Hierarchically Micro- and Mesoporous Zeolitic Imidazolate Frameworks Through Selective Ligand Removal.

A new method to engineer hierarchically porous zeolitic imidazolate frameworks (ZIFs) through selective ligand removal (SeLiRe) is presented. This innovative approach involves crafting mixed-ligand ZIFs (ML-ZIFs) with varying proportions of 2-aminobenzimidazole (NH2-bIm) and 2-methylimidazole (2-mIm), followed by controlled thermal treatments. This process creates a dual-pore system, incorporating both micropores and additional mesopores, suggesting selective cleavage of metal-ligand coordination bonds. Achieving this delicate balance requires adjustment of heating conditions for each mixed-ligand ratio, enabling the targeted removal of NH2-bIm from a variety of ML-ZIFs while preserving their inherent microporous framework. Furthermore, the distribution of the initial thermolabile ligand plays a pivotal role in determining the resulting mesopore architecture. The efficacy of this methodology is aptly demonstrated through the assessment of hierarchically porous ZIFs for their potential in adsorbing diverse organic dyes in aqueous environments. Particularly striking is the performance of the 10%NH2-ZIF-2 h, which showcases an astonishing 40-fold increase in methylene blue adsorption capacity compared to ZIF-8, attributed to larger pore volumes that accelerate the diffusion of dye molecules to adsorption sites. This versatile technique opens new avenues for designing micro/mesoporous ZIFs, particularly suited for liquid media scenarios necessitating efficient active site access and optimal diffusion kinetics, such as purification, catalysis, and sensing.

Nanostructurally Engineering Covalent Organic Frameworks for Boosting CO2 Photoreduction.

Herein, a series of imine-linked covalent organic frameworks (COFs) are developed with advanced ordered mesoporous hollow spherical nanomorphology and ultra-large mesopores (4.6 nm in size), named OMHS-COF-M (M = H, Co, and Ni). The ordered mesoporous hollow spherical nanomorphology is revealed to be formed via an Ostwald ripening mechanism based on a one-step self-templated strategy. Encouraged by its unique structural features and outstanding photoelectrical property, the OMHS-COF-Co material is applied as the photocatalyst for CO2-to-CO reduction. Remarkably, it delivers an impressive CO production rate as high as 15 874 µmol g-1 h-1, a large selectivity of 92.4%, and a preeminent cycling stability. From in/ex situ experiments and density functional theory (DFT) calculations, the excellent CO2 photoreduction performance is ascribed to the desirable cooperation of unique ordered mesoporous hollow spherical host and abundant isolated Co active sites, enhancing CO2 activation, and improving electron transfer kinetics as well as reducing the energy barriers for intermediates *COOH generation and CO desorption.

Ordering Bimetallic Cu-Pd Catalysts onto Orderly Mesoporous SrTiO3-Crystal Nanotubular Networks for Efficient Carbon Dioxide Photoreduction.

Artificial photosynthesis of fuels has garnered significant attention, with SrTiO3 emerging as a potential candidate for photocatalysis due to its exceptional physicochemical properties. However, selectively converting CO2 into fuels with desired reaction products remains a grand challenge. Herein, we design an updated method via an aging strategy based on the electrospinning technique to synthesize a single-crystalline Al-doped SrTiO3 nanotubular networks with self-assembled orderly mesopores, further modified by Cu-Pd alloy. It exhibits both high crystallinity and superior cross-linked mesoporous structures, effectively facilitating charge carrier transfer, photon utilization, and mass transfer, with a remarkable enhancement from 0.025 mmol h-1 m-2 to 1.090 mmol h-1 m-2 in the CO production rate. Meanwhile, the ordered arrangement of Cu and Pd atoms on the (111) surface can promote the rate-determining step (*CO2 to *COOH), which is also responsible for its good activity. The presence of CuO in the reaction confers a significant advantage for CO desorption, leading to a remarkable CO selectivity of 95.54 %. This work highlights new insights into developing advanced heterogeneous photocatalysts.

Defect-Engineered ZIF-Derived Non-Pt Cathode Catalyst at 1.5 mg cm-2 Loading for Proton Exchange Membrane Fuel Cells.

Due to the sluggish kinetics of the oxygen reduction reaction (ORR) by non-Pt based catalyst, high loading of catalyst is required to achieve satisfactory fuel cell performance, which inevitably leads to the increase of the catalyst layer thickness with serious mass transport resistance. Herein, a defective zeolitic imidazolate framework (ZIF) derived Co/Fe-N-C catalyst with small mesopores (2-4 nm) and high density of CoFe atomic active sites are prepared by regulating the Fe dosage and pyrolysis temperature. Molecular dynamics simulation and electrochemical tests indicate that > 2 nm mesopores show insignificant influence on the diffusion process of O2 and H2 O molecules, leading to the high utilization of active sites and low mass transport resistance. The proton exchange membrane fuel cell (PEMFC) shows a high-power density of 755 mW cm-2 with only 1.5 mg cm-2 of non-Pt catalyst in the cathode. No apparent performance loss caused by concentration difference can be observed, in particular in the high current density region (1 A cm-2 ). This work emphasizes the importance of small mesopore design in the Co/Fe-N-C catalyst, which is anticipated to provide essential guidance for the application of non-Pt catalysts.

Mesoporous Matrices as a Promising New Generation of Carriers for Multipolymorphic Active Pharmaceutical Ingredient Aripiprazole.

The enhancement of the properties (i.e., poor solubility and low bioavailability) of currently available active pharmaceutical ingredients (APIs) is one of the major goals of modern pharmaceutical sciences. Among different strategies, a novel and innovative route to reach this milestone seems to be the application of nanotechnology, especially the incorporation of APIs into porous membranes composed of pores of nanometric size and made of nontoxic materials. Therefore, in this work, taking the antipsychotic API aripiprazole (APZ) infiltrated into various types of mesoporous matrices (anodic aluminum oxide, native, and silanized silica) characterized by similar pore diameters (d = 8-10 nm) as an example, we showed the advantage of incorporated systems in comparison to the bulk substance considering the crystallization kinetics, molecular dynamics, and physical stability. Calorimetric investigations supported by the temperature-dependent X-ray diffraction measurements revealed that in the bulk system the recrystallization of polymorph III, which next is converted to the mixture of forms IV and I, is visible, while in the case of confined samples polymorphic forms I and III of APZ are produced upon heating of the molten API with different rates. Importantly, the two-step crystallization observed in thermograms obtained for the API infiltrated into native silica templates may suggest crystal formation by the interfacial and core molecules. Furthermore, dielectric studies enabled us to conclude that there is no trace of crystallization of spatially restricted API during one month of storage at T = 298 K. Finally, we found that in contrast to the crystalline and amorphous bulk samples, all examined confined systems show a logarithmic increase in API dissolution over time (very close to a prolonged release effect) without any sign of precipitation. Our data demonstrated that mesoporous matrices appear to be interesting candidates as carriers for unstable amorphous APIs, like APZ. In addition to protecting them against crystallization, they can provide the desired prolonged release effect, which may increase the drug concentration in the blood (resulting in higher bioavailability). We believe that the "nanostructirization" in terms of the application of porous membranes as a novel generation of drug carriers might open unique perspectives in the further development of drugs characterized by prolonged release.

Mesoporous NiO/Ni2O3 nanoflowers for favorable visible light photocatalytic degradation of 4-chlorophenol.

The present study highlights the treatment of industrial effluent, which is one of the most life-threatening factors. Herein, for the first time, two types of NiO (green and black) photocatalysts were prepared by facile chemical precipitation and thermal decomposition methods separately. The synthesized NiO materials were demonstrated with various instrumental techniques for finding their characteristics. The X-ray diffraction studies (XRD) and X-ray photoelectron spectroscopy (XPS) revealed the presence of Ni2O3 in black NiO material. The transmission electron microscopic (TEM) images engrained the nanospherical shaped green NiO and nanoflower shaped black NiO/Ni2O3 materials. Further, the band gap of black NiO nanoflower was 2.9 eV compared to green NiO having 3.8 eV obtained from UV-vis spectroscopy. Meanwhile, both NiO catalysts were employed for visible light degradation, which yields a 60.3% efficiency of black NiO comparable to a 4.3% efficiency of green NiO within 180 min of exposure. The higher degrading efficiency of black NiO was due to the presence of Ni2O3 and the development of pores, which was evident from the Barrett-Joyner-Halenda (BJH) method. Type IV hysteresis was observed in black NiO nanoflowers with high surface area and pore size measurements. This black NiO/Ni2O3 synthesized from the thermal decomposition method has promoted better photocatalytic degradation of 4-chlorophenol upon exposure to visible light and is applicable for other industrial pollutants.

Resol/triblock copolymer composite-guided smart fabrication of carbonized mesopores for efficiently decoding exosomal glycans.

Soft-template carbonized mesopores were developed for the purpose of enriching urinary exosomal glycans through organic-organic self-assembly using block copolymers and resol precursors. With a high surface area of 229 m2 g-1, a small pore size of 3.1 nm, and a significant amount of carbon that specifically interacts with oligosaccharides in glycans, this carbonized mesopore material exhibits high selectivity and low limits of detection (5 ng µL-1) towards glycans. Our analysis of complex urine samples from healthy volunteers and bladder carcinoma patients successfully profiled 48 and 56 exosomal glycans, respectively, and 16 of them were significantly changed. Moreover, one upregulated bisecting N-acetylglucosamine (GlcNAc)-type glycan with core fucose, two upregulated and two downregulated terminal-sialylated glycans were revealed to be linked to bladder carcinoma. This approach is of significant importance for understanding diseases that arise from protein glycosylation mutations, and it may contribute to the development of novel diagnostic and therapeutic strategies for bladder carcinoma.

Design of Nickel Supported Hierarchical ZSM-5/USY Zeolite Bifunctional Catalysts for One-Pot Menthol Synthesis via Liquid-Phase Citral Hydrogenation.

Nickel-supported hierarchical zeolite catalysts were prepared through a desilication reassembly process under optimized conditions and applied in one-pot menthol synthesis. In this work, the hierarchical zeolite-supported metal bifunctional catalysts were prepared with the help of desilication re-assembly and wetness impregnation techniques and applied in menthol synthesis via citral hydrogenation. The prepared catalysts were characterized using PXRD, BET, FE-TEM, NH3-TPD, H2-TPR, pyridine adsorption, and ICP-OES techniques. As a result, the physicochemical and acidic properties, such as mesopore surface area, metal dispersion, acidity, catalytic activity, and strong Lewis acid sites of pure microporous ZSM-5/USY zeolites, were significantly improved. Consequently, with the occurrence of superior physicochemical and acidic properties, the Ni/HZ-0.5 M catalyst exhibited outstanding catalytic activity (100% conversion, TOF 7.12 h-1) and menthol selectivity (83%, 4 h) with uniform stability at 100 °C, 1.0 MPa hydrogen. Similarly, the cracking rate decreased with the decrease in Bronsted acid sites.

Constructing Intrapenetrated Hierarchical Zeolites with Highly Complete Framework via Protozeolite Seeding.

Creation of intrapenetrated mesopores with open highway from external surface into the interior of zeolite crystals are highly desirable that can significantly improve the molecular transport and active sites accessibility of microporous zeolites to afford enhanced catalytic properties. Here, different from traditional zeolite-seeded methods that generally produced isolated mesopores in zeolites, nanosized amorphous protozeolites with embryo structure of zeolites were used as seeds for the construction of single-crystalline hierarchical ZSM-5 zeolites with intrapenetrated mesopores (mesopore volume of 0.51 cm3 g-1 ) and highly complete framework. In this strategy, in contrast to the conventional synthesis, only a small amount of organic structure directing agents and a low crystallization temperature were adopted to promise the protozeolites as the dominant growth directing sites to induce crystallization. The protozeolite nanoseeds provided abundant nucleation sites for surrounding precursors to be crystallized, followed by oriented coalescence of crystallites resulting in the formation of intrapenetrated mesopores. The as-prepared hierarchical ZSM-5 zeolites exhibited ultra-long lifetime of 443.9 hours and a high propylene selectivity of 47.92 % at a WHSV of 2 h-1 in the methanol-to-propylene reaction. This work provides a facile protozeolite-seeded strategy for the synthesis of intrapenetrated hierarchical zeolites that are highly effective for catalytic applications.

Cation-Selective Oxide Semiconductor Mesoporous Membranes for Biomimetic Ion Rectification and Light-Powered Ion Pumping.

Artificial membranes precisely imitating the biological functions of ion channels and ion pumps have attracted significant attention to explore nanofluidic energy conversion. Herein, inspired by the cyclic ion transport for the photosynthesis in purple bacteria, a bilayer inorganic membrane (TiO2 /AAO) composed of oxide semiconductor (TiO2 ) mesopores on anodic alumina (AAO) macropores is we developed. This inorganic membrane achieves the functions of ion channels and ion pumps, including the ion rectification and light-powered ion pumping. The asymmetric charge distribution across the bilayer membrane contributes to the cationic selectivity and ion rectification characteristics. The electrons induced by ultraviolet irradiation introduce a built-in electric field across TiO2 /AAO membrane, which pumps the active ion transport from a low to a high concentration. This work integrates the functions of biological ion channels and ion pumps within an artificial membrane for the first time, which paves the way to explore multifunctional membranes analogous to its biological counterpart.

Unraveling the Intercorrelation Between Micro/Mesopores and K Migration Behavior in Hard Carbon.

Pore-structure design with increased ion-diffusion ability is usually regarded as an effective strategy to improve K-storage performance in hard carbon (HC). However, the relationship between porous structure and K+ migration behavior remains unclear and requires further exploration. Herein, a series of chemically activated hard carbon spheres (denoted as AHCSs) with controllable micro/mesopores structure are successfully synthesized to explore intercorrelation between micro/mesopores and K migration behavior. The experimental results indicate AHCSs have two different K+ storage ways, that is, adsorption behavior at high potential region and intercalation process at low potential region. These behaviors are closely related to the pores structure evolution: the micropores afford extra active sites for efficient K-ions adsorption, and therefore positive correlation between micropores and adsorption-contributed capacity is confirmed; the mesopores permit more K-ions intercalation/deintercalation by offering adequate pathways, and as a result positive correlations between mesopores and intercalation-contributed capacity as well as initial Coulombic efficiency are revealed. All these together contribute to achieving excellent reversible capacity, and exceptional rate capability with an ultra-long cycle lifespan in PIBs, and simultaneously exhibit a high energy density as well as considerable cycling stability for potassium-ion full cells. These results promote a fundamental understanding of K+ migration behaviors in hard carbon.

Photodynamic and Its Concomitant Ion-Interference Synergistic Therapies Based on Functional Hierarchically Mesoporous MOFs.

Although ion-interference therapy (IIT) has become an intriguing option for cancer treatment, the generation of interference ions on-demand remains a challenge. Herein, a nanoplatform based on hierarchically mesoporous metal-organic frameworks (HMMOFs) is adopted to integrate black phosphorus quantum dots (BPQDs) and meso-tetra(4-carboxyphenyl) porphine (TCPP) to realize controllable phosphate anions (PAs) production in a specific cancerous region for IIT. The uniform large mesopores of HMMOFs could guarantee the selective screening and immobilization of ultra-small and monodispersed BPQDs. The TCPP in microporous domains of HMMOFs could effectively produce 1 O2 , which not only serves as photosensitizer for photodynamic therapy (PDT), but also switches on the release of PAs from BPQDs in the adjacent mesoporous domains to trigger the concomitant synergetic IIT. The elaborated nanoplatform (BP@HMUiO-66-TCPP) presents good biocompatibility, biodegradability as well as enhanced synergetic therapeutic effects. In murine models treated with BP@HMUiO-66-TCPP, the tumor inhibition rate is as high as ≈98.24% as compared to that of the control group after 14 days treatment. Moreover, the tumor volumes in the synergetic group are only 19.6% of those in the PDT alone treated group. Such a concept of exogenous photo-controlled synergistic therapeutics might be extended to a broad range of IIT for an improved antitumor efficacy.

Surface-Enhanced Raman Scattering from Dye Molecules in Silicon Nanowire Structures Decorated by Gold Nanoparticles.

Silicon nanowires (SiNWs) prepared by metal-assisted chemical etching of crystalline silicon wafers followed by deposition of plasmonic gold (Au) nanoparticles (NPs) were explored as templates for surface-enhanced Raman scattering (SERS) from probe molecules of Methylene blue and Rhodamine B. The filling factor by pores (porosity) of SiNW arrays was found to control the SERS efficiency, and the maximal enhancement was observed for the samples with porosity of 55%, which corresponded to dense arrays of SiNWs. The obtained results are discussed in terms of the electromagnetic enhancement of SERS related to the localized surface plasmon resonances in Au-NPs on SiNW's surfaces accompanied with light scattering in the SiNW arrays. The observed SERS effect combined with the high stability of Au-NPs, scalability, and relatively simple preparation method are promising for the application of SiNW:Au-NP hybrid nanostructures as templates in molecular sensorics.

Micro-mesoporous submicron silica particles with pore size tunable in a wide range: synthesis, properties and prospects for LED manufacturing.

An approach has been developed that allows the synthesis of submicron spherical silica particles with a controlled micro-mesoporous structure possessing a large specific surface area (up to 1300 m2g-1). Particle synthesis is carried out by the hydrolysis of a mixture of various organosilanes mostly associated either with CTAB or with each other. A change in the concentration of CTAB in the reaction mixture apparently leads to a change in the formation mechanism of nuclei for the silica particle growth, which allows for varying the diameter of the synthesized particles in the range from 40-450 nm. The effect of the composition of the silica precursor ([3-(methacryloyloxy)propyl]trimethoxysilane, (3-aminopropyl)triethoxysilane and tetraethoxysilane) on the formation process and porosity of the resulting particles is studied. It was shown that by simply varying the ratio of organosilanes in the composition of the precursor, one can control the pore diameter of the particles in a wide range from 0.6-15 nm. The large-pore (up to 15 nm) silica particles are used as a matrix for the spatial distribution of luminescent carbon dots. The incorporation of carbon dots into SiO2particles prevents their aggregation leading to emission quenching after drying, thus allowing us to obtain highly luminescent composite particles. LEDs based on the obtained composite material show bright visible luminescence with spectral characteristics similar to that of a commercial cold white LED.

Mesoporous Manganese Oxide/Lignin-Derived Carbon for High Performance of Supercapacitor Electrodes.

This study explores the modification of lignin with surfactants, which can be used as a template to make mesoporous structures, and can also be used in combination with manganese oxide to produce manganese oxide/lignin-derived carbon. Organosolv extraction, using ethanol (70%) at 150 °C, was carried out to extract lignin from oil palm wood. Lignin was then mixed with Pluronic F-127, with and without Mn(NO3)2, and then crosslinked with acidic formaldehyde, resulting in a carbon precursor-based modified lignin. Carbonization was carried out at 900 °C to produce lignin-derived carbon and manganese oxide/lignin-derived carbon. The characterization materials included Fourier transform infrared (FTIR) spectroscopy, scanning electron microscope-energy dispersive X-ray (SEM-EDX) mapping, X-ray diffraction (XRD), and N2-sorption analysis. FTIR curves displayed the vibration bands of lignin and manganese oxide. SEM images exhibited the different morphological characteristics of carbon from LS120% (lignin with a Pluronic surfactant of 120%) and LS120%Mn20% (lignin with a Pluronic of 120% and Mn oxide of 20%). Carbon LS120% (C-LS120%) showed the highest specific surface area of 1425 m2/g with a mean pore size of 3.14 nm. The largest mean pore size of 5.23 nm with a specific surface area of 922 m2/g was exhibited by carbon LS120%-Mn20% (C-LS120%-Mn20%). C-LS120%Mn20% features two phases of Mn oxide crystals. The highest specific capacitance of 345 F/g was exhibited by C-LS120%-Mn20%.

About the Dominance of Mesopores in Physisorption in Amorphous Materials.

Amorphous, porous materials represent by far the largest proportion of natural and men-made materials. Their pore networks consists of a wide range of pore sizes, including meso- and macropores. Within such a pore network, material moisture plays a crucial role in almost all transport processes. In the hygroscopic range, the pores are partially saturated and liquid water is only located at the pore fringe due to physisorption. Therefore, material parameters such as porosity or median pore diameter are inadequate to predict material moisture and moisture transport. To quantify the spatial distribution of material moisture, Hillerborg's adsorption theory is used to predict the water layer thickness for different pore geometries. This is done for all pore sizes, including those in the lower nanometre range. Based on this approach, it is shown that the material moisture is almost completely located in mesopores, although the pore network is highly dominated by macropores. Thus, mesopores are mainly responsible for the moisture storage capacity, while macropores determine the moisture transport capacity, of an amorphous material. Finally, an electrical analogical circuit is used as a model to predict the diffusion coefficient based on the pore-size distribution, including physisorption.

Transformable Honeycomb-Like Nanoassemblies of Carbon Dots for Regulated Multisite Delivery and Enhanced Antitumor Chemoimmunotherapy.

Tumor fibrotic stroma forms complex barriers for therapeutic nanomedicine. Although nanoparticle vehicles are promising in overcoming biological barriers for drug delivery, fibrosis causes hypoxia, immunosuppression and limited immunocytes infiltration, and thus reduces antitumor efficacy of nanosystems. Herein, we report the development of cancer-associated fibroblasts (CAFs) responsive honeycomb-like nanoassemblies of carbon dots (CDs) to spatially program the delivery of multiple therapeutics for enhanced antitumor chemoimmunotherapy. Doxorubicin (DOX) and immunotherapeutic enhancer (Fe ions) are immobilized on the surface of CDs, whereas tumor microenvironment modifier (losartan, LOS) is encapsulated within the mesopores. The drugs-loaded nanoassemblies disassociate into individual CDs to release LOS to mitigate stroma and hypoxia in response to CAFs. The individual CDs carrying DOX and Fe ion efficiently penetrate deep into tumor to trigger intensified immune responses. Our in vitro and in vivo studies show that the nanoassemblies exhibit effective T cells infiltration, tumor growth inhibition and lung metastasis prevention, thereby providing a therapeutic platform for desmoplasia solid tumor.

Directing Gold Nanoparticles into Free-Standing Honeycomb-Like Ordered Mesoporous Superstructures.

2D mesoporous materials fabricated via the assembly of nanoparticles (NPs) not only possess the unique properties of nanoscale building blocks but also manifest additional collective properties due to the interactions between NPs. In this work, reported is a facile and designable way to prepare free-standing 2D mesoporous gold (Au) superstructures with a honeycomb-like configuration. During the fabrication process, Au NPs with an average diameter of 5.0 nm are assembled into a superlattice film on a diethylene glycol substrate. Then, a subsequent thermal treatment at 180 °C induces NP attachment, forming the honeycomb-like ordered mesoporous Au superstructures. Each individual NP connects with three neighboring NPs in the adjacent layer to form a tetrahedron-based framework. Mesopores confined in the superstructure have a uniform size of 3.5 nm and are arranged in an ordered hexagonal array. The metallic bonding between Au NPs increases the structural stability of architected superstructures, allowing them to be easily transferred to various substrates. In addition, electron energy-loss spectroscopy experiments and 3D finite-difference time-domain simulations reveal that electric field enhancement occurs at the confined mesopores when the superstructures are excited by light, showing their potential in nano-plasmonic applications.

Variation of Aluminium Distribution in Small-Sized ZSM-5 Crystals during Desilication.

Hollow ZSM-5 zeolites of size below one micrometer can be produced by desilication of crystals with aluminium zoning. The parent crystals have a core-shell structure: the core part has nearly no aluminium, whereas the aluminium content in the shell increases when extending to exterior surface. Transmission electron microscopy confirmed the preservation of the crystalline shell after base leaching, but could not identify its subtle change. An increase of the Si/Al ratio of the surface was detected upon leaching the parent material to form the hollow zeolite by using ambient pressure X-ray photoelectron spectroscopy and infrared spectroscopy of substituted alkylpyridines. 27 Al MAS NMR showed that base leaching results in a reduced percentage of distorted tetrahedrally coordinated aluminium. The reprecipitation of dissolved species occurs and tetrahedrally coordinated tin atoms can thus be introduced to the shell framework. Overall, the formation of hollow ZSM-5 zeolites by desilication involves not only the removal of silicon-rich core, but also a reduced percentage of exterior aluminium-related acid sites, which should be considered while using hollow zeolites in acid-catalyzed reactions.

The Link between ZSM-5 Zeolite Crystallization and Mesopore Formation by Leaching.

Acid or base leaching are well-established tools in the synthesis of mesoporous zeolites. Previous studies suggest an inherent link between the structure-property relationship of mesoporous zeolites, that is, chemical resistance, pore diameter and distribution, with zeolite synthesis or crystallization conditions. The exact nature and/or origin of this link is currently however, poorly established. Here, we provide evidence how zeolite crystallization conditions influence the leaching behavior and thus structure of mesoporous zeolites. Electron microscopy and in situ small angle X-ray scattering both confirmed the crystallization of ZSM-5 to utilize both nanoparticles and oligomers as elemental building blocks. Utilization of these species is highly depended on supersaturation. The precursor solution of decreased water content favored a faster consumption of nanoparticles compared to its oligomers at the early stage of crystallization. Then the addition of oligomers can heal the surface imperfections and thus the resulting zeolite showed a higher resistance against acid leaching. In contrast, within the precursor solution of increased water content the slower consumption of nanoparticles led to crystals with a less robust rim. Defects existed in the rim due to limited healing by oligomers and, as such, mesopores can be created by the following post-treatment. Precise control over selected crystallization conditions can therefore further aid the design of optimized mesoporous zeolites.