case of Y) to facilitate subsequent efficient desilication. Alkaline treatment of Y and USY zeolites with low Si/Al ratios (～4–6) led to an abundance of Al‐rich debris, which could be removed by a subsequent mild acid wash. On the other hand, severely steamed and dealuminated, hence Si‐rich, USY zeolites (Si/Al = 15 and 30) proved extremely sensitive to the alkaline solution, displaying facile dissolution and substantial amorphization. For the latter group of ultra‐stable Y zeolites, the presence of TPA⁺ in the alkaline solution enables to protect the zeolite structures upon the introduction of mesoporosity by desilication, preserving crystallinity and micropore volume. The sorption and catalytic properties of the hierarchical Y and USY zeolites were superior compared to the conventional counterparts.