Angew Chem Int Ed Engl
January 2025
Metal/zeolite hybrid nanoframes featuring highly accessible compartmental environments, abundant heterogeneous interfaces, and diverse chemical compositions are expected to possess significant potential for heterogeneous catalysis, yet their general synthetic methodology has not yet been established. In this study, we developed a two-step -kinetics transformation approach to prepare metal/ZSM-5 hybrid nanoframes with exceptionally open nanostructures, tunable metal compositions, and abundant accessible active sites. Initially, the process involved the formation of single-crystalline ZSM-5 nanoframes through an anisotropic etching and recrystallization kinetic transformation process.
View Article and Find Full Text PDFTwo-dimensional (2D) hierarchically porous metal-organic framework (MOF) nanoarchitectures with tailorable meso-/macropores hold great promise for enhancing mass transfer kinetics, augmenting accessible active sites, and thereby boosting performance in heterogeneous catalysis. However, achieving the general synthesis of 2D free-standing MOF nanosheets with controllable hierarchical porosity and thickness remains a challenging task. Herein, we present an ingenious "hard" emulsion-induced interface super-assembly strategy for preparing 2D hierarchically porous UiO-66-NH nanosheets with highly accessible pore channels, tunable meso-/macropore sizes, and adjustable thicknesses.
View Article and Find Full Text PDFColloidal metal-organic framework (MOF) nanoparticles, with tailored asymmetric nanoarchitectures and hierarchical meso-/microporosities, have significant implications in high-performance nanocatalysts, nanoencapsulation carriers, and intricate assembly architectures. However, the methodology that could achieve precise control over the anisotropic growth of asymmetric MOF particles with tailored distributions of meso- and microporous regions has not yet been established. In this study, we introduce a facile anisotropic interface successive assembly approach to synthesize asymmetric core-shell MOF (ZIF-67) nanobowls with worm-like mesopores in the core and intrinsic micropores in the shell.
View Article and Find Full Text PDFHollow multi-shell mesoporous metal-organic framework (MOF) particles with accessible compartmentalization environments, plentiful heterogeneous interfaces, and abundant framework diversity are expected to hold great potential for catalysis, energy conversion, and biotechnology. However, their synthetic methodology has not yet been established. In this work, a facile dual-template-directed successive assembly approach has been developed for the preparation of monodisperse hollow multi-shell mesoporous MOF (UiO-66-NH) particles through one-step selective etching of successively grown multi-layer MOFs with alternating two types of mesostructured layers.
View Article and Find Full Text PDFUltrasmall CsPbBr perovskite quantum dots (PQDs) as promising blue-emitting materials are highly desired for full-color display and lighting applications, but their inferior efficiency and poor ambient stability hinder extensive applications. Herein, a "break-and-repair" strategy has been developed to tightly confine monodispersed ultrasmall CsPbBr PQDs in a zeolite. In this strategy, the CsPbBr PQDs are introduced into the zeolite a high temperature evaporation method, wherein the perovskite precursors break the zeolite framework, and amino acids and silane are then used to fix the damaged framework and lock the perovskite QDs within the matrix.
View Article and Find Full Text PDFAs a unique class of modular nanomaterials, metal-organic framework (MOF) nanoparticles have attracted widespread interest for use in various fields because of their diverse chemical functionalities, intrinsic microporosity, and three-dimensional (3D) nanoarchitectures. However, endowing MOF nanomaterials with precisely controlled structural symmetries and hierarchical macro/mesoporosities remains a formidable challenge for the researchers. Herein, we report a facile noncentrosymmetric pore-induced anisotropic assembly strategy to prepare a series of 3D dendritic MOF (UiO-66) nanomaterials with highly controllable structural symmetries and hierarchical macro/meso/microporosities.
View Article and Find Full Text PDFThe anisotropic surface functionalization of microporous zeolites with mesoporous materials into hierarchically porous heterostructures with distinctive physical and chemical properties is expected to significantly extend their applicability to catalysis. However, the precise control of the surface chemistry of zeolite crystals through site-specific interconnection with mesoporous materials remains a grand challenge. Here, we report a regioselective surface assembly strategy for the region-specific growth of mesoporous polymer/carbon on zeolite nanocrystals.
View Article and Find Full Text PDFWe report an anisotropic-kinetics transformation strategy to prepare single-crystalline aluminosilicate MFI zeolites (ZSM-5) with highly open nanoarchitectures and hierarchical porosities. The methodology relies on the cooperative effect of in situ etching and recrystallization on the evolution of pure-silica MFI zeolite (silicalite-1) nanotemplates under hydrothermal conditions. The strategy enables a controllable preparation of ZSM-5 nanostructures with diverse open geometries by tuning the relative rate difference between etching and recrystallization processes.
View Article and Find Full Text PDFEfficient charge separation can promote photocatalysis of semiconductors. Herein, a hollow-structured TiO sphere decorated with spatially separated bifunctional cocatalysts was designed, which exhibited enhanced photocatalytic hydrogen generation. Ultrasmall-sized MO (M = Pd, Co, Ni, or Cu) nanoparticles (NPs) were first introduced into a zeolite via confinement synthesis, and then, hollow TiO was fabricated by using the zeolite as a sacrificial template forming MO@TiO.
View Article and Find Full Text PDFConstructing ordered hierarchical porous structures while maintaining their overall crystalline order is highly desirable but remains an arduous challenge. Herein, we successfully achieve the growth of single-crystalline metal-organic frameworks (MOFs) in three-dimensional (3D) ordered macroporous template voids by a saturated solution-based double-solvent-assisted strategy with precise control over the nucleation process. The as-prepared single-crystalline ordered macro-microporous Co-based MOFs (SOM ZIF-67) exhibit an ordered macro-microporous structure with robust single-crystalline nature.
View Article and Find Full Text PDFLithium-sulfur batteries show advantages for next-generation electrical energy storage due to their high energy density and cost effectiveness. Enhancing the conductivity of the sulfur cathode and moderating the dissolution of lithium polysulfides are two key factors for the success of lithium-sulfur batteries. Here we report a sulfur host that overcomes both obstacles at once.
View Article and Find Full Text PDFNickel and cobalt incorporated MoS nanoboxes are synthesized via the reaction between Ni-Co Prussian blue analogue nanocubes and ammonium thiomolybdate. Due to the structural and compositional advantages, these well-defined nanoboxes manifest enhanced electrochemical activity as an electrocatalyst for hydrogen evolution reaction.
View Article and Find Full Text PDFHybrid hollow nanostructures with tailored shell architectures are attractive for electrochemical energy storage applications. Starting with metal-organic frameworks (MOFs), we demonstrate a facile formation of hybrid nanoboxes with complex shell architecture where a CoSe-enriched inner shell is intimately confined within a carbon-enriched outer shell (denoted as CoSe@carbon nanoboxes). The synthesis is realized through manipulation of the template-engaged reaction between Co-based zeolitic imidazolate framework (ZIF-67) nanocubes and Se powder at elevated temperatures.
View Article and Find Full Text PDFA multistimuli-responsive drug carrier is designed and successfully synthesized by self-assembly of thiol-modified periodic mesoporous organosilica (PMO) nanoparticles, coated gold nanoparticles (AuNPs), and mesostructured titanium dioxide (TiO2). Dye-loaded PMO-Au@TiO2 nanotablets are shown to respond to environmental changes (pH, temperature, and light) to achieve controlled release.
View Article and Find Full Text PDFHollow structures with high complexity in shell architecture and composition have attracted tremendous interest because of their great importance for both fundamental studies and practical applications. Herein we report the designed synthesis of novel box-in-box nanocages (NCs) with different shell compositions, namely, Co3O4/NiCo2O4 double-shelled nanocages (DSNCs). Uniform zeolitic imidazolate framework-67/Ni-Co layered double hydroxides yolk-shelled structures are first synthesized and then transformed into Co3O4/NiCo2O4 DSNCs by thermal annealing in air.
View Article and Find Full Text PDFMegranate-like nanoparticles possess a unique structure that is composed of multiple cores and shells, which is different from simple yolk-shell nanoparticles. Megranate-like nanoparticles can combine the properties of each component and be used as nanoreactors. This study describes the preparation of bifunctional megranate-like nanoreactors, consisting of multiple metal cores and thiol modified mesoporous SiO2 shells.
View Article and Find Full Text PDFNovel hierarchical spinous hollow titania hexagonal prisms are prepared through a facile fluorine-free self-template route using Ti2O3(H2O)2(C2O4)·H2O (TC) hexagonal prisms as a precursor. The hollowing transformation can be elucidated by the template-free Kirkendall effect, and diverse nanostructures can also be synthesized during the conversion process, such as the spinous core-shell and yolk-shell nanocomposites. The hierarchical hollow microparticles are composed of ultrathin nanobelts of 50-100 nm in length and about 10 nm in thickness, and possess a higher surface area of up to 163 m(2) g(-1) compared with solid microparticles (49 m(2) g(-1)).
View Article and Find Full Text PDFChem Commun (Camb)
October 2013
A new magnesium aluminophosphate JU92-300 with novel zeotype structure and 8-ring channels has been prepared by calcination of microporous JU-92 under 300 °C. Well dispersed C-dots are prepared by using JU92-300 as a support host. Such C-dots@zeolite materials exhibit excitation-dependent photoluminescent behavior, as well as tunable fluorescence with high quantum yields.
View Article and Find Full Text PDFA very simple cooperative template-directed coating method is developed for the preparation of core-shell, hollow, and yolk-shell microporous carbon nanocomposites. Particularly, the cationic surfactant C16TMA(+)·Br(-) used in the coating procedure improves the core dispersion in the reaction media and serves as the soft template for mesostructured resorcinol-formaldehyde resin formation, which results in the uniform polymer and microporous carbon shell coating on most functional cores with different surface properties. The core diameter and the shell thickness of the nanocomposites can be precisely tailored.
View Article and Find Full Text PDFA general synthetic procedure for highly ordered and well-dispersed periodic mesoporous organosilica (PMO) nanoparticles is reported based on a single cationic surfactant cetyltrimethylammonium bromide (CTAB) and simple silica sources with organic bridging groups via an ammonia-catalyzed sol-gel reaction. By changing the bridging group in the silica sources, the pore structures of the as-made particles with three-dimensional hexagonal (P6(3)/mmc), cubic (Pm3n), two-dimensional hexagonal (P6mm), and wormlike structure were evidenced by powder X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM). The size range of the nanoparticles can be adjusted from 30 nm to 500 nm by variation of the ammonia concentration or the co-solvent content of the reaction medium.
View Article and Find Full Text PDFThe biosynthesis of nanoparticles has received increasing attention due to the growing need to develop safe, cost-effective and environmentally friendly technologies for nano-materials synthesis. In this report, silver nanoparticles (AgNPs) were synthesized using a reduction of aqueous Ag(+) ion with the culture supernatants of Aspergillus terreus. The reaction occurred at ambient temperature and in a few hours.
View Article and Find Full Text PDFA novel design strategy to synthesize highly ordered hexagonally mesostructured metal-organic framework materials was successfully explored, which means the realization of directly cooperative self-assembly of metal ions, bridging ligands and surfactants in an aqueous system.
View Article and Find Full Text PDFOne advanced synthesis strategy for monodisperse silica cross-linked micellar core-shell nanoparticles (SCMCSNs) involves the use of organosilane termination agent R(n)Si(OR')(4 - n). In this study, we investigated the effects of the organosilane termination agent in the formation of SCMCSNs. Experimental data (synthesis results, (29)Si MAS NMR, molecule probe fluorescence spectra, etc.
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