A facile and fast microwave-assisted approach without any other pre/post-treatment has been proposed to hydrothermally synthesize six kinds of MFI-type heteroatom (Mn, Ga, Ti, Sn, Cr, Zr) zeolites. By comparing with oven heating mode, it is found that microwave field displays a positive effect on the introduction of partial heteroatoms in the zeolite framework. Moreover, differing from the conventional heating, microwave irradiation displays different influences on the different heteroatom zeolites because different heteroatoms cause different polarities and wave-absorption abilities of M–O bonds under microwave irradiation. Furthermore, this positive effect of microwave is embodied not only on heteroatom zeolite synthesis and heteroatom state in zeolite framework but also the resultant catalytic performance. This finding provides an easy route for the synthesis of novel heteroatom zeolite being difficult to prepare by conventional mode, along with a new direction for the exploration of microwave effect.

Highly efficient transformations of biomass-derived sugars into various valuable chemicals are of topical interest. Tetrose with a four-carbon bone is the root of most of biomass-derived C4 products, but its extreme instability obstructs the blossoming of C4 products presently. Herein, we describe a borate-stabilized catalytic strategy to accumulate erythrose from C6 aldose in a highly selective manner via retro-aldol and aldol processes in alcohol solvent. In our proposed mechanism, borate can stabilize erythrose and avoid its further retro-aldol splitting or isomerization, and induce the production of erythrose again via the aldol condensation of the above-generated glycolaldehyde.Keywords: biomass; C4 aldose; heterogeneous catalysis; retro-aldol/aldol condensation; stabilizing effect;

A specific microwave effect on the Sn- and Ti-MFI zeolite synthesis is exactly demonstrated by separating it from thermal effects through using Pyrex and SiC reaction vessels. Different from the reported conventional thermal effect on the organic reactions, this finding is of great significance to further investigate the microwave effect.

Tremendous efforts have been made in recent years to synthesize ordered mesoporous zeolite materials, because of the accelerating demands of industrial bulky molecule conversion. Here, we develop a novel gradient acidic assembly growth strategy to prepare ordered highly zeolitized mesoporous aluminosilicate (SBA-16) materials in a mixed template system. This gradient acidic assembly growth strategy can achieve the high zeolitization of mesoporous aluminosilicate walls without any ordering loss of the mesostructure. The resultant highly zeolitized mesoporous materials, composed of the intergrown zeolite subcrystal particles (2–3 nm), exhibit high surface area (∼834 m2 g–1) and pore volume (∼0.64 cm3 g–1), typical channel of MFI framework (0.52 nm), and uniform mesopore (∼5.75 nm), respectively. Moreover, these highly ordered crystallized mesostructures endow them with high exposed active sites and excellent hydrothermal stability, which consequently make their catalytic activities in bulky molecule transformations at least 10 times higher than conventional zeolites or amorphous mesoporous materials. Without the use of any special surfactants, this general synthetic process provides a brand new view for the synthesis and application of highly crystalline ordered mesoporous materials.

A facile microexplosion approach has been successfully developed to produce an interwoven mesopore network in zeolite crystals via the rushing-out of gases generated by decomposition of H2O2 under microwave irradiation. This “gas imprint” method creates the mesopores from the interior crystal toward the exterior, in line with the direction of the pristine microporous channels, and is different from the previous methods in which the reagent starts an attack from the crystal surface and perforates inward. The created mesopores extend throughout the whole crystal and highly blend into the intrinsic micropores around. The acidity of zeolite is also well preserved due to this unique mechanism of pore creation. The continuous high quality hierarchical architecture with intact acidity leads to a notable increase both in the conversion of 2-methoxynaphthalene acylation and in the selectivity to the target molecule of 2-acetyl-6-methoxynapthalene. This microexplosion approach offers an efficient synthesis protocol of zeolitic hierarchy integrating intersected mesoporosity and zeolitic microporosity and opens the way to the rational organization of meso- and microporosity for maximal advantage in applications.

Cellulose without any pretreatment was directly converted into levulinic acid (LA) in a microwave-assisted acidic catalytic system with a high ionic strength. The highest LA yield could reach 67.3 mol% within 60 min even when the cellulose concentration was as high as 10 wt%. It is concluded that high ion strength and microwave irradiation were jointly responsible for the fast cellulose conversion and high LA yield, and a cooperative acceleration mechanism is finally proposed. The high ion concentration provided by alkali metal halides not only accelerated the cellulose hydrolysis but also facilitated glucose conversion into LA by shifting the weak acid ionization equilibria, and microwave irradiation further promoted this salt effect by its characteristic heating way of ion conduction. Such a one-pot catalytic system provides a possibility of practical application for direct highly efficient conversion of cellulose due to its green properties, low cost and efficient characteristics.

Nano-/hierarchical zeolites have received increasing attention due to their catalytic performance preferable to that of conventional zeolites. The two major textural features of nano-/hierarchical zeolites, i.e. short microporous channel and large external surface area, can provide them with high activity and lifetime as well as high selectivity for products during catalysis. This perspective focuses on the most representative behavior of nano-/hierarchical zeolites in gaseous phase and liquid phase catalytic systems, considering whether the reaction is predominantly catalyzed within the micropore or at the external surface, and whether it is shape-selective. The catalytic characteristics and future prospects of nano-/hierarchical zeolites are highlighted in their applications in gaseous and liquid phase reactions.

Gd3+-loaded nanozeolite sodalite (SOD) is fast prepared through sequential hydrothermal synthesis, detemplation, and Gd3+ ions exchange under microwave irradiation. This microwave-assisted synthesis procedure provides nanozeolite Gd3+-SOD with a uniform particle size of 30 ± 2 nm and well framework structure. The result of its water proton relaxation rate indicates that its positive relaxivity per Gd3+ ion or per nanozeolite particle is relatively high, due to the efficient immobilization and enrichment of Gd3+ ions in the micropores as well as the large surface-to-volume ratio of nanozeolite. Furthermore, the relaxivity per Gd3+ ion displays clear position dependence, i.e., the exchanged Gd3+ ions near the external surface of nanozeolite pay major contribution to the total relaxivity. Moreover, the irreversible ion exchange process indicates that leaching of Gd3+ ion from nanozeolite Gd3+-SOD can be suppressed. The cell viability test shows low toxicity of nanozeolite Gd3+-SOD in vitro. The biodistribution and clearance data demonstrate the fast elimination of nanozeolite Gd3+-SOD by the reticuloendothelial system and steady accumulation in the liver and spleen for a long time, which indicates the negligible leaching of Gd3+ ion in vivo considering the highly stable framework structure of zeolite. In addition, the in vivo MRI demonstrates a brighter contrast enhancement in T1-weighted image compared to the pre-contrast image in the liver. This remarkable stable nanozeolite Gd3+-SOD with a positive relaxivity not only is a potential contrast agent for magnetic resonance imaging but also provides new insight into the utilization of nanozeolite with a unique framework structure.

A core–shell nanozeolite@enzyme bi-functional catalyst is constructed, which greatly improves selectivity and stereoselectivity of products in dynamic kinetic resolution of aromatic secondary alcohols compared with mixed catalysts, especially those involving small acyl donors.

The highly selective isomerization and dehydration of various carbohydrates (glucose, xylose, cellobiose and cellulose) are one-pot conversions conducted in a simple borate-containing phosphate buffer solution (PBS) under microwave irradiation. It is demonstrated that the key to glucose converting into 5-hydromethylfurfural (5-HMF) with a high selectivity is matching the isomerization and dehydration processes of glucose at the appropriate boron/glucose mole ratio (B/G) and pH of PBS with the aid of microwave irradiation. Moreover, the interaction between borate and glucose in the isomerization process has been demonstrated by both Raman spectra and theoretical calculations. Furthermore, the reusability of such a PBS system with borate has been accomplished by the successive addition of glucose and by the continual removal of 5-HMF in a biphasic system. These results not only deepen the understanding of the isomerization and dehydration behavior of glucose, but also provide the possibility for practical applications, owing to the appealing green, inexpensive and sustainable characteristics of such a catalytic system.

An acidic phosphate buffer system is developed to highly-selectively catalyze ketoses/aldoses dehydrating into 5-HMF without undesirable rehydration under microwave irradiation.

An in situ microwave-assisted Fenton-like oxidation has been developed for detemplation of the nanozeolite β without any pretreatment. The influencing factors on the removal of structure-directing agents (SDAs) in the nanozeolite β, such as the composition of Fenton-like reagents (pH, H2O2/TEA+, Fe3+/H2O2) and microwave operation conditions, are investigated, to find that the SDAs in the micropores and solution of the as-prepared nanozeolites could be completely eliminated within 15 min. In comparison with those obtained by the traditional high-temperature calcination, the Fenton-treated nanozeolite particles not only preserve their monodispersity and large external surface area, but also avoid the formation of extra-framework aluminum, which renders an enhanced catalytic performance in fructose dehydration.

An improved polymerization-induced colloid aggregation (im-PICA) method was developed to prepare zeolite microspheres (ZMSs) with a hierarchical porous structure and a uniform size, which could easily be carried out within half an hour by simply adding urea and formaldehyde into an acidic pH-pre-controlled colloidal solution as-obtained from a hydrothermal crystallization process. This procedure successfully avoided the repeated ultrasonic washing and high-speed centrifugation of the nanozeolite colloid during the traditional PICA method, and thereby became energy and time-economical. After removing the polymeric component, solid and hollow ZMSs as well as the mono-dispersed nanozeolite can be obtained under different preparation conditions. The structural transformation could be attributed to the correlation of the polymerization velocity on the zeolite nanocrystal surface and in the bulk solution with variation of acidity. Due to the short diffusion routes and abundant exposed active sites of nanozeolites as well as their unique secondary mesopore architecture, ZMSs displayed a clear advantage on catalysis reactions compared to commercial zeolite catalysts, such as the dehydration of fructose into 5-hydromethyl furfural.

Zeolite nanoparticles with various organosilanized surfaces have been synthesized in situ by a one-step approach which provides not only a functionalized surface for diverse host–guest interactions but also an attractive path for preparation of monodispersed template-free zeolite nanoparticles.

The preparation and mechanism investigation of mesoporosity and morphology are extremely important in the field of mesoporous materials. By using neutral amines as templates and alcohols as co-solvents, a series of HMS with different morphologies and mesoporosities are obtained. When long alkyl chain surfactant (n ⩾ 16) and short alkyl chain alcohol (CH3OH and C2H5OH) are employed, the increasing alcohol content induces the morphological transformation from lotus-leaf-like flake, to aggregated flake, potato-like vesicle, sphere, and finally to solid nanoparticle. When using short alkyl chain surfactant (n ⩽ 14) and long alkyl chain alcohol (C3H7OH), hollow vesicle, cracked sphere, sphere and mesoporous nanoparticle are successively obtained with the increase of alcohol content. Compared with the conventional mesoporous materials, HMS with these special morphologies has a unique regionally distributed dual meso-structure. By systematically analyzing the effects of co-solvent and surfactant, it is found that the morphology of the product is mainly determined by the initial surfactant micelle which can be adjusted by the type and concentration of surfactant and alcohol. Moreover, with progress of reaction, the decrease of surfactant concentration and the increase of silica polymerization degree would induce the mesophase evolution of product from 2D lamella-like to 3D wormholelike meso-structures, leading to the formation of dual meso-structured HMS products. The understanding of these processes is helpful for preparing mesoporous materials with various morphology and meso-structure for catalysis, separation and other application fields.

A series of multiradiate calcium phosphate patterns have been observed by a gradating chitosan-polyaspartatic acid (PAsp) system, and their morphology evolution reveals the effect of chitosan and PAsp on the interfacial biomineralization.

In the present work, a microwave-assisted two-step hydrothermal procedure was proposed successfully to prepare various zeolite nanocrystals (e.g., silicalite-1, ZSM-5, LTL, BEA and LTA) with controllable size, morphology and SiO2/Al2O3 ratio. The effects of the starting gel composition (such as water content, alkalinity and ratio of SiO2/Al2O3) as well as the hydrothermal synthesis condition (temperature and time) on the size of the zeolite nanocrystals have been studied in detail. It is found that high synthesis temperature and long reaction time benefit the growth of all the referred zeolite nanocrystals. However, the effects of the gel composition are very complex to different kinds of nanozeolites. For the nanozeolites crystallized in low alkalinity systems (e.g., ZSM-5, BEA and LTA), both increasing the alkalinity and decreasing the water content accelerate their nucleation process and thereby result in the decrease of their crystal size. On the contrary, for those prepared in high alkalinity systems (e.g., LTL and silicalite-1), an inversed trend could be observed. Moreover, the change of SiO2/Al2O3 ratio in the starting gel greatly affects the size of nanozeolite ZSM-5 and LTL, but slightly influences that of nanozeolite BEA. These results would provide a solid foundation to fully exploit the traditional and untraditional applications of various nanozeolites.

Organic species are thought to exert an important effect on the formation of the mineral materials by their electrostatic attraction with the cations of minerals. In this work, a series of polyaspartic acids with different hydroxylation degrees (PAsp-x%OH) have been used as crystal growth modifiers to direct the synthesis of calcium phosphate. The change of x in the PAsp-x%OH can precisely adjust its electrostatic interaction with calcium ions and, thereby, modulate the formation process and property of calcium phosphate, such as morphology, crystallinity, organic component content and calcium-to-phosphate ratio. Two competitive reactions are suggested in this system, that is, the combination of calcium ions to PAsp-x%OH and the precipitation of calcium hydrogen phosphate dihydrate. The trends of these two reactions are determined by variation of x in the PAsp-x%OH: lower value of x tends to involve the former, while the higher tends to latter. It has been found that the mineralization process involving PAsp-15%OH displayed a special point to counterbalance the two competitive reactions, leading to the longest induction time. These findings indicate that how an organic species controls the morphology and the formation dynamics of inorganic crystals in biomineralization by the slight modification of its molecular structure.

In this study, nanozeolites LTL with different exposed crystal planes and sizes were synthesized as excellent model material to study the effects of the crystal plane and size of the nanozeolite on the protein adsorption behaviors. A larger protein adsorption amount is observed on the smaller nanocrystals due to their larger surface area. More importantly, it is found that the (001) crystal plane with a 12-membered ring channel array has a larger contribution for protein adsorption on zeolite LTL nanocrystals than the other two dimensions with a very small pore opening (1.5 Å). It is proposed that the difference of protein adsorption on various crystal planes could be attributed to abundant exposed pore openings on the top (bottom) surface and curved surface of the side surface in columned nanozeolites LTL. This fact shows that the nanoscaled topography is also an important factor determining protein adsorption on the surface of nanozeolites, and efforts in the future should be focused on the synthesis of nanozeolites LTL with abundant exposed (001) planes. This observation will provide a new view for bioapplication and design of crystalline nanomaterials.

A biocompatible surface has been constructed on the electrode surface via layer-by-layer assembly of beta-nanozeolites and polydiallyldimethylammonium (PDDA) for the adsorption of enzymes towards sensitive biosensing. The film assembly process and enzyme adsorption were monitored by Quartz Crystal Microbalance measurements. The nanozeolite film exhibited an amazing adsorption capacity (about 350 mg g−1) for tyrosinase as a model enzyme. The tyrosinase biosensor showed a high sensitivity (400 μA mM−1), short response time (reaching 95% within 5 s), broad linear response range from 10 nM to 18 μM, very low detection limit (0.5 nM) and high operational and storage stability (more than 2 months). The apparent Michaelis–Menten constant KMapp was calculated to be 24 μM using phenol as the substrate. The assembly-controlled nanozeolite film could provide a biocompatible surface for the interaction study between enzymes and target molecules.

Controlled release and conversion of guest species (CO2) in zeolite microcapsules was achieved thanks to the high microporosity and the thermal and chemical stability of the zeolite shells.

The extensive applications of nanoparticle materials in biomedical and biotechnological fields trigger the rapid development of nanotoxicology, because nanoparticles are reported to cause more damage than larger ones when human exposure to them. In the present manuscript, we prepared a series of zeolite nanocrystals with different frameworks, sizes, compositions and shapes, and provided the first report on their toxic difference. As our results, the toxicities of zeolite nanoparticles depend on their size, composition and shape when they are exposed to HeLa cells. The pure-silica nanozeolite silicalite-1 displays nontoxicity, but aluminum-containing nanozeolites, such as ZSM-5, LTL, and LTA, show a dose-dependent toxic manner. The different shapes of nanozeolites can lead to different cytotoxicities, while the influences of the surface charge differences of various nanozeolites on their toxicities are unconspicuous. More importantly, caspase-3 activity and LDH released assays showed that the toxic nanozeolites seem to induce cell necrosis rather than cell apoptosis by the damnification for the cell membranes. These results are expected to direct the applications of nanozeolites with different structures and shapes in biomedicine and clinic science.

The platinum-encapsulated zeolitically microcapsular catalyst, associated with the immobilized Candida antartica lipase B (Novozyme®435), is successfully employed in the dynamic kinetic resolution of phenylethylamine. A conversion of 80% and a selectivity of 95% are achieved, and negligible loss of activity is detected even after reaction of 5 runs. It is found that the existence of the silicalite-1 shell not only effectively prevents the deactivation of both enzyme and Pt by isolating them in different regions of reaction system, but also significantly reduces the formation of by-products on the Pt nanoparticles within the protected space of zeolitic microcapsule. Such features of zeolitic shell should further promote the designing of various catalysts for multistep reaction network.Graphical abstractPlatinum-encapsulated zeolitic microcapsules are successfully employed in dynamic kinetic resolution of phenylethylamine with high activity and selectivity due to promising protective effect of the zeolitically microcapsular structure.Download high-res image (109KB)Download full-size imageHighlights► Platinum-encapsulated ZMCs are successfully employed in DKR of phenylethylamine. ► ZMC structure of catalyst promises its activity, selectivity and reusability. ► Isolation effect of zeolitic shell prohibits the deactivation of Pt and enzyme. ► The protected space within ZMC limits the formation of by-product.

The combination of bio- and chemocatalysts in one-pot is regarded as a breakthrough both for development of new catalytic concepts and for preparation of high-value chemicals. Zeolite nanocrystals (nanozeolites) have been proved as the most used chemical catalysts and as promising supports for enzyme immobilization. These capabilities of nanozeolites endow them with new possibilities for constructing desired platforms for the combination of bio- and chemocatalysis. In this article, several strategies are proposed to develop a one-pot flow microchannel reactor (MCR) by combining enzyme and chemocatalysis via a nanozeolite assembly approach, and the compatibilities of different types of active centers in various assembly strategies are systematically discussed on the basis of the catalytic results of dynamic kinetic resolution (DKR) of sec-alcohol. By precisely controlling the spatial distribution and the ratio of acidic and enzymatic active sites, as well as the reaction conditions, nanozeolite-modified MCR can achieve fast and highly selective one-pot DKR of sec-alcohol within 30 min.Graphical abstractThree assembly strategies for combining bio- and chemocatalysis for one-pot dynamic kinetic resolution (DKR) based upon nanozeolite-modified flow microchannel reactors (MCR), listed as co-assembled MCR (a), segment-assembled MCR (b), and region-assembled MCR (c), are performed and discussed. The one-pot DKR process of the sec-alcohol can be accomplished quickly and highly selectively in the flow MCR under the optimum assembly design within 30 min.Download high-res image (80KB)Download full-size imageHighlights► Nanozeolite-modified MCR is employed for the one-pot combination of bio- and chemocatalysts. ► Three assembly strategies in such MCR are proposed to develop the one-pot DKR of 1-PE. ► Three assembly strategies display different compatibilities for different active centers. ► The optimum DKR of 1-PE achieves 97% conversion and 99% selectivity in 30 min.

In this paper, uniform H-β nanozeolite microsphere (β-ZMS) prepared by polymerization-induced colloid aggregation, combined with an immobilized lipase B from Candida antarctica (commercially available Novozym® 435), is applied as a racemization catalyst to the one-pot dynamic kinetic resolution (DKR) of aromatic sec-alcohols. The DKRs of various aromatic sec-alcohols can be carried out with high selectivity and conversion under optimum conditions. Importantly, it is found that, compared to commercial zeolites β (C-β), β-ZMSs display high selectivity for small sec-alcohol molecules because their shorter microporous channels reduce the diffusion time of substrate/product in the three-dimensional framework, and thereby decrease the possibility of secondary reactions. However, the β-ZMSs show a high racemization rate in the DKR of large sec-alcohol molecules, such as racemic 1-(1-naphthyl)-ethanol, thanks to their abundant accessible active sites. This observation will not only benefit the performance of acidic zeolite catalysts in one-pot DKR systems but also provide a new perspective on the application of nanozeolites in catalysis.Graphical abstractUniform H-β nanozeolite microsphere (β-ZMS) performs excellently in the racemization of aromatic sec-alcohols in DKR processes. It is found that β-ZMSs show different advantages for the one-pot DKR of small and large substrate molecules, owing to their special shorter micropore channels and more accessible acidic sites compared to commercial zeolites β.Download high-res image (166KB)Download full-size imageHighlights► β-ZMS is applied as racemization catalyst to one-pot DKR of various aromatic sec-alcohols. ► The use of β-ZMS greatly improves the performance of zeolite catalyst in one-pot DKR system. ► β-ZMS shows very different advantages for the DKR of small and large sec-alcohols molecules. ► β-ZMS displays high racemization selectivity for small aromatic sec-alcohols. ► β-ZMS shows high racemization rate for large aromatic sec-alcohols.

A core–shell nanozeolite@enzyme bi-functional catalyst is constructed, which greatly improves selectivity and stereoselectivity of products in dynamic kinetic resolution of aromatic secondary alcohols compared with mixed catalysts, especially those involving small acyl donors.

A series of multiradiate calcium phosphate patterns have been observed by a gradating chitosan-polyaspartatic acid (PAsp) system, and their morphology evolution reveals the effect of chitosan and PAsp on the interfacial biomineralization.

An improved polymerization-induced colloid aggregation (im-PICA) method was developed to prepare zeolite microspheres (ZMSs) with a hierarchical porous structure and a uniform size, which could easily be carried out within half an hour by simply adding urea and formaldehyde into an acidic pH-pre-controlled colloidal solution as-obtained from a hydrothermal crystallization process. This procedure successfully avoided the repeated ultrasonic washing and high-speed centrifugation of the nanozeolite colloid during the traditional PICA method, and thereby became energy and time-economical. After removing the polymeric component, solid and hollow ZMSs as well as the mono-dispersed nanozeolite can be obtained under different preparation conditions. The structural transformation could be attributed to the correlation of the polymerization velocity on the zeolite nanocrystal surface and in the bulk solution with variation of acidity. Due to the short diffusion routes and abundant exposed active sites of nanozeolites as well as their unique secondary mesopore architecture, ZMSs displayed a clear advantage on catalysis reactions compared to commercial zeolite catalysts, such as the dehydration of fructose into 5-hydromethyl furfural.

Gd3+-loaded nanozeolite sodalite (SOD) is fast prepared through sequential hydrothermal synthesis, detemplation, and Gd3+ ions exchange under microwave irradiation. This microwave-assisted synthesis procedure provides nanozeolite Gd3+-SOD with a uniform particle size of 30 ± 2 nm and well framework structure. The result of its water proton relaxation rate indicates that its positive relaxivity per Gd3+ ion or per nanozeolite particle is relatively high, due to the efficient immobilization and enrichment of Gd3+ ions in the micropores as well as the large surface-to-volume ratio of nanozeolite. Furthermore, the relaxivity per Gd3+ ion displays clear position dependence, i.e., the exchanged Gd3+ ions near the external surface of nanozeolite pay major contribution to the total relaxivity. Moreover, the irreversible ion exchange process indicates that leaching of Gd3+ ion from nanozeolite Gd3+-SOD can be suppressed. The cell viability test shows low toxicity of nanozeolite Gd3+-SOD in vitro. The biodistribution and clearance data demonstrate the fast elimination of nanozeolite Gd3+-SOD by the reticuloendothelial system and steady accumulation in the liver and spleen for a long time, which indicates the negligible leaching of Gd3+ ion in vivo considering the highly stable framework structure of zeolite. In addition, the in vivo MRI demonstrates a brighter contrast enhancement in T1-weighted image compared to the pre-contrast image in the liver. This remarkable stable nanozeolite Gd3+-SOD with a positive relaxivity not only is a potential contrast agent for magnetic resonance imaging but also provides new insight into the utilization of nanozeolite with a unique framework structure.

Zeolite nanoparticles with various organosilanized surfaces have been synthesized in situ by a one-step approach which provides not only a functionalized surface for diverse host–guest interactions but also an attractive path for preparation of monodispersed template-free zeolite nanoparticles.

Nano-/hierarchical zeolites have received increasing attention due to their catalytic performance preferable to that of conventional zeolites. The two major textural features of nano-/hierarchical zeolites, i.e. short microporous channel and large external surface area, can provide them with high activity and lifetime as well as high selectivity for products during catalysis. This perspective focuses on the most representative behavior of nano-/hierarchical zeolites in gaseous phase and liquid phase catalytic systems, considering whether the reaction is predominantly catalyzed within the micropore or at the external surface, and whether it is shape-selective. The catalytic characteristics and future prospects of nano-/hierarchical zeolites are highlighted in their applications in gaseous and liquid phase reactions.