Ultrahigh Porosity Research Articles

Fire-resistant and thermal insulation performance of SiC nanofiber batt fabricated from cotton fiber batt

The cotton fiber batt is one of the most commonly used thermal insulator in our lives at room temperature because of its flexible and porous structure. The SiC nanofibers have excellent mechanical, physical, and chemical properties such as high mechanical strength and modulus, low density, high-temperature resistance, which is a promising material for high temperature structural materials or thermal insulator. In this work, a flexible SiC nanofiber batt was fabricated from the cotton fiber batt by sol-gel carbothermal reduction reaction. The fluffy carbonized porous cotton batt was used as a template for the fabrication of sponge-liked SiC nanofiber batt composed of single crystalline β-SiC fibers. It exhibits good compressive flexibility, ultra-high porosity (a specific surface area was 30.90 m²/g), excellent high-temperature stability (ranging from −196 °C in liquid nitrogen to 1300 °C under the flame of butane blowtorch) and low thermal conductivity (0.02 W/(m·K) at room temperature). The SiC nanofiber batt, which has low density, excellent high-temperature resistance and oxidation resistance, is a promising material for high-temperature structural materials or thermal insulators under extreme conditions. The facile fabrication method of SiC nanofiber batt from common cotton batt provides a novel technique for economic industrial production of high temperature thermal insulation material.

Facile fabrication of microfibrillated cellulose-based aerogels incorporated with nisin/β-cyclodextrin microcapsule for channel catfish preservation

In this study, a hydrophobic and antibacterial pad was prepared to preserve Channel Catfish (Ictalurus punctatus). The pad composite the microfibrillated cellulose and β-cyclodextrin/nisin microcapsules. The hydrophobic pad ensures a dry surface in contact with the fish, reducing microbial contamination. The pad has a low density and high porosity, making it lightweight and suitable for packaging applications, while also providing a large surface area for antibacterial activity. Results demonstrated that this antibacterial pad exhibits an ultralow density of 9.0 mg/cm3 and an ultrahigh porosity of 99.10%. It can extend the shelf life of Channel Catfish fillets to 9 days at 4 °C, with a total volatile base nitrogen below 20 mg/100 g. The study proposes a novel solution for preserving aquatic products by combining antibacterial substances with the natural base material aerogel. This approach also extends the utilization of aerogel and nisin in food packaging.

MOF-Based Membranes for Remediated Application of Water Pollution.

Membrane separation plays a crucial role in the current increasingly complex energy environment. Membranes prepared by metal-organic framework (MOF) materials usually possess unique advantages in common, such as uniform pore size, ultra-high porosity, enhanced selectivity and throughput, and excellent adsorption property, which have been contributed to the separation fields. In this comprehensive review, we summarize various designs and synthesized strategies of free-standing MOF and composite MOF-based membranes for water treatment. Special emphases are given not only on the effects of MOF on membrane performance, removal efficiencies, and elimination mechanisms, but also on the importance of MOF-based membranes for the applications of oily and micro-pollutant removal, adsorption, separation, and catalysis. The challenges and opportunities in the future for the industrial implementation of MOF-based membranes are also discussed.

Expanding the Reticular Chemistry Building Block Library toward Highly Connected Nets: Ultraporous MOFs Based on 18-Connected Ternary, Trigonal Prismatic Superpolyhedra.

The chemistry of metal-organic frameworks (MOFs) continues to expand rapidly, providing materials with diverse structures and properties. The reticular chemistry approach, where well-defined structural building blocks are combined together to form crystalline open framework solids, has greatly accelerated the discovery of new and important materials. However, its full potential toward the rational design of MOFs relies on the availability of highly connected building blocks because these greatly reduce the number of possible structures. Toward this, building blocks with connectivity greater than 12 are highly desirable but extremely rare. We report here the discovery of novel 18-connected, trigonal prismatic, ternary building blocks (tbb's) and their assembly into unique MOFs, denoted as Fe-tbb-MOF-x (x: 1, 2, 3), with hierarchical micro- and mesoporosity. The remarkable tbb is an 18-c supertrigonal prism, with three points of extension at each corner, consisting of triangular (3-c) and rectangular (4-c) carboxylate-based organic linkers and trigonal prismatic [Fe3(μ3-Ο)(-COO)6]+ clusters. The tbb's are linked together by an 18-c cluster made of 4-c ligands and a crystallographically distinct Fe3(μ3-Ο) trimer, forming overall a 3-D (3,4,4,6,6)-c five nodal net. The hierarchical, highly porous nature of Fe-tbb-MOF-x (x: 1, 2, 3) was confirmed by recording detailed sorption isotherms of Ar, CH4, and CO2 at 87, 112, and 195 K, respectively, revealing an ultrahigh BET area (4263-4847 m2 g-1) and pore volume (1.95-2.29 cm3 g-1). Because of the observed ultrahigh porosities, the H2 and CH4 storage properties of Fe-tbb-MOF-x were investigated, revealing well-balanced high gravimetric and volumetric deliverable capacities for cryoadsorptive H2 storage (11.6 wt %/41.4 g L-1, 77 K/100 bar-160 K/5 bar), as well as CH4 storage at near ambient temperatures (367 mg g-1/160 cm3 STP cm-3, 5-100 bar at 298 K), placing these materials among the top performing MOFs. The present work opens new directions to apply reticular chemistry for the construction of novel MOFs with tunable porosities based on contracted or expanded tbb analogues.

Dibromomethane Knitted Highly Porous Hyper-Cross-Linked Polymers for Efficient High-Pressure Methane Storage.

Hyper-cross-linked polymers (HCPs) with ultra-high porosity, superior physicochemical stability, and excellent cost-effectiveness are attractive candidates for methane storage. However, the construction of HCPs with BET surface areas exceeding 3000 m2 g-1 remains extremely challenging. In this work, a newly developed DBM-knitting method with a slow-knitting rate is employed to increase the cross-linking degree, in which dichloromethane (DCM) is replaced by dibromomethane (DBM) as both solvent and electrophilic cross-linker, resulting in highly porous and physicochemically stable HCPs. The BET surface areas of DBM-knitted SHCPs-Br are 44%-120% higher than that of DCM-knitted SHCPs-Cl using the same building blocks. Remarkably, SHCP-3-Br exhibits an unprecedentedly high porosity (SBET = 3120m2g-1) among reported HCPs, and shows a competitive volumetric 5-100bar working methane capacity of 191 cm3 (STP) cm-3 at 273K calculated by using real packing density, which outperforms sate-of-art metal-organic framework (MOFs) at comparable conditions. This facile and versatile low-knitting-rate strategy enables effective improvement in the porosity of HCPs for porosity-desired applications.

Highly Efficient Fabrication of Biomimetic Nanoscaled Tendrils for High-Performance PM0.3 Air Filters.

Particulate matter pollution has become a serious public health issue, especially with the outbreak of new infectious diseases. However, most existing air filtration materials face challenges such as being too bulky, having high resistance, and a trade-off between filtration efficiency and air permeability. Here, a unique electro-blown spinning technique is used to prepare an air filter made of biomimetic nanoscaled tendril nonwovens (Nano-TN). The introduction of an airflow field significantly increases the whipping frequency and the strain mismatch of composite jets, achieving large-scale and highly efficient preparation of Nano-TN. The resultant Nano-TN has an ultrahigh porosity (97%) and a small pore size (2.9 μm). At the same filtration level, its air resistance is 37% lower than that of traditional straight nanofibrous nonwovens and has a higher dust-holding capacity. Moreover, compared with traditional three-dimensional air filters, the Nano-TN filter is thinner, offering tremendous application prospects in various environmental purification and personal protection fields.

Tunable gas absorption capability for graphene doped silica aerogel by wrinkle structure: Effects of gas absorption, mechanical properties and thermal insulation

Gas absorption capability of material proposes a dominant role in the energy storage, selective gas absorption/capture. Aerogels with ultra-high porosity, ultra-low thermal conductivity have been widely used in gas absorption. However, a persistent limitation of these materials is their static and unalterable gas absorption capacity. In this work, a wrinkled graphene structure is proposed to adjust the gas capability. A series of molecular dynamics (MD) simulations are carried out to propose an atomic-level understanding of the effects of wrinkled structure, including effects of pressure, surface wettability, number of gas molecules, thermal insulation, and mechanical properties. It is found that the gas capability can be reduced by 20% with wrinkle structure. Notably, the linear response between pressure and gas absorption capability is observed. Moreover, wrinkle structure functions as a thermal resistance to restrict solid heat transfer. The mechanical property of the aerogel composite is improved by a doped graphene sheet with a high wrinkle degree. This work will pave the way for the development of aerogel with high and selective gas absorption capability.

Arsenic removal from aqueous solution using PWN-type zeolite membrane: A theoretical investigation

Arsenic contamination in drinking water is a global health concern due to its extreme toxicity. This study explores the efficacy of PWN-type zeolite membranes in selectively removing dissolved arsenic ions. Molecular dynamics simulations analyze the permeation of aqueous arsenic solutions through the zeolite membrane under pressure-driven flow (5 to 600 MPa over 5 ns). The goal is to assess PWN-type zeolites as nanofiltration membranes for arsenic removal. The zeolite's nanoporous structure immobilizes arsenic ions while permitting water transport. Remarkably, the membrane exhibits high ion rejection, even at pressures up to 600 MPa. These findings underscore the potential of PWN-type zeolite membranes for separating As (III) ions from water supplies. With ultra-high porosity and selectivity, these nanoengineered membranes enable effective mechanical filtration processes for arsenic removal. In summary, this theoretical investigation highlights the significant promise of PWN-type zeolites as high-performance membranes for arsenic decontamination, crucial for safeguarding human health.

The design, synthesis and application of metal-organic framework-based fluorescence sensors.

Fluorescence-based chemical sensors have garnered significant attention due to their rapid response, high sensitivity, cost-effectiveness and ease of operation. Recently, metal-organic frameworks (MOFs) have been extensively utilized as platforms for constructing fluorescence sensors, owing to their ultra-high porosity, flexible tunability, and excellent luminescent properties. This feature article summarizes the progress made mainly by our research group in recent years in the construction strategies, principles, and types of MOF sensors, as well as their applications in quantitative sensing, qualitative identification analysis, and multimodal/multifunctional analysis. In addition, the challenges and an outlook on the future progression of MOF-based sensors are discussed, highlighting how these studies can contribute to addressing these issues. Hopefully, this feature article can provide some valuable guidance for the construction and application of MOFs in fluorescence sensing, thereby broadening their practical applications.

Ultra-high porosity of open-cell alumina ceramic foams prepared by adding tiny amounts of γ-AlO(OH) sol

A creative and environmentally friendly preparation of high-porosity open-cell ceramic foams was investigated. The samples were prepared from the ?-Al2O3 slurry with 25 wt.% solid loading in which a tiny amount of boehmite (?-AlO(OH)) sol was added for the formation of particle-stabilized foams without introducing any sacrificial phases. The volumetric shrinking of ?-AlO(OH) enables the formation of open-cell while avoiding the generation of polluting gases. The resulting alumina ceramic foams have a synergistic increase in porosity and compressive strength, reaching a compressive strength of 1.17MPa and an ultra-high porosity of 94.8%. This is due to the fact that the pore struts (connecting neighbouring cells) are almost defect-free, while the high sintering activity of ?-AlO(OH) promotes the sintering of ceramic phase and formation of alumina with small grains which has the strengthening effect on the obtained structures. By achieving open-cell, the heat conduction path increased, which reduces the thermal conductivity of the ceramic foam. This work provides an alternative and environmentally friendly new strategy for open-cell ceramics processing.

Design of a photocatalyst combining graphdiyne (g-CnH2n-2) nanosheets with a PVP-modified co-metal coordination polymer and its hydrogen-evolution performance.

Metal coordination polymers are organometallic frameworks in which a metal and an organic ligand are linked via a dative bond. The material in question exhibits ultra-high porosity, large specific surface area, and abundant active sites, which can be customised in terms of morphology, size, and electronic structure through rational design. Graphdiyne, a novel two-dimensional carbon allotrope, boasts structural stability and enhanced electrical conductivity due to its hybridization of sp2 and sp carbons. A metal-organic framework of Co (MOF-67) was synthesized via hydrothermal synthesis. The introduction of polyvinyl pyrrolidone (PVP) served as a structural regulator and surfactant to obtain a more active metal coordination polymer (Co-MCPS). PVP, in its dual role, significantly amplified the catalytic performance of metal coordinate polymers, as demonstrated in a number of experiments. The incorporation of GDY onto the surfaces of MOF-67 and Co-MCPS induced an electron-rich isolation layer, which could effectively sequester oxidation sites, thereby enhancing the rate of charge carrier separation and hydrogen precipitation evolution efficiency.

Advances and Applications of Metal-Organic Frameworks (MOFs) in Emerging Technologies: A Comprehensive Review.

Metal-organic frameworks (MOFs) that are the wonder material of the 21st century consist of metal ions/clusters coordinated to organic ligands to form one- or more-dimensional porous structures with unprecedented chemical andstructural tunability, exceptional thermal stability, ultrahigh porosity, and a large surface area, making them an ideal candidate for numerous potential applications. In this work, the recent progress in the design and synthetic approaches of MOFs and explore their potential applications in the fields of gas storage and separation, catalysis, magnetism, drug delivery, chemical/biosensing, supercapacitors, rechargeable batteries and self-powered wearable sensors based on piezoelectric and triboelectric nanogenerators are summarized. Lastly, this work identifies present challenges and outlines future opportunities in this field, which can provide valuable references.

Engineering biomimetic scaffolds by combining silk protein nanofibrils and hyaluronic acid

Nanofibrous scaffolds mimicking important features of the native extracellular matrix (ECM) provide a promising strategy for tissue regeneration. However, 3D scaffolds mimicking natural protein nanofibers and bioactive glycosaminoglycans remain poorly developed. In this study, a biomimetic nanofibrous scaffold composed of natural silk protein nanofibers and glycosaminoglycan hyaluronic acid (HA) was developed. HA functionalization significantly improved the hydrophilicity and bioactivity of silk nanofibers (SNFs). SNFs can be assembled into nanofibrous aerogel scaffolds with low density and desirable shapes on a large scale. More importantly, with the assistance of HA, the silk nanofibrous aerogel scaffolds with ultra-high porosity, natural bioactivity, and structural stability in aqueous environment can be fabricated. In the protease/hyaluronidase solution, the SNF scaffolds with 10.0 % HA can maintain their monolithic shape for >3 weeks. The silk nanofibrous scaffolds not only imitate the composition of ECM but also mimic the hierarchical structure of ECM, providing a favorable microenvironment for cell adhesion and proliferation. These results indicate that this structurally and functionally biomimetic system is a promising tissue engineering scaffold.

Defective ferrocene-based metal–organic frameworks for efficient solar-powered water oxidation via the ligand competition and etching effect

Two-dimensional metal–organic frameworks are considered to be promising electrocatalytic materials due to their ultrathin lamellar structure, ultrahigh porosity and large surface area, but there are still many challenges such as the embedding of organic ligands leading to low density of active sites and poor conductivity. Herein, we synthesize two-dimensional ferrocene-based metal–organic frameworks nanosheet electrocatalysts via the one-step hydrothermal hydrogen peroxide etching method. The prepared FcNi-BDC-H2O2/NF exhibits excellent oxygen evolution reaction performance with a current density of 100 mA·cm-2 at only 258 mV and a small driving potential of 1.542 V (10 mA·cm-2) is required to achieve overall water splitting. Significantly, an overall water-cracked cell using a solar cell assembly achieves the solar hydrogen conversion efficiency of 19.5%. The introduction of high electronegativity ferrocene and the etching of H2O2 increase the Ni3+ content of FcNi-BDC-H2O2, and expose more unsaturated active sites, which improve the intrinsic activity of the catalysts and the mass transfer rate during the catalytic process. Moreover, the FcNi-BDC-H2O2/NF demonstrates significant urea oxidation reaction performance, achieving a potential of 1.35 V and producing 10 mA·cm-2. This study presents a viable approach to investigating highly efficient electrocatalysts for oxygen evolution reaction and urea oxidation reaction using MOF-based bifunctional catalysts.

Flexible Block Copolymer Metamaterials Featuring Hollow Ordered Nanonetworks with Ultra-High Porosity and Surface-To-Volume Ratio.

By utilizing bicontinuous and nanoporous ordered nanonetworks, such as double gyroid (DG) and double diamond (DD), metamaterials with exceptional optical and mechanical properties can be fabricated through the templating synthesis of functional materials. However, the volume fraction range of DG in block copolymers is significantly narrow, making it unable to vary its porosity and surface-to-volume ratio. Here, the theoretically limited structural volume of the DG phase in coil-coil copolymers is overcome by enlarging the conformational asymmetry through the association of mesogens, providing fast access to achieving flexible structured materials of ultra-high porosities. The new materials design, dual-extractable nanocomposite, is created by incorporating a photodegradable block with a solvent-extractable mesogen (m) into an accepting block, resulting in a new hollow gyroid (HG) with the largely increased surface-to-volume ratio and porosity of 77 vol%. The lightweight HG exhibits a low refractive index of 1.11 and a very high specific reduced modulus, almost two times that of the typical negative gyroid (porosity≈53%) and three times that of the positive gyroid (porosity≈24%). This novel concept can significantly extend the DG phase window of block copolymers and the corresponding surface-to-volume ratio, being applicable for nanotemplate-synthesized nanomaterials with a great gain of mechanical, catalytic, and optoelectronic properties.

Concomitant role of metal clusters and ligands in the synthesis and control of porosity in Metal-Organic Frameworks: A literature review

A clossal increase in the number of research articles on metal–organic frameworks (MOFs) have recently been anticipated as next-generation functional materials. The characteristic coordination behavior between metal ion and organic linker in MOFs provide them hydrid functional features of both the moieties. For the substantial improved performance of MOFs and to achieve widespread applications of MOFs in diverse fields, it is essential to develop effective synthetic strategies and understand the role of metal ion cluster or coordination sphere or secondary building units (SBU’s) and organic linker in detail. The augmentation in porosity and large surface area with multitude in diverse topologies provide a boost for the application of these materials in diverse allied fields. This review article provides a detailed introduction of the porous MOF materials; encompassing the role of secondary building units or metal cluster and organic linkers in defining the porosity of MOF materials. Detailed investigations about the role of metal ion clusters and expanded organic linkers that lead to MOFs with ultrahigh porosity have been done and portrayed carefully. The structural aspects of zirconium, zinc and copper cluster based porous MOFs and organic linkers (porphyrin and pyrene based) have been thoroughly portrayed owing to their various application in various fields. This review article will provide better understanding about the various factors involved in synthesis and controll of the porosity toward desired applications.

One pot synthesis of hydrophobic nanochitin aerogel via tert-butyl alcohol/water binary solvents as antibacterial and renewable oil superabsorbent

In this study, hydrophobic nanochitin aerogels are synthesized via one-pot synthesis strategy and subsequent freeze-drying technique, employing nanochitin, hexanal and formaldehyde as primary components. The tert-butyl alcohol (TBA)/water binary solvents are found efficient for well mixing of hydrophilic nanochitin and hydrophobic hexanal, which is fundamental for fabricating hydrophobic aerogels with water contact angle as high as 105°. Schiff base reaction between amino groups in nanochitin and aldehyde groups in hexanal is believed to be the main reason for the successful hydrophobization of nanochitin aerogels. Additionally, formaldehyde is employed to enhance the mechanical properties of aerogels via ice templated crosslinking technique. Nanochitin aerogels prepared in this work possess surface area as high as 237 m2 g−1, which are believed benefiting from the TBA/water binary solvents with lower density, smaller ice crystal and convenience in freeze-drying. The ultralow density, ultrahigh porosity, and hydrophobicity nature also lead to the advanced oil adsorption (as high as 210 g g−1) of nanochitin aerogels. The simple preparation process, nature sustainability and excellent adsorption performance is believed rendering nanochitin aerogels as a viable alternative for the remediation of oil spills.

One-Step Synergistic Effect to Produce Two-Dimensional N-Doped Porous Carbon Nanosheets with Ultrahigh Porosity from Biomass for High-Performance Supercapacitors

One-Step Synergistic Effect to Produce Two-Dimensional N-Doped Porous Carbon Nanosheets with Ultrahigh Porosity from Biomass for High-Performance Supercapacitors

Understanding the Heat Transfer Performance of Zeolitic Imidazolate Frameworks upon Gas Adsorption by Molecular Dynamics Simulations.

Metal-organic frameworks (MOFs) with ultrahigh specific surface area and porosity have emerged as promising nanoporous materials for gas separation, storage, and adsorption-driven thermal energy conversion systems such as adsorption heat pumps. However, an inadequate understanding of the thermal transport of MOFs with adsorbed gases hampers the thermal management of such systems in practical applications. In this work, an in-depth investigation on the mechanistic heat transfer performance of three topological zeolitic imidazolate frameworks (ZIFs) upon hydrogen, methane, and ethanol adsorption was carried out by molecular dynamics simulations. It is revealed that the trade-off between the additional heat transfer pathway and phonon scattering resulting from adsorbed gases determines the thermal conductivity of ZIFs. It is found that the increased thermal conductivity with the increased number of adsorbed gases is correlated with the overlap energy between the vibrational density of states of gases and Zn atoms, suggesting the additional heat transfer pathways formed between gas molecules and frameworks. Moreover, the gas spatial distribution and diffusion also impose remarkable impacts on the heat transfer performance. Both the homogeneous gas distribution and the fast gas diffusion are conducive to form effective heat transfer pathways, leading to enhanced thermal conductivity. This study provides molecular insight into the mechanism of the improved thermal conductivity of ZIFs upon gas adsorption, which may pave the way for effective thermal management in MOF-related applications.

The metal organic framework of UiO-66-NH2 reinforced nanofiltration membrane for highly efficient ion sieving

Metal organic framework (MOF) with fine pore structures, ultra-high porosity and large specific surface area can provide more water transport channels while achieving precise sieving of different sizes of ions, which is a promising material for high efficiency desalination. However, particle agglomeration, interface incompatibilities and interface defects severely restrict the performance of MOF-based membranes. It is still a challenge to construct MOF-based desalination membranes with both high water permeability and high ion sieving. Herein, the UiO-66-NH2 based nanofiltration membrane was fabricated by in-situ growth of UiO-66-NH2 on Nylon membrane and composed with polyamide (PA) layer by interfacial polymerization (IP). With 12 h solvothermal reaction, the UiO-66-NH2 nanoparticles are found uniformly loaded on the Nylon substrate. Therefore, the water molecule transport channels provided by UiO-66-NH2 nanoparticles reduce the transport resistance, which can improve the water permeability. More importantly, UiO-66-NH2 nanoparticles are found to be involved in the IP process, which can reduce the interfacial defects and thus enhance the bonding force between the PA layer and base film. The synergistic effect of the UiO-66-NH2 and PA layer improves the nanofiltration performance of the membrane with rejection rate of 92.97% for Na2SO4 and the pure water permeance (PWP) of 11.55 L m−2 h−1 bar−1. The N-UN12 @PA membrane also has excellent antifouling performance (flux recovery ratio (FRR) of 95.86%, reversible fouling ratio (Rr) of 33.93%, irreversible fouling ratio (Rir) of 4.14%). Unlike the mixed-matrix membrane (MMM) and polycrystalline MOF membrane, this strategy provides a promising method to prepare high-performance nanofiltration membrane for desalination.