The development of three-dimensional (3D) covalent organic frameworks (COFs) with large pores and high specific surface areas is of critical for practical applications. However, it remains a tremendous challenge to reconcile the contradiction between high porosity and high specific surface areas, and increasing the length of building blocks leads to structural interpenetration in 3D COFs. Here, we report the preparation of mesoporous three-dimensional COF by a new steric hindrance engineering method. By incorporating adamantane into the monomers instead of carbon centers, we successfully achieve 2-fold interpenetrated diamondoid-structured 3D COFs, featuring permanent mesopores (up to 33 Å), exceptionally high surface areas (>3400 m2 g-1), and low crystal densities (0.123 g cm-3). These properties far surpass those of most conventional 3D COFs with similar topologies. This work not only aims to construct 3D COFs with low interpenetration but also to establish a foundation for the systematic design and structural control of 3D COFs.

Mesoporous catalysts with a high specific surface area, accessible pore structures, and appropriate band edges are desirable for optimal charge transfer across the interfaces, suppress electron-hole recombination, and promote redox reactions at the active sites. The present study demonstrates the rational design of mesoporous ZnFe2O4@g-C3N4 magnetic nanocomposites (MNCs) with different pore sizes and pore volumes following a combination of facile thermal itching and thermal impregnation methods. The MNCs preserve the structural, morphological, and physical attributes of their counterparts while ensuring their effectiveness and superior catalytic capabilities. The morphological analysis confirms the successful grafting and confinement of ZnFe2O4 nanoparticles with the polymeric g-C3N4 nanosheets to form heterojunctions with numerous interfaces. The MNCs possess uniformly distributed small mesopores (pore size <4 nm), ample active sites, and a high specific surface area of 62.50 m2/g. The mesoporous ZnFe2O4@g-C3N4 notably improve hydrogen evolution rate and methylene blue dye degradation. The optimal loading weight of ZnFe2O4 is 20%, in which the MNCs display the highest hydrogen evolution rate of 1752 µmolg-1h-1 and photo-Fenton dye degradation rate constants of 0.147 min-1, upon solar-light illumination. Furthermore, the photocatalysts demonstrate recyclability over five consecutive cycles, confirming their stability, while easy separation using a simple magnet underscores practical utility.

Fe single atoms (Fe SAs) based catalysts have received much attention in electrocatalytic oxygen reduction reaction (ORR) due to its low-cost and high activity. Yet, the facile synthesis of efficient and stable Fe SAs catalysts are still challenging. Here, we reported a Fe SAs anchored on N-doped mesoporous carbon microspheres (NC) catalyst via spraying drying and pyrolysis processes. The highly active Fe SAs are uniformly distributed on the NC matrix, which prevented the aggregation benefiting from the enhanced Fe-N bonds. Also, the mesoporous carbon structure is favorable for fast electron and mass transfer. The optimized Fe@NC-2-900 catalyst shows positive half wave potential (E1/2 = 0.86 V vs reversible hydrogen electrodes (RHE)) and starting potential (Eonset = 0.98 V vs RHE) in ORR, which is comparable to the commercial Pt/C catalyst (E1/2= 0.87 V, Eonset = 1.08 V). Outstanding stability with a current retention rate of 92.5% for 9 hours and good methanol tolerance are achieved. The assembled zinc-air batteries showed good stability up to 500 hours at a current density of 5 mA cm-2. This work shows potentials of Fe SAs based catalysts for the practical application in ORR and pave a new avenue for promoting their catalytic performances.

Multimaterial heterostructures have led to characteristics surpassing the individual components. Nature controls the architecture and placement of multiple materials through biomineralization of nanoparticles (NPs); however, synthetic heterostructure formation remains limited and generally departs from the elegance of self-assembly. Here, a class of block polymer structure-directing agents (SDAs) are developed containing repeat units capable of persistent (covalent) NP interactions that enable the direct fabrication of nanoscale porous heterostructures, where a single material is localized at the pore surface as a continuous layer. This SDA binding motif (design rule 1) enables sequence-controlled heterostructures, where the composition profile and interfaces correspond to the synthetic addition order. This approach is generalized with 5 material sequences using an SDA with only persistent SDA-NP interactions (\"P-NP1-NP2\"; NPi = TiO2, Nb2O5, ZrO2). Expanding these polymer SDA design guidelines, it is shown that the combination of both persistent and dynamic (noncovalent) SDA-NP interactions (\"PD-NP1-NP2\") improves the production of uniform interconnected porosity (design rule 2). The resulting competitive binding between two segments of the SDA (P- vs D-) requires additional time for the first NP type (NP1) to reach and covalently attach to the SDA (design rule 3). The combination of these three design rules enables the direct self-assembly of heterostructures that localize a single material at the pore surface while preserving continuous porosity.

In this study, phosphoric acid activation was employed to synthesize nitrogen-doped mesoporous activated carbon (designated as MR1) from Lentinus edodes (shiitake mushroom) residue, while aiming to efficiently remove acetaminophen (APAP), carbamazepine (CBZ), and metronidazole (MNZ) from aqueous solutions. We characterized the physicochemical properties of the produced adsorbents using scanning electron microscopy (SEM), nitrogen adsorption isotherms, and X-ray photoelectron spectroscopy (XPS). MR1, MR2, and MR3 were prepared using phosphoric acid impregnation ratios of 1, 2, and 3 mL/g, respectively. Notably, MR1 exhibited a significant mesoporous structure with a volume of 0.825 cm3/g and a quaternary nitrogen content of 2.6%. This endowed MR1 with a high adsorption capacity for APAP, CBZ, and MNZ, positioning it as a promising candidate for water purification applications. The adsorption behavior of the contaminants followed the Freundlich isotherm model, suggesting a multilayer adsorption process. Notably, MR1 showed excellent durability and recyclability, maintaining 95% of its initial adsorption efficiency after five regeneration cycles and indicating its potential for sustainable use in water treatment processes.

Changing the morphology is an excellent option for altering the textural parameters of SBA-15 materials. This study provides a guide on how the properties of mesoporous structures behave according to their morphology and their contribution to thermal stability. The objective of this work was to synthesize different morphologies (spherical, hexagonal prisms, rice-like grains, rods, and fibers) of SBA-15 materials and evaluate the existing textural changes. The materials were synthesized by varying the temperature of the synthesis gel from 25 °C to 55 °C, with stirring at 300 or 500 rpm. The results of X-ray diffraction, Fourier transform infrared spectroscopy, N2 adsorption and desorption, and scanning electron microscopy were evaluated. Thermal stability tests were also conducted in an inert atmosphere. The materials were successfully synthesized, and it was observed that they all exhibited different characteristics, such as their ordering, interplanar distance, mesoporous parameter, specific surface area, micropore and mesopore volumes, external mesoporous area, and wall thickness. They also presented different thermal stabilities. The rice grain morphology had the highest specific surface area (908.8 cm2/g) and the best thermal stability, while the rod morphology had the best pore diameter (7.7 nm) and microporous volume (0.078 cm3/g).

The widespread use of organic dyes in various industrial applications, driven by rapid industrialization, has become a significant environmental concern. Thus, highly efficient and reusable adsorbent for removal of pollutant dyes have gained increasing attention in water treatment. In this study, we present TiO2 nanoparticle-embedded mesoporous starch-based microparticle (TiO2@MSMP) with hierarchical rose-like structure were synthesis by using acetone precipitation of short-chain glucan (SCG) obtained from waxy maize starch. The resulting TiO2@MSMP exhibits an A-type crystalline polymorph and mean particle size of approximately 2 μm, displaying a type IV adsorption isotherm with a mean pore diameter of 19 nm and an average surface area of 12.34 m2/g. The adsorption ability of TiO2@MSMP towards methyl orange (MO) and crystal violet (CV) were 85.8 mg/g and 103.8 mg/g, respectively. The reusability of TiO2@MSMP was achieved by UV irradiation, which resulted in photodegradation of the adsorbed dye over 80 % while maintaining good absorption ability and structural stability during the recycling process. Given its cost-effectiveness, high adsorption capacity, and excellent reusability, TiO2@MSMP holds promise as an effective and environmentally friendly adsorbent with significant potential for removing dyes from aqueous solutions and purifying water.

BACKGROUND: A highly efficient superior catalyst of Ni (II) and VO (IV) metal complexes supported on MCM-41 has been synthesized and developed for chemoselective oxidation of sulfides to sulfoxides and oxidative coupling of thiols to their corresponding disulfides using H2O2 as a green and efficient procedure. All sulfoxides and disulfides were obtained in short reaction times with excellent yields. The over-oxidation of sulfides or thiols was not observed and all products were synthesized in high purity. These catalysts could be recovered and reused several times without any significant loss in their catalytic activity. Compared to the old catalysts in the literature, these catalysts showed better activity and selectivity for the synthesis of sulfoxide and disulfide derivatives, which shows the novelty of this work.
METHODS: At first, the mesoporous MCM-41 was synthesized, and further, its surface was modified by (3-chloropropyl)-triethoxysilane (CPTES). Then, the modified MCM-41 (nPrCl-MCM- 41) was functionalized by adenine. In the next step, the functionalized MCM-41 (6AP-MCM- 41) was used as support for the immobilization of nickel and oxo-vanadium as final catalysts (Ni-6AP-MCM-41 or VO-6AP-MCM-41). The structure and properties of these catalysts have been identified by XRD, SEM, TGA, FT-IR, and AAS spectral analyses. These catalysts were used in the chemoselective oxidation of sulfides and oxidative coupling of thiols.
RESULTS: These complexes catalyzed all reactions well at room temperature. According to the results obtained, the hydroxyl groups of some derivatives, including 2-(methylthio) ethanol or 2,2-(phenylthio) ethanol, remained unchanged during the reaction.
CONCLUSIONS: The method has been found to possess the advantages of low cost, high efficiency, high yields, recovery, and reusability for several runs without significant loss in the catalytic activity.

cis-Diol-containing molecules, an essential type of compounds in living organisms, have attracted intensive research interest from various fields. The analysis of cis-diol-containing molecules is still suffering from some drawbacks, including low abundance and abundant interference. Metal-organic frameworks (MOFs) have proven to be an ideal sorbent for sample preparation. However, most of the reported MOFs are mainly restricted to a microporous regime (pore size <2 nm), which greatly limits the application. Herein, a facile strategy is established to construction of boronate affinity MOFs via the postsynthetic ligand-exchange process. Owing to the fact that the ligand-exchange process was assisted by the structural integrity of the primitive metal-organic framework and the great compatibility of click chemistry, the obtained EPBA-PCN-333(Fe) is able to realize the maximum maintaining the porosity and crystallinity of the parent material. Several intriguing features of EPBA-PCN-333(Fe) (e.g., excellent selectivity, efficient diffusion, good accessibility, and size exclusion effect) are experimentally demonstrated via a series of cis-diol-containing molecules with different molecular sizes (small molecules, glycopeptides, and glycoproteins). The binding performance of EPBA-PCN-333(Fe) is evaluated by employing catechol as the test molecule (binding capacity: 0.25 mmol/g, LOD: 200 ng/mL). Finally, the real-world applications of EPBA-PCN-333(Fe) were demonstrated by the detection of nucleosides of human urine samples.

OBJECTIVE: Composites with copper-doped mesoporous bioactive nanospheres (Cu-MBGN) were developed to prevent secondary caries by imparting antimicrobial and ion-releasing/remineralizing properties.
METHODS: Seven experimental composites containing 1, 5 or 10 wt% Cu-MBGN, the corresponding inert controls (silica) and bioactive controls (bioactive glass 45S5) were prepared. The temperature rise during light curing, cross-linking density by ethanol softening test, monomer elution and their potential adverse effects on the early development of zebrafish Danio rerio was investigated.
RESULTS: Materials combining Cu-MBGN and silica showed the highest resistance to ethanol softening, as did the bioactive controls. Cu-MBGN composites showed significant temperature rise and reached maximum temperature in the shortest time. Bisphenol A was not detected, while bis-GMA was found only in the control materials and TEGDMA in the eluates of all materials. There was no increase in zebrafish mortality and abnormality rates during exposure to the eluates of any of the materials.
CONCLUSIONS: The composite with 5 wt% Cu-MBGN combined with nanosilica fillers showed the lowest ethanol softening, indicating the polymer\'s highest durability and cross-linking density. Despite the TEGDMA released from all tested materials, no embryotoxic effect was observed.