Showing papers on "Mesoporous material published in 2021"

MIL-101-Derived Mesoporous Carbon Supporting Highly Exposed Fe Single-Atom Sites as Efficient Oxygen Reduction Reaction Catalysts.

Abstract: Fe single-atom catalysts (Fe SACs) with atomic FeNx active sites are very promising alternatives to platinum-based catalysts for the oxygen reduction reaction (ORR). The pyrolysis of metal-organic frameworks (MOFs) is a common approach for preparing Fe SACs, though most MOF-derived catalysts reported to date are microporous and thus suffer from poor mass transfer and a high proportion of catalytically inaccessible FeNx active sites. Herein, NH2 -MIL-101(Al), a MOF possessing a mesoporous cage architecture, is used as the precursor to prepare a series of N-doped carbon supports (denoted herein as NC-MIL101-T) with a well-defined mesoporous structure at different pyrolysis temperatures. The NC-MIL101-T supports are then impregnated with a Fe(II)-phenanthroline complex, and heated again to yield Fe SAC-MIL101-T catalysts rich in accessible FeNx single atom sites. The best performing Fe SAC-MIL101-1000 catalyst offers outstanding ORR activity in alkaline media, evidenced by an ORR half-wave potential of 0.94 V (vs RHE) in 0.1 m KOH, as well as excellent performance in both aqueous primary zinc-air batteries (a near maximum theoretical energy density of 984.2 Wh kgZn -1 ) and solid-state zinc-air batteries (a peak power density of 50.6 mW cm-2 and a specific capacity of 724.0 mAh kgZn -1 ).

Atomic Fe Dispersed Hierarchical Mesoporous Fe–N–C Nanostructures for an Efficient Oxygen Reduction Reaction

Abstract: Due to the scarcity and high cost of precious metals, the hydrogen economy would ultimately rely on non-platinum-group-metal (non-PGM) catalysts. The non-PGM-catalyzed oxygen reduction reaction, wh...

Synthesis of core–shell Co@S-doped carbon@ mesoporous N-doped carbon nanosheets with a hierarchically porous structure for strong electromagnetic wave absorption

Abstract: Electromagnetic wave absorbents with hierarchically porous and core–shell structures have significantly positive influence on the electromagnetic wave absorption because of the enhanced interfacial polarization. Furthermore, the core–shell structure also introduces components with strong dielectric loss and good resistance to chemical corrosion. Herein, the cobalt–metal–organic frameworks @mesoporous polydopamine (Co–MOF@MPDA) composites with a core–shell structure are prepared by the bottom-up monomicelle assembly. After calcination, the Co@S-doped carbon core and mesoporous N-doped carbon shell (Co@SC@MNC) were obtained. Through adjusting the calcination temperature, the dielectric and magnetic loss can be tuned, resulting in the strong absorption capability for the electromagnetic wave. The minimum reflection loss reaches −72.3 dB, while the effective absorption bandwidth is as broad as 6.0 GHz. The unique structure and the formation of internal cavity between Co@SC and MNC contribute to the interfacial polarization. The enhancement of the dipole polarization loss and conduction loss are ascribed to the S, N-doped hierarchically porous carbon. Importantly, the presence of Co nanoparticles facilitates the magnetic–dielectric synergy to improve the impedance matching due to the introduction of magnetic loss. The novel structural design has potential application in the electromagnetic wave absorption field.

Highly active and stable Ni dispersed on mesoporous CeO2-Al2O3 catalysts for production of syngas by dry reforming of methane

Abstract: Ni-based mesoporous mixed CeO2-Al2O3 oxide catalysts prepared by one pot Evaporation Induced Self Assembly (EISA) were tested in dry reforming of methane. The textural, structural and physicochemical properties of the catalysts were studied by N2 adsorption-desorption, TEM-EDS, XRD and elemental analysis. The mobility of oxygen in the structure and the redox properties were investigated by OSCC measurements, TPR and in situ DRIFTS. Finally, the post-reaction samples were analyzed by TGA, RAMAN and TEM. The calcined catalysts prepared by EISA method present mesoporous structures with highly dispersed Ni in the form of NiAl2O4 spinel clusters. After reduction, small size metallic Ni particles are observed (

N-Doped Graphene-Decorated NiCo Alloy Coupled with Mesoporous NiCoMoO Nano-sheet Heterojunction for Enhanced Water Electrolysis Activity at High Current Density

Abstract: Developing highly effective and stable non-noble metal-based bifunctional catalyst working at high current density is an urgent issue for water electrolysis (WE). Herein, we prepare the N-doped graphene-decorated NiCo alloy coupled with mesoporous NiCoMoO nano-sheet grown on 3D nickel foam (NiCo@C-NiCoMoO/NF) for water splitting. NiCo@C-NiCoMoO/NF exhibits outstanding activity with low overpotentials for hydrogen and oxygen evolution reaction (HER: 39/266 mV; OER: 260/390 mV) at ± 10 and ± 1000 mA cm−2. More importantly, in 6.0 M KOH solution at 60 °C for WE, it only requires 1.90 V to reach 1000 mA cm−2 and shows excellent stability for 43 h, exhibiting the potential for actual application. The good performance can be assigned to N-doped graphene-decorated NiCo alloy and mesoporous NiCoMoO nano-sheet, which not only increase the intrinsic activity and expose abundant catalytic activity sites, but also enhance its chemical and mechanical stability. This work thus could provide a promising material for industrial hydrogen production.

Three-Dimensional Ordered Mesoporous Carbon Spheres Modified with Ultrafine Zinc Oxide Nanoparticles for Enhanced Microwave Absorption Properties

Abstract: Currently, electromagnetic radiation and interference have a significant effect on the operation of electronic devices and human health systems. Thus, developing excellent microwave absorbers have a huge significance in the material research field. Herein, a kind of ultrafine zinc oxide (ZnO) nanoparticles (NPs) supported on three-dimensional (3D) ordered mesoporous carbon spheres (ZnO/OMCS) is prepared from silica inverse opal by using phenolic resol precursor as carbon source. The prepared lightweight ZnO/OMCS nanocomposites exhibit 3D ordered carbon sphere array and highly dispersed ultrafine ZnO NPs on the mesoporous cell walls of carbon spheres. ZnO/OMCS-30 shows microwave absorbing ability with a strong absorption (− 39.3 dB at 10.4 GHz with a small thickness of 2 mm) and a broad effective absorption bandwidth (9.1 GHz). The outstanding microwave absorbing ability benefits to the well-dispersed ultrafine ZnO NPs and the 3D ordered mesoporous carbon spheres structure. This work opened up a unique way for developing lightweight and high-efficient carbon-based microwave absorbing materials.

Interfacial Assembly and Applications of Functional Mesoporous Materials.

Abstract: Functional mesoporous materials have gained tremendous attention due to their distinctive properties and potential applications. In recent decades, the self-assembly of micelles and framework precursors into mesostructures on the liquid-solid, liquid-liquid, and gas-liquid interface has been explored in the construction of functional mesoporous materials with diverse compositions, morphologies, mesostructures, and pore sizes. Compared with the one-phase solution synthetic approach, the introduction of a two-phase interface in the synthetic system changes self-assembly behaviors between micelles and framework species, leading to the possibility for the on-demand fabrication of unique mesoporous architectures. In addition, controlling the interfacial tension is critical to manipulate the self-assembly process for precise synthesis. In particular, recent breakthroughs based on the concept of the "monomicelles" assembly mechanism are very promising and interesting for the synthesis of functional mesoporous materials with the precise control. In this review, we highlight the synthetic strategies, principles, and interface engineering at the macroscale, microscale, and nanoscale for oriented interfacial assembly of functional mesoporous materials over the past 10 years. The potential applications in various fields, including adsorption, separation, sensors, catalysis, energy storage, solar cells, and biomedicine, are discussed. Finally, we also propose the remaining challenges, possible directions, and opportunities in this field for the future outlook.

Perovskite Quantum Dots Encapsulated in a Mesoporous Metal-Organic Framework as Synergistic Photocathode Materials.

Abstract: Metal halide perovskite quantum dots, with high light-absorption coefficients and tunable electronic properties, have been widely studied as optoelectronic materials, but their applications in photocatalysis are hindered by their insufficient stability because of the oxidation and agglomeration under light, heat, and atmospheric conditions. To address this challenge, herein, we encapsulated CsPbBr3 nanocrystals into a stable iron-based metal-organic framework (MOF) with mesoporous cages (∼5.5 and 4.2 nm) via a sequential deposition route to obtain a perovskite-MOF composite material, CsPbBr3@PCN-333(Fe), in which CsPbBr3 nanocrystals were stabilized from aggregation or leaching by the confinement effect of MOF cages. The monodispersed CsPbBr3 nanocrystals (4-5 nm) within the MOF lattice were directly observed by transmission electron microscopy and corresponding mapping analysis and further confirmed by powder X-ray diffraction, infrared spectroscopy, and N2 adsorption characterizations. Density functional theory calculations further suggested a significant interfacial charge transfer from CsPbBr3 quantum dots to PCN-333(Fe), which is ideal for photocatalysis. The CsPbBr3@PCN-333(Fe) composite exhibited excellent and stable oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic activities in aprotic systems. Furthermore, CsPbBr3@PCN-333(Fe) composite worked as the synergistic photocathode in the photoassisted Li-O2 battery, where CsPbBr3 and PCN-333(Fe) acted as optical antennas and ORR/OER catalytic sites, respectively. The CsPbBr3@PCN-333(Fe) photocathode showed lower overpotential and better cycling stability compared to CsPbBr3 nanocrystals or PCN-333(Fe), highlighting the synergy between CsPbBr3 and PCN-333(Fe) in the composite.

Highly Curved Nanostructure-Coated Co, N-Doped Carbon Materials for Oxygen Electrocatalysis.

Abstract: Nitrogen-doped graphene could catalyze the electrochemical reduction and evolution of oxygen, but unfortunately suffers from sluggish catalytic kinetics. Herein, for the first time, we report an onion-like carbon coated Co, N-doped carbon (OLC/Co-N-C) material, which possesses multilayers of highly curved nanostructures that form mesoporous architectures. These unique nanospheres are produced when surfactant micelles are introduced to synthesis precursors. Owing to the combined electronic effect and nanostructuring effect, our OLC/Co-N-C materials exhibit high bifunctional oxygen reduction/evolution reaction (ORR/OER) activity, showing a promising application in rechargeable Zn-air batteries. Experimental results are rationalized by theoretical calculations, showing that the curvature of graphitic carbon plays a vital role in promoting activities of meta-carbon atoms near graphitic N and ortho/meta carbon atoms close to pyridinic N.

Tailored Mesoporous Inorganic Biomaterials: Assembly, Functionalization, and Drug Delivery Engineering

Abstract: Infectious or immune diseases have caused serious threat to human health due to their complexity and specificity, and emerging drug delivery systems (DDSs) have evolved into the most promising therapeutic strategy for drug-targeted therapy. Various mesoporous biomaterials are exploited and applied as efficient nanocarriers to loading drugs by virtue of their large surface area, high porosity, and prominent biocompatibility. Nanosized mesoporous nanocarriers show great potential in biomedical research, and it has become the research hotspot in the interdisciplinary field. Herein, recent progress and assembly mechanisms on mesoporous inorganic biomaterials (e.g., silica, carbon, metal oxide) are summarized systematically, and typical functionalization methods (i.e., hybridization, polymerization, and doping) for nanocarriers are also discussed in depth. Particularly, structure-activity relationship and the effect of physicochemical parameters of mesoporous biomaterials, including morphologies (e.g., hollow, core-shell), pore textures (e.g., pore size, pore volume), and surface features (e.g., roughness and hydrophilic/hydrophobic) in DDS application are overviewed and elucidated in detail. As one of the important development directions, advanced stimuli-responsive DDSs (e.g., pH, temperature, redox, ultrasound, light, magnetic field) are highlighted. Finally, the prospect of mesoporous biomaterials in disease therapeutics is stated, and it will open a new spring for the development of mesoporous nanocarriers.

Nitrogen doping-mediated oxygen vacancies enhancing co-catalyst-free solar photocatalytic H2 production activity in anatase TiO2 nanosheet assembly

Abstract: Introducing oxygen vacancies (Vo) into TiO2 photocatalyst has been considered an effective strategy for improving co-catalyst-free solar photocatalytic activity. However, the methods used to synthesize it require high pressure/temperature and/or hazardous/costly reagents. Here we propose Vo introduction, concomitant with N-doping in TiO2, as an alternative strategy for achieving efficient co-catalyst-free solar photocatalytic activity under less extreme conditions. After calcination at 450 °C of mesoporous spherical assemblies of a layered titanate nanosheet containing N,N-dimethylformamide as its synthesis solvent in the structure, we successfully synthesized mesoporous spherical assemblies of nanosheets composed of anatase TiO2 nanoparticles with Vo mediated by N doping. This material exhibits good co-catalyst-free solar photocatalytic activity for hydrogen evolution via water splitting under irradiation with simulated solar light, which is considerably higher than that of typical co-catalyst-free defective TiO2 materials. We discuss the possible role of the introduced Vo in facilitating charge separation and raising photocatalytic efficiency.

Crystal engineering of MOF@COF core-shell composites for ultra-sensitively electrochemical detection

Abstract: Exploration and construction of novel porous core-shell composites is of crucial significance due to their prospectively enhanced performances and far-ranging applications. Herein, microporous UiO-66-NH2 as a MOF core is coated by a mesoporous TAPB-DMTP−COF shell to construct the UiO-66-NH2@COF composite via a covalent linking approach. Importantly, the composite with retentive crystallinity and hierarchical porosity significantly improves the electrochemical detection performance, for instance ATP and antibiotic, because this composite has the high affinity between the phosphate groups of aptamers and dense Zr(IV) sites, and strong π-π stacking interaction between aptamers and this MOF@COF. The synthetic strategy in this systematic research expands a rational design for other MOF@COF core-shell hybrid materials to expand their promising applications.

NixAl1O2-δ mesoporous catalysts for dry reforming of methane: The special role of NiAl2O4 spinel phase and its reaction mechanism

Abstract: The structure evolution of surface NiAl2O4 spinel phase in NixAl1O2-δ mesoporous catalysts, synthesized by the citric acid sol-gel method, was systematically investigated. Small-size Ni nanoparticles, obtained by partial reduction from NiAl2O4 spinel in NixAl1O2-δ catalysts with low Ni contents at high temperature, can effectively inhibit the carbon formation from kinetics, while the irreducible NiAl2O4 counterpart can participate in elimination of carbon deposition. The constructed structure of Ni0-NiAl2O4 interfaces, produced by exsolution of Ni from NiAl2O4 spinel, is responsible for its high long-term stability and excellent resistance to coking and sintering for dry reforming of methane (DRM) reaction. The structure sensitivity and kinetic compensation effect of CH4 dissociation on Ni0 active sites are observed. DRM reaction proceeds via a Langmuir-Hinshelwood mechanism accompanied by an additional redox mechanism. It is noteworthy that the active oxygen species generated by filling the oxygen vacancies of NiAl2O4 spinel by CO2 provide another rapid redox route to eliminate carbon species.

Polyimide Aerogel Fibers with Superior Flame Resistance, Strength, Hydrophobicity, and Flexibility Made via a Universal Sol-Gel Confined Transition Strategy.

Abstract: Aerogel fibers with ultrahigh porosity, large specific surface area, and ultralow density have shown increasing interest due to being considered as the next generation thermal insulation fibers. However, it is still a great challenge to fabricate arbitrary aerogel fibers via the traditional wet-spinning approach due to the obvious conflict between the static sol-gel transition of the aerogel bulks and the dynamic wet-spinning process of aerogel fibers. Herein, a sol-gel confined transition (SGCT) strategy was developed for fabricating various mesoporous aerogel fibers, in which the aerogel precursor solution was first driven by the surface tension into the capillary tubes, then the gel fibers were easily formed in the confined space after static sol-gel process, and finally the mesoporous aerogel fibers were obtained via the supercritical CO2 drying process. As a typical case, the polyimide (PI) aerogel fiber prepared via the SGCT approach has exhibited a large specific surface area (up to 364 m2/g), outstanding mechanical property (with elastic modulus of 123 MPa), superior hydrophobicity (with contact angle of 153°), and excellent flexibility (with curvature radius of 200 μm). Therefore, the aerogel woven fabric made from PI aerogel fibers has possessed an excellent thermal insulation performance in a wide temperature window, even under the harsh environment. Besides, arbitrary kinds of aerogel fibers, including organic aerogel fibers, inorganic aerogel fibers, and organic-inorganic hybrid aerogel fibers, have been fabricated successfully, suggesting the universality of the SGCT strategy, which not only provides a way for developing aerogel fibers with different components but also plays an irreplaceable role in promoting the upgrading of the fiber fields.

Interfacial synergistic catalysis over Ni nanoparticles encapsulated in mesoporous ceria for CO2 methanation

Abstract: An ordered mesoporous ceria, mpCeO2, was synthesized using nanocasting, followed by strong electrostatic adsorption to prepare Ni nanoparticles encapsulated in mpCeO2 for CO2 methanation. At 225 °C, TOF of Ni/mpCeO2 catalyst (0.183 s−1) is 3 times higher than that of Ni catalyst supported on conventional CeO2 prepared by the same method (0.057 s−1). Characterization results indicate that encapsulated structure provides rich Ni-CeO2 interface with more oxygen vacancies, playing a key role in CO2 activation. As evidenced by in-situ DRIFTS experiments, CO2 activation over Ni/mpCeO2 catalyst occurs through combined associative and dissociative mechanisms. Moreover, small and highly dispersed Ni nanoparticles in channels of mpCeO2 facilitate H2 dissociation, supplying sufficient *H for CO hydrogenation with *HCO intermediate species and leading to high CH4 selectivity. In addition to enhanced low-temperature activity and selectivity, Ni/mpCeO2 catalyst is very stable throughout 70 h since metal sintering can be inhibited by confinement effect of mesoporous structure.

Mesoporous Assembly of Aluminum Molecular Rings for Iodine Capture.

Abstract: The effective capture and storage of radioiodine are of worldwide interest for sustainable nuclear energy. However, the direct observation of ambiguous binding sites that accommodate iodine is extremely rare. We presented herein a crystallographic visualization of the binding of iodine within mesoporous cages assembled from aluminum molecular rings. These nanocages are formed through π-π interactions between adjacent aluminum molecular rings. Compared with the general nanotubes arrangement, the supramolecular nanocage isomer exhibits better iodine adsorption behavior. The robust molecular nanocages demonstrate a high iodine vapor saturation uptake capacity of 50.3 wt % at 80 °C. Furthermore, the resulting adsorbent can be recycled. Single-crystal X-ray diffraction reveals binding sites of molecular I2 within the pores of the phenyl-based linkers stabilized by the strong I···π interactions. These compounds represent an excellent model to deduce the trapping mechanism of guest molecules interacting with the host. In addition, this work develops a promising cluster-based aluminum material as iodine adsorbents.