Mesoporous Framework Research Articles

Multifunctional Integrated Interdigital Microsupercapacitors and Self-Powered Iontronic Tactile Pressure Sensor for Wearable Electronics.

Multifunctionality and self-powering are key technologies for next-generation wearable electronics. Herein, an interdigitated MXene/TiS2-based self-powered intelligent pseudocapacitive iontronic sensor system is designed, realizing integration of energy storage and pressure-sensitive sensing function into one device. The intercalation of TiS2 nanosheet can effectively prevent self-stacking of MXene and results in mesoporous cross-linked framework, therefore exposing more active sites and broadening the electron/ion transport channels. The pressure sensing performance together with developed all-solid-state microsupercapacitor is explored systematically. When applied in a symmetrical microsupercapacitor, it presents a satisfactory energy density of 31.6 Wh/kg at 400 W/kg and 79.8% capacitance retention after 10 000 cycles. Meanwhile, with MXene/TiS2//MXene/TiS2 interdigitated structure as flexible self-powering pressure sensor, it illustrates outstanding pressure-sensing response toward external pressure, realizing accurate and continuous detection of human body motion signals. It is believed that this work proposes a feasible strategy by integrating pressure-sensing with a self-powering function for the next-generation self-powered E-skin electronics.

MIL-101-Cr/Fe/Fe-NH2 for Efficient Separation of CH4 and C3H8 from Simulated Natural Gas.

Adsorptive separation based on porous solid adsorbents has emerged as an excellent effective alternative to energy-intensive conventional separation methods in a low energy cost and high working capacity manner. However, there are few stable mesoporous metal-organic frameworks (MOFs) for efficient purification of methane from other light hydrocarbons in natural gas. Herein, we report a series of stable mesoporous MOFs, MIL-101-Cr/Fe/Fe-NH2, for efficient separation of CH4 and C3H8 from a ternary mixture CH4/C2H6/C3H8. Experimental results show that all three MOFs possess excellent thermal, acid/basic, and hydrothermal stability. Single-component adsorption suggested that they have high C3H8 adsorption capacity and commendable selectivity for C3H8 and C2H6 over CH4. Transient breakthrough experiments further certified the ability of direct separation of CH4 from simulated natural gas and indirect recovery of C3H8 from the packing column. Theoretical calculations illustrated that the van der Waals force proportional to the molecular weight is the key factor and that the structural integrity and defect can impact separation performances.

Amorphous Ultra-Small Fe-Based Nanocluster Engineered and ICG Loaded Organo-Mesoporous Silica for GSH Depletion and Photothermal-Chemodynamic Synergistic Therapy.

Intracellular oxidative amplification can effectively destroy tumor cells. Additionally, Fe-mediated Fenton reaction often converts cytoplasm H2 O2 to generate extensive hypertoxic hydroxyl radical (• OH), leading to irreversible mitochondrion damage for tumor celleradication, which is widely famous as tumor chemodynamic therapy (CDT). Unfortunately, intracellular overexpressed glutathione (GSH) always efficiently scavenges • OH, resulting in the significantly reduced CDT effect. To overcome this shortcoming and improve the oxidative stress in cytoplasm, Fe3 O4 ultrasmall nanoparticle encapsulated and ICG loaded organo-mesoporous silica nanovehicles (omSN@Fe-ICG) are constructed to perform both photothermal and GSH depletion to enhance the Fenton-like CDT, by realizing intracellular oxidative stress amplification. After this nanoagents are internalized, the tetrasulfide bonds in the dendritic mesoporous framework can be decomposed with GSH to amplify the toxic ROS neration by selectively converting H2 O2 to hydroxyl radicals through the released Fe-based nanogranules. Furthermore, the NIR laser-induced hyperthermia can further improve the Fenton reaction rate that simultaneously destroyed the mitochondria. As a result, the GSH depletion and photothermal assisted CDT can remarkably improve the tumor eradication efficacy.

Oxygen vacancy-mediated amorphous GeOx assisted polysulfide redox kinetics for room-temperature sodium-sulfur batteries

The practical applications of room-temperature sodium-sulfur (RT Na-S) batteries have been greatly hindered by the natural sluggish reaction kinetics of sulfur and the shuttle effect of sodium polysulfide (NaPSs). Herein, oxygen vacancy (OV)-mediated amorphous GeOx/nitrogen doped carbon (donated as GeOx/NC) composites were well designed as sulfur hosts for RT Na–S batteries. Experimental and density functional theory studies show that the introduction of oxygen vacancies on GeOx/NC can effectively immobilize polysulfides and accelerate the redox kinetics of polysulfides. Meanwhile, the micro-and mesoporous framework, acting as a reactor for storing active S, is conducive to alleviating the expansion of S during the charging/discharging process. Consequently, the S@GeOx/NC cathode affords a reversible capacity of 1017 mA h g−1 at 0.1 A g−1 after 100 cycles, outstanding rate capability of 333 mA h g−1 at 10.0 A g−1 and long lifespan cyclability of 385 mAh g−1 at 1 A g−1 after 1200 cycles. This work furnishes a new way for the rational design of metal oxides with oxygen vacancies and boosts the application for RT Na-S batteries.

Atomically dispersed iron enables high-efficiency electrocatalytic conversion of nitrate to dinitrogen on a N-coordinated mesoporous carbon architecture

Conversion of nitrate to dinitrogen (N2) is a great challenge in environmental remediation, because it is difficult to control a complete N–N coupling reaction for N2 generation. Herein, we report an atomically dispersed iron coordinated with nitrogen on an ordered mesoporous carbon framework (Meso-Fe–N–C) by a multicomponent co-assembly to improve the selectivity of electrocatalytic denitrification. Impressively, the N2 conversion rate (2176 mg N h−1 g−1 Fe) is 1–3 orders of magnitude higher than that of other iron-based and previously reported materials. Both of N coordination and geometric distortion derived from mesostructure tune the electronic structure of Fe site. This leads to a modest adsorption binding strength with key intermediate to balance the amounts of the surface-bound and solvated nitric oxide (NO). Meanwhile, mesochannels confine solvated NO for dimerization via the Eley-Rideal mechanism to promote N2 formation. The applicability over a wide pH range and long-term stability demonstrates potential practical application.

Enriching SO42− Immobilization on α-Fe2O3 via Spatial Confinement for Robust NH3-SCR Denitration

The application of iron oxide to NH3-SCR is attractive but largely hindered by its poor acid properties, and surface sulfation is proven to be a prominent way of enhancing the acidity. As such, the method of enriching the sulfate species on iron oxide is crucial for improving the NH3-SCR performance. In the present study, by employing ammonium bisulfate (ABS) as the source of gaseous SO2 for the purpose of trapping, we reported an effective strategy for enhancing the SO42− immobilization on α-Fe2O3 catalyst via spatial confinement in a mesoporous SBA-15 framework. Interestingly, although the presence of the mesopore channel had an adverse effect on the ABS decomposition, which was expected to produce less available SO2, the measured SO42− immobilized on α-Fe2O3 in the mesoporous SBA-15 system was significantly greater than that of the regular SiO2, demonstrating the promoting effect of the spatial confinement on the SO42− enrichment. Further characterizations of the NH3-TPD, NO oxidation, and NH3-SCR performance tests proved that, as a result of the enhanced acidity, the enrichment of SO42− on α-Fe2O3 displayed a clear correlation with the SCR activity. The results of the present study provide an effective strategy for boosting the catalytic performance of iron oxide in NH3-SCR via SO42− enrichment.

Macrolactonization of methyl 15-hydroxypentadecanoate to cyclopentadecanolide using KF-La/γ-Al2O3 catalyst.

It has been a challenge to synthesize macrolide musk in excellent yields with high purity. KF-La/γ-Al2O3 catalyst was prepared from a highly basic mesoporous framework using a mild method. The prepared KF-La/γ-Al2O3 catalyst was employed for the synthesis of cyclopentadecanolide from methyl 15-hydroxypentadecanoate. The morphology and structure of prepared catalysts were characterized using XRD, TG-DTG, SEM, EDX, TEM, BET and CO2-TPD. The results revealed that the K3AlF6 and LaOF are produced on the surface of KF-La/γ-Al2O3, and LaO can promote the dispersion of KF on the surface of Al2O3. Catalysts pore size main distribution ranges between 10 and 30 nm, the maximum CO2 desorption temperature is 715°C when the La loading is 25%. Because F− ion has a higher electronegativity than O2− ion, the KF-promoted metal oxide (Al2O3 or/and La2O3) contained more strong basic sites, compared with that of the corresponding metal oxide. The yield of cyclopentadecanolide obtained at 0.5 g KF-25La/γ-Al2O3 catalyst and a reaction temperature of 190°C for 7 h were 58.50%, and the content after reactive distillation is 98.8%. The KF-La/γ-Al2O3 catalyst has a larger pore size and basic strength, which is more conducive to the macrolactonization of long-chain hydroxy ester.

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.

Metal-Chelatable Porphyrinic Frameworks for Single-Cell Multiplexing with Mass Cytometry.

Single-cell multiplexing is key to exploration of the heterogeneous cell populations in biological systems. Although the state-of-the-art mass cytometry (CyTOF) possesses high resolution and multiple dimensions, the lack of suitable marker materials prohibits fully exploiting the available CyTOF detection channels. Here we report a new design strategy for CyTOF markers using functionalized mesoporous porphyrinic frameworks (MPFs) as scaffolds for chelating metals that have been unachievable by conventional approaches. We developed surface modification for stably dispersing the MPF nanoparticles (<40 nm) during the metalation and antibody conjugation processes. Our markers exhibit higher sensitivity and comparable specificity compared with a polymer-based commercial benchmark. Compatibility with commercial markers during co-staining was also confirmed. Furthermore, our markers show promising performance for immunophenotyping and potential implementation in CyTOF systems.

Metal‐Chelatable Porphyrinic Frameworks for Single‐Cell Multiplexing with Mass Cytometry

AbstractSingle‐cell multiplexing is key to exploration of the heterogeneous cell populations in biological systems. Although the state‐of‐the‐art mass cytometry (CyTOF) possesses high resolution and multiple dimensions, the lack of suitable marker materials prohibits fully exploiting the available CyTOF detection channels. Here we report a new design strategy for CyTOF markers using functionalized mesoporous porphyrinic frameworks (MPFs) as scaffolds for chelating metals that have been unachievable by conventional approaches. We developed surface modification for stably dispersing the MPF nanoparticles (&lt;40 nm) during the metalation and antibody conjugation processes. Our markers exhibit higher sensitivity and comparable specificity compared with a polymer‐based commercial benchmark. Compatibility with commercial markers during co‐staining was also confirmed. Furthermore, our markers show promising performance for immunophenotyping and potential implementation in CyTOF systems.

Co3O4 Nanoparticles Accommodated Mesoporous TiO2 framework as an Excellent Photocatalyst with Enhanced Photocatalytic Properties

Designing effective heterojunction photocatalysts with facile synthesis and low cost exists challenges and is demand for antibiotics degradation under visible illumination. Here, we focus on an advanced nanocomposite based on a mesoporous TiO2 framework accommodated with Co3O4 NPs with variation Co3O4 percentages through soft template and impregnation procedure. The obtained heterojunction Co3O4/TiO2 nanocomposites possess a mesoporous structure with high large surface area (184 m2 g−1). The obtained heterojunction Co3O4/TiO2 photocatalyst was examined for the photooxidation of ciprofloxacin (CIP) under visible exposure. The optimal 1.5% Co3O4/TiO2 nanocomposite revealed the highest degradation performance ∼100% within 60 min. The 1.5% Co3O4/TiO2 photocatalyst indicated the highest apparent rate constant (0.0157 min−1), about 13 times larger than pristineTiO2 (0.0012 min−1). The synthesized Co3O4/TiO2 photocatalyst exhibited superb photodegradation efficiency and excellent stability (five cycles) without loss in photocatalytic ability. The construction of S-scheme Co3O4/TiO2 p–n heterojunction with synergistic effect can boost migration of photoinduced carriers and build the close interface, thereby producing more active oxidative species for photodegradation of CIP. This work provides the construction and design of S-scheme heterojunction photocatalysts for practical applications under visible light.

Hierarchically mesoporous imidazole-functionalized covalent triazine framework: An efficient metal- and halogen-free heterogeneous catalyst towards the cycloaddition of CO2 with epoxides

The conversion of CO2 into value-added cyclic carbonates over metal- and halogen-free heterogeneous catalyst has attracted much attention but remains a huge challenge. Herein, a covalent triazine framework (CTF) with hierarchical microstructure was synthesized from cyanuric chloride and 1,4-phenylenediamine by a simple solvothermal approach compared to traditional ionothermal trimerization methods. While functionalizing the CTF framework with imidazole (IM) groups, the resultant CTF-IM exhibits excellent catalytic activity for the synthesis of cyclic carbonate from CO2 and epoxides under metal-, halogen- and solvent-free conditions. Under optimal reaction conditions, the representative epoxide, epichlorohydrin, afforded the corresponding cyclic carbonate in almost quantitative yield (94.6%), which is 5.4 times than that obtained over the parent CTF. The Lewis acidic C2-H and Lewis basic nitrogen atom play vital roles in the activation of epoxide and CO2, respectively, which help the cycloaddition reaction to proceed faster. In addition, CTF-IM has good chemical stability and recyclability, as well as could be applicable to a wide range of substituted epoxides.

Unusual Mesoporous Titanium Niobium Oxides Realizing Sodium‐Ion Batteries Operated at −40 °C

The sodium-ion batteries (SIBs) are promising candidate for grid-scale energy storage, however, the sluggish ion diffusion kinetics brought by the large radius of Na+ seriously limits the SIBs' performances, let alone at low temperatures. Herein, we propose a confined acid-base pair self-assembly strategy to synthesize unusual Ti0.88 Nb0.88 O4- x @C for high performance SIBs operated at room and low temperatures. The confinement self-assembly of acid-base pair around the micelles and confined crystallization by carbon layer realize the formation of ordered and stoichiometric mesoporous frameworks with opened ion channels. Thus, the mesoporous Ti0.88 Nb0.88 O4- x @C exhibits rapid Na+ diffusion kinetics at 25 and -40°C, which are one order higher than that of the nonporous one. A high reversible capacity of 233 mAh g-1 , excellent rate (a specific capacity of 103 mAh g-1 at 50 C) and cycling performances (<0.03% fading per cycle) can be observed at 25°C. More importantly, even at -40°C, the mesoporous Ti0.88 Nb0.88 O4- x @C can still deliver the 161 mAh g-1 capacity, a high initial Coulombic efficiency of 60% and outstanding cycling stability (99 mAh g-1 at 0.5 C after 500 cycles). We believe this strategy opens a new avenue for constructing novel mesoporous electrode materials for low-temperature energy storage. This article is protected by copyright. All rights reserved.

Rhodium-Containing Mesoporous Aromatic Frameworks as Catalysts for Hydroformylation of Unsaturated Compounds

Rhodium-Containing Mesoporous Aromatic Frameworks as Catalysts for Hydroformylation of Unsaturated Compounds

Templated synthesis of crystalline mesoporous CeO2 with organosilane-containing polymers: balancing porosity, crystallinity and catalytic activity

We report the synthesis of ordered mesoporous ceria (mCeO2) with highly crystallinity and thermal stability using hybrid polymer templates consisting of organosilanes. Those organosilane-containing polymers can convert into silica-like nanostructures that further serve as thermally stable and mechanically strong templates to prevent the collapse of mesoporous frameworks during thermal-induced crystallization. Using a simple evaporation-induced self-assembly process, control of the interaction between templates and metal precursors allows the co-self-assembly of polymer micelles and Ce3+ ions to form uniform porous structures. The porosity is well-retained after calcination up to 900 °C. After the thermal engineering at 700 °C for 12 h (mCeO2-700-12 h), mCeO2 still has a specific surface area of 96 m2 g−1 with a pore size of 14 nm. mCeO2 is demonstrated to be active for electrochemical oxidation of sulfite. mCeO2-700-12 h with a perfect balance of crystallinity and porosity shows the fastest intrinsic activity that is about 84 times more active than bulk CeO2 and 5 times more active than mCeO2 that has a lower crystallinity.

Analogy Powered by Prediction and Structural Invariants: Computationally Led Discovery of a Mesoporous Hydrogen-Bonded Organic Cage Crystal.

Mesoporous molecular crystals have potential applications in separation and catalysis, but they are rare and hard to design because many weak interactions compete during crystallization, and most molecules have an energetic preference for close packing. Here, we combine crystal structure prediction (CSP) with structural invariants to continuously qualify the similarity between predicted crystal structures for related molecules. This allows isomorphous substitution strategies, which can be unreliable for molecular crystals, to be augmented by a priori prediction, thus leveraging the power of both approaches. We used this combined approach to discover a rare example of a low-density (0.54 g cm–3) mesoporous hydrogen-bonded framework (HOF), 3D-CageHOF-1. This structure comprises an organic cage (Cage-3-NH2) that was predicted to form kinetically trapped, low-density polymorphs via CSP. Pointwise distance distribution structural invariants revealed five predicted forms of Cage-3-NH2 that are analogous to experimentally realized porous crystals of a chemically different but geometrically similar molecule, T2. More broadly, this approach overcomes the difficulties in comparing predicted molecular crystals with varying lattice parameters, thus allowing for the systematic comparison of energy–structure landscapes for chemically dissimilar molecules.

Synthesis and Characterization of Feldspar Aluminosilicate Minerals/MCM-48 Composite, Micropore and Mesopore Framework

Synthesis and Characterization of Feldspar Aluminosilicate Minerals/MCM-48 Composite, Micropore and Mesopore Framework

Insight into the development of silica-based materials as photocatalysts for CO2 photoconversion towards CH3OH: A review and recent progress

High exploitation of fossil fuel energy has resulted in substantial CO2 emissions into the atmosphere, leading to severe global warming. Tremendous strategies have been developed to explore possible approaches in minimizing the content of CO2 in the atmosphere. CO2 photoconversion into CH3OH has been put forward as a promising strategy since anthropogenic CO2 is utilized to generate valuable CH3OH assisting by clean solar energy. Silica-based materials have emerged as potential candidates for photocatalysts is accredited to their mesoporous framework with a large surface area, flexible tunability pore sizes, excellent thermal stability, and capability to suppress metal particle growth. Thus, this review encompasses the current progress on applying and developing silica-based materials as photocatalysts for CO2 photoconversion into CH3OH. Apart from that, fundamental aspects of the mechanism, the factors affecting performance, and the efficiency of silica-based materials in CO2 photoconversion to CH3OH are also comprehensively highlighted. The difficulties and prospects of CO2 photoconversion into CH3OH via silica-based materials are also discussed. In general, the most recent scenarios recommended further investigation to explore these materials since CO2 photoconversion to CH3OH has not been adequately investigated in the literature.

Robust Mesoporous Functional Hydrogen-Bonded Organic Framework for Hypochlorite Detection.

Although tremendous progress has been achieved in the field of hydrogen-bonded organic frameworks (HOFs), the low stability, small/none pores, and difficult functionality severely obstruct their development. Herein, a novel robust mesoporous HOF (HOF-FAFU-1) decorated with a high density of free hydroxy moieties has been designed and readily synthesized in the de novo synthesis. In HOF-FAFU-1, the planar building blocks are connected to each other by typical intermolecular carboxylate dimers to form two-dimensional (2D) layers with sql topology, which are further connected to their adjacent layers by face-to-face π-π interactions to obtain a three-dimensional (3D) open mesoporous framework. Owing to the high density of intermolecular hydrogen bonding and strong π-π interactions, HOF-FAFU-1 is very stable, allowing it to retain its structure in aqueous solutions with a pH range of 1-9. Benefiting from the decorated hydroxy moieties, HOF-FAFU-1 was exploited as a fluorescent sensor for hypochlorite detection in water media by a turn-off mode, which cannot be realized by its nonhydroxy groups anchoring counterpart (HOF-TCBP). The proposed sensing system is highly efficient, validated by a very broad linear range (0-0.45 mM), fast response (15 s), and small limit of detection (LOD) (1.32 μM). The fluorescent quenching of HOF-FAFU-1 toward hypochlorite was also investigated, mainly being ascribed to the transformation of building blocks from the fluorescent reduced state to the nonfluorescent oxidative state. This work not only demonstrates that HOFs integrated with high stability and large pores as well as high density of functional groups can be simultaneously realized by judicious design of building blocks but also conceptually elucidates that such HOFs can effectively extend the application fields of HOFs.

Rational design of imine‐linked three‐dimensional mesoporous covalent organic frameworks with bor topology

AbstractThree‐dimensional (3D) covalent organic frameworks (COFs) possess great potential applications in various fields. Constructing 3D COFs with large pore sizes is extremely challenging due to the interpenetration and collapse. Herein, we report a series of crystalline imine‐linked 3D COFs (3D‐bor‐COF‐1, 3D‐bor‐COF‐2, 3D‐bor‐COF‐3) with mesoporous channels through rationally designing the topology configuration. These 3D‐bor‐COFs display permanent porosity and Brunauer–Emmett–Teller (BET) surfaces of 3205.5, 1752.7, and 2077.3 m2 g−1 (SLangmuir = 4277.7, 2480.3, and 2698.0 m2 g−1), respectively. The pore sizes of 3D‐bor‐COFs were confirmed by the lattice fringes from high‐resolution transmission electron microscopy, as well as structural simulation and nitrogen adsorption isotherm analysis. 3D‐bor‐COFs display large pore sizes (3.8 nm for 3D‐bor‐COF‐3), which is among the highest record of 3D COFs. Owing to the unstacked‐aromatic pore environment and high specific surface area, 3D‐bor‐COFs display excellent adsorption capacity for benzene vapor (1203.9 mg g−1 for 3D‐bor‐COF‐3) under 298 K, which is three times higher than that of the best‐reported 2D COF. This work not only provides inspiration for designing 3D mesoporous imine‐COFs, but also demonstrates a strategy for constructing aromatics adsorption materials.