Mesoporous Core Research Articles

Mesoporous ruthenium metal organic framework core shell templated CdS/rGO nanosheets catalyst for efficient bifunctional electro-catalytic oxygen reactions

This paper presents the first report of the excellent bi-functional electro-catalytic activity and durability of a structure that consists of a highly active inner core of a ruthenium metal organic framework with a mesoporous silica based shell covered with templated CdS nanoparticle electro-catalysts and reduced graphene oxide nanosheets. Excellent electro-catalytic activity toward both the oxygen reduction and oxygen evolution reactions is achieved by selecting a highly active core-shell of silica with CdS and rGO nanosheets as co-catalysts. In particular, the excellent catalytic activity of the 2 wt. % rGO/CdS/ silica nanocapsule catalyst for both reactions can be attributed to the large surface area and mesoporous nature, because they facilitate facile electrochemical activity, and lower the overpotentials and smaller Tafel values than other catalysts. In addition, it is more tolerant to methanol fuel crossover than commercial Pt/C, and exhibits long-term durability.

Ceria coated hexagonal mesoporous silica core–shell composite particle abrasives for improved chemical–mechanical planarization performance

The structure design of abrasive particles provides an available approach for improving both surface roughness and polishing efficiency in chemical–mechanical planarization/polishing (CMP) applications. In this work, the hexagonal mesoporous silica (H-mSiO2) particles with parallel channels were prepared via a modified tyltrimethylammonium bromide-assisted template method. And the ceria nanoparticles attached to H-mSiO2 was achieved by a solution synthesis technique. The core–shell structure of the as-prepared H-mSiO2–CeO2 composites was characterized in terms of X-ray diffraction, field emission scanning electron microscope, high-resolution transmission electron microscope, nitrogen adsorption/desorption measurement, and STEM–EDX mapping techniques. The oxide–CMP performance of the H-mSiO2–CeO2 composite particles as abrasives was evaluated in terms of surface finish and material removal rate. For comparison, the commercial ceria abrasives and solid silica (sSiO2)–CeO2 composite particles with non-porous sSiO2 cores were also tested under the same CMP conditions. Oxide–CMP results revealed that the H-mSiO2–CeO2 composite abrasives contributed to the finish reduction, efficiency improvement, and scratch elimination with respect to conventional ceria abrasives. By comparing with rigid solid silica (sSiO2)–CeO2 particles, the non-rigid H-mSiO2–CeO2 composites revealed a reduced surface roughness (0.17 nm vs. 0.33 nm, root-mean-square values), a low topographical variation (± 0.4 nm vs. ± 0.8 nm), and an improved removal rate (203 nm/min vs. 144 nm/min). The improved CMP performance might be attributed to the enhanced overall elastic response and reduced particle density, resulting from their hexagonal meso-silica cores with abundant parallel channels. Moreover, the increased Ce3+ concentration also contributed the improvement of polishing efficiency. This work describes an effort to explore the relationship between the meso-silica structure and finishing performance of the ceria-based core–shell abrasives for optimizing oxide–CMP characteristics.

Mesoporous multi-silica layer-coated Y2O3:Eu core-shell nanoparticles: Synthesis, luminescent properties and cytotoxicity evaluation

Mesoporous multi-layered silica-coated luminescent Y2O3:Eu nanoparticles (NPs) were prepared by a urea-based decomposition process, and their surfaces were gradually modified with nanoporous and mesoporous silica layers using modified sol-gel methods. The synthesized luminescent core-shell NPs were characterized thoroughly to investigate their structural, morphological, thermal, optical, photo luminescent properties and their surface chemistry. The morphology of the core NPs were nearly spherical in shape and were nano-sized grains. The observed luminescent efficiency of the mesoporous multi-layered silica-coated luminescent core NPs was gradually reduced because of bond formation between the Y2O3:Eu core and the amorphous silica shell via YOSiOH bridges on the surface of the NPs; the bonds suppressed the non-radiative transition pathways. Biocompatibility tests on Human breast cancer cells using the 3‑(4,5‑Dimethylthiazol‑2‑yl)‑2,5‑diphenyltetrazolium bromide and lactate dehydrogenase assays indicated that the core-shell NPs were non-toxic even at high concentrations. The mesoporous SiO2 layer played a key role in perfecting the solubility, biocompatibility, and non-toxicity of the NPs. The zeta potential, surface chemistry (Fourier transform infrared spectroscopy), and optical absorption spectral analyses revealed the high hydrophilicity of the as-prepared core-shell NPs because of the active surface-functionalized silanol (SiOH) groups, which could potentially offer many exciting opportunities in photonic-based biomedical applications.

Encapsulating highly crystallized mesoporous Fe3O4 in hollow N-doped carbon nanospheres for high-capacity long-life sodium-ion batteries

High capacity transition metal oxides have attracted much attention as potential sodium-ion batteries (SIBs) anodes. However, the fast capacity fading greatly limits their practical applications. In this study, highly crystallized mesoporous Fe3O4 nanoparticles encapsulated in the hollow nitrogen-doped carbon nanospheres (denoted as HCM-Fe3O4@void@N-C) have been synthesized and then explored as anode materials for SIBs. The resultant HCM-Fe3O4@void@N-C nanospheres possess a uniform particle size of ~ 180 nm with highly crystallized mesoporous Fe3O4 cores (~ 100 nm in diameter), a large surface area of ~ 250 m2 g−1 and a nitrogen-doped carbon shell (~ 7.6 wt%). Notably, a high discharge capacity of 372 mA h g−1 is obtained after the first five cycles at 160 mA g−1, which can gradually increase and be maintained at an ultrahigh specific capacity of 522 mA h g−1 even after 800 cycles. Besides, remarkable rate performance with a capacity of 196 mA h g−1 at a current density of 1200 mA g–1 and a high Coulombic efficiency (~ 100%) are obtained. Such good performance can be attributed to the unique yolk-shell nanostructure with a high crystallized mesoporous Fe3O4 core, a high conductive N-doped carbon shell, and a suitable void space, paving a new way to design and synthesize high-performance anode materials for SIBs.

Development and evaluation of hollow mesoporous silica microspheres bearing on enhanced oral delivery of curcumin

The aim of this work is to develop curcumin-loaded hollow mesoporous silica microspheres (HMSMs@curcumin) to improve the poor oral bioavailability of curcumin. Hollow mesoporous silica microspheres (HMSMs) were synthesized in facile route using a hard template. HMSMs and HMSMs@curcumin were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption/desorption measurements, differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), and X-ray diffraction (XRD). In addition, to demonstrate the potential application of the HMSMs@curcumin, cytotoxicity, in vitro release behavior and in vivo pharmacokinetics of curcumin loaded in these HMSMs were investigated by using of Caco-2 cells and Sprague-Dawley (SD) rats, respectively. These mono-dispersed HMSMs exhibited high drug loading ratio and encapsulation efficiency due to the mesoporous shell and hollow core. The excellent characteristics of HMSMs such as mono-dispersed morphology, smooth surface, uniform, ordered and size-narrowing mesopores resulted in a good in vitro release profile of curcumin from HMSMs@curcumin. Moreover, an impressive improvement in the oral absorption of curcumin and prolonged systemic circulation time were achieved in the in vivo animal studies. In addition, the good biocompatibility of developed HMSMs with Caco-2 cells was confirmed based on the in vitro cytotoxicity assay. In conclusion, this system demonstrated a great potential for efficient delivery of curcumin in vitro and in vivo, suggesting a good prospect for its application in clinic for therapeutic drug delivery in future.

Side effects-avoided theranostics achieved by biodegradable magnetic silica-sealed mesoporous polymer-drug with ultralow leakage

The development of drug delivery vehicles without side effects to normal physiological tissues represents an urgent challenge for safety and effective nanomedicine. Herein, a multifunctional drug delivery vehicle with ultralow leakage was presented, containing an ordered mesoporous resin as a polymer core and homogeneous Fe nanodots-doped silica as the biodegradable shell. In this core-shell structure, the Fe-doped silica shell acts as a compact inorganic cap to seal doxorubicin into the mesoporous polymer cores, but also serves as a superparamagnetic agent for magnetic targeting and magnetic resonance imaging (MRI). Importantly, the caps can be opened via Fe extraction-induced degradation to slowly release the loaded drug under the acidic tumor environment, while achieving ultralow drug leakage under normal in vivo blood circulation (physiological environment). This unique core-shell nanospheres with ultralow drug leakage were demonstrated to achieve side effects-avoided targeting chemotherapy guided by MRI with improved therapeutic outcomes, which showing great potential for efficient cancer theranostics.

Electron bridging structure glued yolk-shell hierarchical porous carbon/sulfur composite for high performance Li-S batteries

Despite various carbon materials have been extensively applied in lithium-sulfur (Li-S) battery, efficient optimization of the material structure for further performance improvement is remaining a great challenge. Herein, we fabricated electron bridging structure glued yolk-shell hierarchical porous carbon (HPC) nanospheres containing a microporous shell and a mesoporous core as cathode host for Li-S battery. In which, the inner mesoporous core acts as a sulfur reservoir to entrap polysulfide species, and the outer micropores shell provides not only large contact area between sulfur and conductive substrate, but also physical confinement and chemical adsorption to trap polysulfide. This yolk-shell HPC was further glued by an electron bridging structure consisting of carbon nanotube (CNT) decorated polyaniline (PANi), who can further suppress the shuttle effect benefit from PANi and afford a highly conductive network by affording a “point-to-plane” type electron transport mode instead of the “point-to-point”. As a result, this designed cathode material exhibits a high initial specific capacity of 1372 mAh g−1 at 0.2 A g−1, and excellent cycling stability with a capacity decay of 0.083% per cycle over 500 cycles at 2 A g−1. This strategy provides a promising approach for the design of multifunctional carbon materials for high performance Li-S batteries.

Peptide-Functionalized Hydrogel Cubes for Active Tumor Cell Targeting.

Conjugation of bioactive targeting molecules to nano- or micrometer-sized drug carriers is a pivotal strategy to improve their therapeutic efficiency. Herein, we developed pH- and redox-sensitive hydrogel particles with a surface-conjugated cancer cell targeting ligand for specific tumor-targeting and controlled release of the anticancer drug doxorubicin. The poly(methacrylic acid) (PMAA) hydrogel cubes of 700 nm and 2 μm with a hepsin-targeting (IPLVVPL) surface peptide are produced through multilayer polymer assembly on sacrificial cubical mesoporous cores. Direct peptide conjugation to the disulfide-stabilized hydrogels through a thiol-amine reaction does not compromise the structural integrity, hydrophilicity, stability in serum, or pH/redox sensitivity but does affect internalization by cancer cells. The cell uptake kinetics and the ultimate extent of internalization are controlled by the cell type and hydrogel size. The peptide modification significantly promotes the uptake of the 700 nm hydrogels by hepsin-positive MCF-7 cells due to ligand-receptor recognition but has a negligible effect on the uptake of 2 μm PMAA hydrogels. The selectivity of 700 nm IPLVVPL-PMAA hydrogel cubes to hepsin-overexpressing tumor cells is further confirmed by a 3-10-fold higher particle internalization by hepsin-positive MCF-7 and SK-OV-3 compared to that of hepsin-negative PC-3 cells. This work provides a facile method to fabricate enhanced tumor-targeting carriers of submicrometer size and improves the general understanding of particle design parameters for targeted drug delivery.

Engineering of large-pore lipid-coated mesoporous silica nanoparticles for dual cargo delivery to cancer cells

Lipid-coated mesoporous silica nanoparticles (LC-MSNs) have recently emerged as a next-generation cargo delivery nanosystem combining the unique attributes of both the organic and inorganic components. The high surface area biodegradable inorganic mesoporous silica core can accommodate multiple classes of bio-relevant cargos in large amounts, while the supported lipid bilayer coating retains the cargo and increases the stability of the nanocarrier in bio-relevant media which should promote greater bio-accumulation of LC-MSNs in cancer sites. In this contribution, we report on the optimization of various sol–gel synthesis (pH, stirring speed) and post-synthesis (hydrothermal treatment) procedures to enlarge the MSN pore size and tune the surface chemistry so as to enable loading and delivery of large biomolecules. The proof of concept of the dual cargo-loaded nanocarrier has been demonstrated in immortalized cervical cancer HeLa cells using MSNs of various fine-tuned pore sizes.

Trimetallic Au@PtPd Mesoporous Nanorods as Efficient Electrocatalysts for the Oxygen Reduction Reaction

Porous Pt-based nanostructures are highly promising electrocatalysts for fuel cells, because of their high catalytic surface area and sufficient catalytically active sites. Herein, we adopt a facile method in aqueous solution to synthesize the Au@PtPd mesoporous nanorod (Au@PtPd MNR) in which a Au nanorod (NR) serves as core, and mesoporous PtPd acts as shell. Because of the mesoporous core–shell structure and composition effect, Au@PtPd MNR exhibits superior catalytic activity and durability for the oxygen reduction reaction (ORR), as compared with PtPd mesoporous sphere (MS), Au@Pt MNR, and commercial Pt/C catalyst. This synthetic strategy is appropriate for preparation of other mesoporous core–shell structures for various promising applications.

Optoacoustic imaging identifies ovarian cancer using a microenvironment targeted theranostic wormhole mesoporous silica nanoparticle

At the intersection of the newly emerging fields of optoacoustic imaging and theranostic nanomedicine, promising clinical progress can be made in dismal prognosis of ovarian cancer. An acidic pH targeted wormhole mesoporous silica nanoparticle (V7-RUBY) was developed to serve as a novel tumor specific theranostic nanoparticle detectable using multispectral optoacoustic tomographic (MSOT) imaging. We report the synthesis of a small, < 40 nm, biocompatible asymmetric wormhole pore mesoporous silica core particle that has both large loading capacity and favorable release kinetics combined with tumor-specific targeting and gatekeeping. V7-RUBY exploits the acidic tumor microenvironment for tumor-specific targeting and tumor-specific release. In vitro, treatment with V7-RUBY containing either paclitaxel or carboplatin resulted in increased cell death at pH 6.6 in comparison to drug alone (p < 0.0001). In orthotopic ovarian xenograft mouse models, V7-RUBY containing IR780 was specifically detected within the tumor 7X and 4X higher than the liver and >10X higher than in the kidney using both multispectral optoacoustic tomography (MSOT) imaging with secondary confirmation using near infrared fluorescence imaging (p < 0.0004). The V7-RUBY system carrying a cargo of either contrast agent or an anti-neoplastic drug has the potential to become a theranostic nanoparticle which can improve both diagnosis and treatment of ovarian cancer.

Unique SiO2 Nanourchins Enable Amplification in Living Cells for In Situ Imaging of mRNAs

AbstractSufficient delivery of nucleic acid reagents into cells for amplifications with great activities would be significant for in situ intracellular imaging of messenger RNAs in living cells, showing great potentials in chemistry and biology. Herein, SiO2 nanourchins (SNUs) are developed, with two‐pronged pair of primers anchored on enzyme‐functionalized mesoporous SiO2 cores, for in situ imaging of mRNAs in living cells. Endowed by the urchins‐like structure to represent high loading capacity, efficient activity without mutual interference, and sufficient delivery into cells, SNUs maintain sustainable reactivities for amplification through primers' 3′‐end complete exposure and synergistic reagents release by increased dissociation or mobility during hybridization. “One‐step” reverse‐transcription helicase‐dependent isothermal amplifications are employed in living cells with Klenow (exo−) DNA polymerase to accomplish reverse transcriptions and polymerization amplifications. With high efficiency and stability, low toxicity, and good specificity, this method can detect amol of mRNA in dozens of microliter samples (&lt;0.02 molecules per cell) in living cells, providing an ultrasensitive tool for fundamental understanding of mRNAs in cellular processes.

L-Arginine-Catalyzed Synthesis of Nanometric Organosilica Particles through a Waterborne Sol-Gel Process and Their Porous Structure Analysis.

We report an efficient and easy-to-implement waterborne sol-gel process for the synthesis of nanometric organosilica particles. In this process, tetraethyl orthosilicate (TEOS) and 3-(methacryloxy)propyl trimethoxy silane (γ-MPS), employed as silica sources, were heterogeneously delivered in an aqueous solution of l-arginine, a basic amino acid used as a catalyst, from a top organic layer. Co-condensation of TEOS with γ-MPS led to the formation of organosilica particles with diameters between 30 and 230 nm when increasing the γ-MPS content from 0 to 10.1 mol % in the silica source. Nitrogen sorption analyses confirmed the microporous nature of the obtained particles after calcination. The Brunauer-Emmett-Teller (BET) surface areas increased from 27 (before calcination) to 684 m2 g-1 (after calcination) for the organosilica particles containing 10.1 mol % of γ-MPS. Fourier transform infrared spectroscopy and 29Si NMR were employed to analyze the chemical structure of the organosilica spheres and provide insight into the mechanism of particle formation. In the second part, hybrid organosilica particles with a core-shell morphology were synthesized through the combination of Pickering emulsion and the sol-gel process. γ-MPS emulsion droplets stabilized by tiny silica particles (formed in a separate step) were first generated and used as seeds to grow a silica shell on their surface through TEOS addition from the top organic layer. Transmission electron microscopy and pore size analyses of the resulting particles after calcination revealed a unique dual-porosity structure with a mesoporous inner core and a micro/mesoporous silica shell with ink-bottle-type pores.

Synthesis of magnetic gold mesoporous silica nanoparticles core shell for cellulase enzyme immobilization: Improvement of enzymatic activity and thermal stability

Abstract Magnetic gold mesoporous silica nanoparticle core shells (mAu@PSNs) were fabricated as a support and their size, morphology and structure was further characterized by X-Ray diffraction (XRD), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), transmission electron microscopy (TEM), dynamic light scattering (DLS) and thermal gravimetric analysis (TGA). Cellulase (CEL) immobilization on mAu@PSNs was performed via covalent bonding. Fourier transform infrared (FTIR) spectroscopy confirmed the successful binding of enzyme to mAu@PSNs while Bradford assay determined the binding efficiency to be 76%. The enzyme activity was measured at different pHs and temperatures by FPase method using Whatman filter paper as the substrate. The immobilized enzyme maintained 58% of its initial catalytic activity after nine hours. In this research, a new nano-system was designed as a solid support for cellulase immobilization which enhanced its thermal stability and facilitated its long term storage. In addition, the immobilized enzyme can be applied in a broader temperature and pH ranges while enzyme separation can be simply carried out by an external magnet.

Hybrid Mesoporous-Microporous Nanocarriers for Overcoming Multidrug Resistance by Sequential Drug Delivery.

Combination chemotherapy with a modulator and a chemotherapeutic drug has become one of the most promising strategies for the treatment of multidrug resistance (MDR) in cancer therapy. However, the development of nanocarriers with a high payload and sequential release of therapeutic agents poses a significant challenge. In this work, we report a type of hybrid nanocarriers prepared by polydopamine (PDA) mediated integration of the mesoporous MSN core and the microporous zeolite imidazolate frameworks-8 (ZIF-8) shell. The nanocarriers exploit storage capacities for drugs based on the high porosity and molecular sieving capabilities of ZIF-8 for sequential drug release. Particularly, large amounts of an anticancer drug (DOX, 607 μg mg-1) and a MDR inhibitor curcumin (CUR, 778 μg mg-1) were sequentially loaded in the mesoporous core via π-π stacking interactions mediated by PDA and in the microporous shell via the encapsulation during ZIF-8 growth. The sustained release of DOX was observed to follow earlier and faster release of CUR by acid-sensitive dissolution of the ZIF-8 shell. Furthermore, the nanoparticles showed good biocompatibility and effective cellular uptake in in vitro evaluations using drug-resistant MCF-7/ADR cancer cells. More importantly, the preferentially released CUR inhibited the drug efflux function of the membrane P-glycoprotein (P-gp), which subsequently facilitated the nuclear transportation of DOX released from the PDA-MSN core, and, in turn, the synergistic effects on killing MDR cancer cells. The hybrid mesoporous-microporous nanocarrier holds great promise for combination chemotherapy applications on the basis of sequential drug release.

Fabrication of a 3D Hierarchical Sandwich Co9 S8 /α-MnS@N-C@MoS2 Nanowire Architectures as Advanced Electrode Material for High Performance Hybrid Supercapacitors.

Supercapacitors suffer from lack of energy density and impulse the energy density limit, so a new class of hybrid electrode materials with promising architectures is strongly desirable. Here, the rational design of a 3D hierarchical sandwich Co9 S8 /α-MnS@N-C@MoS2 nanowire architecture is achieved during the hydrothermal sulphurization reaction by the conversion of binary mesoporous metal oxide core to corresponding individual metal sulphides core along with the formation of outer metal sulphide shell at the same time. Benefiting from the 3D hierarchical sandwich architecture, Co9 S8 /α-MnS@N-C@MoS2 electrode exhibits enhanced electrochemical performance with high specific capacity/capacitance of 306 mA h g-1 /1938 F g-1 at 1 A g-1 , and excellent cycling stability with a specific capacity retention of 86.9% after 10 000 cycles at 10 A g-1 . Moreover, the fabricated asymmetric supercapacitor device using Co9 S8 /α-MnS@N-C@MoS2 as the positive electrode and nitrogen doped graphene as the negative electrode demonstrates high energy density of 64.2 Wh kg-1 at 729.2 W kg-1 , and a promising energy density of 23.5 Wh kg-1 is still attained at a high power density of 11 300 W kg-1 . The hybrid electrode with 3D hierarchical sandwich architecture promotes enhanced energy density with excellent cyclic stability for energy storage.

Synthesis and Application of Dendritic Fibrous Nanosilica/Gold Hybrid Nanomaterials.

Morphologically unique silica nanoparticles can be used as effective templates to prepare silica–metal hybrid nanomaterials, which are highly applicable in a variety of areas. Mesoporous silica nanoparticles, which have high surface areas and an abundance of pores, can be used to synthesize mesoporous silica core–metal shell nanostructures with catalytically active sites. In this work, dendritic fibrous nanosilica (DFNS) with a high surface area is successfully employed as a template to synthesize DFNS/Au hybrid nanomaterials. Au nanodots are initially synthesized through the selective reduction of Au ions on the surface of the DFNS after surface modification to form DFNS/Au dots. A seed‐mediated growth method is used to controllably grow Au nanoparticles on the DFNS/Au dots to generate DFNS core–Au nanoparticles shell nanohybrids (DFNS/Au NPs) and DFNS core–Au layer shell nanohybrids (DFNS/Au layers). The catalytic activities of DFNS/Au NPs and DFNS/Au layers in the 4‐nitrophenol reduction reaction are compared.

Surface and redox characterization of new nanostructured ZrO2@CeO2 systems with potential catalytic applications

Ceria‐zirconia mixed oxides are widely used as catalysts and catalytic supports. Nevertheless, due to economic and geo‐strategic concerns, reducing and optimizing the lanthanide content in these formulations while preserving or even improving their excellent redox and catalytic properties has become a challenge for current research. In this context, the design of core@shell nanostructures arises as a feasible alternative to achieve the aforesaid goal. In the present work, a new nanostructured ZrO2@CeO2 system based on spherical and mesoporous zirconia cores coated by a well‐dispersed nanometer‐thick ceria layer has been prepared by a novel synthetic approach in 2 different steps: (1) synthesis of the zirconia cores by a sol‐gel method and (2) coating with a thin ceria shell by controlled chemical precipitation. The resulting nanocomposite was characterized by several techniques, which clearly reveal its perfect core@shell nanostructure and enhanced reducibility as compared with pure ceria.

Synthesis of mesoporous silica-polymer composite for the chloridazon pesticide removal from aqueous media

A meso-sorbent silica/polyaniline (MSNPs/PANI) composite was synthesized for the removal of the chloridazon pesticide (n-CLZ) from the aqueous solution. A high adsorption capacity by the n-CLZ molecules could be achieved by the surface-coating functionalization process of a mesoporous silica core by the PANI shell through two consequence steps process in the presence of a cationic surfactant. The formation of the polymeric MSNPs/PANI using MSNPs filler particles in the composite matrix were confirmed and characterized by SEM, HRTEM, XRD, TGA, and FTIR techniques. The removal efficiency of the n-CLZ pesticide from the aqueous solution using the synthesized MSNPs/PANI meso-sorbent was studied by the UV/Vis. Spectrometry and the GC analyses. Freundlich and Langmuir adsorption models were fitted and the thermodynamic parameters were calculated. Our results confirmed that the synthesized MSNPs/PANI meso-sorbent have a good removal efficiency towards n-CLZ pesticide from the aqueous solutions-based on a physical adsorption process.

One‐Step Synthesis of Hybrid Core–Shell Metal–Organic Frameworks

AbstractEpitaxial growth of MOF‐on‐MOF composite is an evolving research topic in the quest for multifunctional materials. In previously reported methods, the core–shell MOFs were synthesized via a stepwise strategy that involved growing the shell‐MOFs on top of the preformed core‐MOFs with matched lattice parameters. However, the inconvenient stepwise synthesis and the strict lattice‐matching requirement have limited the preparation of core–shell MOFs. Herein, we demonstrate that hybrid core–shell MOFs with mismatching lattices can be synthesized under the guidance of nucleation kinetic analysis. A series of MOF composites with mesoporous core and microporous shell were constructed and characterized by optical microscopy, powder X‐ray diffraction, gas sorption measurement, and scanning electron microscopy. Isoreticular expansion of microporous shells and orthogonal modification of the core was realized to produce multifunctional MOF composites, which acted as size selective catalysts for olefin epoxidation with high activity and selectivity.