Porous Materials Research Articles

In Situ Synthesis of Hypercrosslinked Polymer as Stationary Phase for Capillary Gas Chromatography

Hypercrosslinked polymers (HCPs) constructed by the Friedel–Crafts alkylation reaction of aromatic compounds have emerged as a new class of porous materials with unique merit. Herein, a HCP named HCP-TPB was coated onto a capillary column through in situ synthesis. The prepared column exhibited a nonpolar nature, and the column efficiency for n-dodecane was 3003 plates m−1. Moreover, the relative standard deviations of retention time and peak area for six replicate injections of the C3–C6 were lower than 0.1% and 1.5%, respectively. The results of this study showed that it is very promising to utilize HCPs as stationary phases for the separation of C3–C6.

Hydrogen-Bonded Organic Framework and Metal-Organic Framework Assembly of Waterwheel PgC-Noria Molecule: Regulating Microstructure Enables Iodine Transfer.

Hydrogen-bonded organic frameworks (HOFs) are a type of crystalline porous materials self-assembled from organic or metal-organic building blocks via intermolecular hydrogen bonding, which have received increasing attention due to their reversible and flexible hydrogen bonding properties. Currently, it remains a challenge to construct HOFs based on complex or porous organic cages as molecular building blocks. Herein, a 3D HOF (PgC-HOF) featuring honeycomb-shaped channels is crafted utilizing a sizable waterwheel-like PgC-noria organic molecule cage. The pivotal role of intermolecular multipoint hydrogen bonding interactions in upholding structural integrity and stability is underscored by the possession of 36 phenolic hydroxyl groups in PgC-HOF. Interestingly, the introduction of calcium ions into the reaction system results in the formation of the metal-organic framework (PgC-MOF), with the channel dimensions increasing from 6.8 to 9.1Å. Furthermore, I2 sorption/release experiments are conducted on PgC-HOF and PgC-MOF, achieving an increase in the optimal adsorption amount from 1.45 to 2.19gg-1 and a transition from an irreversible adsorbent to a reversible adsorbent.

Synthesis and Characterization of Cobalt–Organic Framework as an Electrocatalyst for Water Splitting Application

ABSTRACTClimate change is seen as a crucial environmental dilemma that humanity will confront in the upcoming decade. For this purpose, the solvothermal‐assisted technique is used to create metal–organic frameworks (MOFs), which are porous materials characterized by strong connections between organic ligands and metal ions. The MOF discussed here contains cobalt as the metal node and a linker derived from 2‐aminobenzoic acid and terephthalaldehyde. The prepared powder underwent analysis using various techniques including Fourier‐transform infrared spectroscopy (FT‐IR), powder X‐ray diffraction (PXRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area measurement, and thermal analysis. BET analysis revealed a surface area of 1587.06 m2/g, a total pore volume of 0.86394 cc/g, and an average pore size of 1.088 nm. The RGO@Co‐MOF prepared was utilized to evaluate water splitting efficiency, demonstrating favorable catalytic activity like most reported modified MOF catalysts under low current density conditions of 10 mA/cm2.

High-temperature carbon dioxide capture in a porous material with terminal zinc hydride sites.

Carbon capture can mitigate point-source carbon dioxide (CO2) emissions, but hurdles remain that impede the widespread adoption of amine-based technologies. Capturing CO2 at temperatures closer to those of many industrial exhaust streams (>200°C) is of interest, although metal oxide absorbents that operate at these temperatures typically exhibit sluggish CO2 absorption kinetics and instability to cycling. Here, we report a porous metal-organic framework featuring terminal zinc hydride sites that reversibly bind CO2 at temperatures above 200°C-conditions that are unprecedented for intrinsically porous materials. Gas adsorption, structural, spectroscopic, and computational analyses elucidate the rapid, reversible nature of this transformation. Extended cycling and breakthrough analyses reveal that the material is capable of deep carbon capture at low CO2 concentrations and high temperatures relevant to postcombustion capture.

Pore configuration control in hybrid azolate ultra-microporous frameworks for sieving propylene from propane.

Developing porous adsorbents for the complete sieving of propylene/propane mixtures represents an alternative method to energy-intensive cryogenic distillation processes. However, the similar physical properties of these molecules and the inherent trade-off among adsorption capacity, selectivity, diffusion kinetic and host-guest binding interactions in molecular sieving adsorbents makes their separation challenging. Here we report the separation of propylene/propane mixtures through a crystalline porous material (HAF-1) that features channels and shrinkage throats-the latter defined as narrower channels that connect the main channels and a molecular pocket-where the throat aperture is between the kinetic diameters of propylene and propane. Single-crystal X-ray diffraction and computational simulation reveal that the shrinkage channels and hanging molecular pockets are key to ensure high sieving efficiency and high propylene adsorption capacity. Dynamic breakthrough experiments show that HAF-1 enables the achievement of high-purity (≥99.7%) propylene with a productivity of 33.9 l kg-1 by just one adsorption-desorption circle from propylene/propane mixtures.

Strong Electrochemiluminescence Response Derived from Ionic Chiral Covalent Organic Frameworks for Enantioselective Discrimination of Amino Acid Enantiomers via an Electrostatic Attraction Effect.

Porous chiral materials accompanied by electrochemiluminescence (ECL) activity are rarely reported for enantioselective discrimination because of the big challenges to integrate the stereogenic center and ECL-active unit in the backbone. In the present study, ionic chiral covalent organic frameworks (iCCOFs) consisting of the pyridinium unit as the ECL-active species were prepared by a facile strategy. We were amazed that such iCCOFs could display strong cathodic ECL responses. Meanwhile, the as-prepared ECL-active iCCOFs performed enantioselective ECL quenching toward amino acid enantiomers, attributed to the enhanced photoinduced electron transfer process derived from the formed complex between the iCCOFs and amino acids via an electrostatic attraction effect. The iCCOF with an (S)-configuration was prone to interact with l-amino acids, producing a lower ECL intensity. The maximum intensity ratio between the d- and l-enantiomers was 33.0. Finally, the enantiomeric compositions of the measured amino acids presented a good linear relation with the obtained ECL intensity, which was fit for the determination of samples with unknown enantiomeric purity. In brief, the obtained results convince us that this study advances a new generation of ECL-active iCCOFs and displays great potential in enantioselective sensing.

Constructing polyolefin-based lithium-ion battery separators membrane for energy storage and conversion

Owing to the escalating demand for environmentally friendly commodities, lithium-ion batteries (LIBs) are gaining extensive recognition as a viable means of energy storage and conversion. LIBs comprise cathode and anode electrodes, electrolytes, and separators. Notably, the separator, a crucial and indispensable element in LIBs that mainly comprises a porous membrane material, necessitates substantial research focus. Scholars have consequently strived to devise novel systems that augment separator efficiency, bolster safety measures, and surmount existing constraints. This review endeavors to equip researchers with comprehensive information on polyolefin-based separator membranes, encompassing performance prerequisites, functional attributes, scientific advancements, and so on. Specifically, it scrutinizes the latest innovations in porous membrane configuration, fabrication, and enhancement that utilize the most prevalent polyolefin materials today. Consequently, robust and enduring membranes fabricated have demonstrated superior effectiveness across diverse applications, facilitating a circular economy that curbs waste materials, reduces operational expenses, and mitigates environmental impact.

Synthesis and Biomedical Applications of Covalent Organic Frameworks for Disease Diagnosis and Therapy.

Covalent organic frameworks (COFs) have emerged as a distinguished class of porous materials. Owing to their ability to be constructed through covalent bonds involving light elements, such as hydrogen, boron, carbon, nitrogen, and oxygen, COFs offer greater stability and lower cytotoxicity than metal organic frameworks do, addressing critical limitations in in vivo applications. Their unique attributes, such as high surface area, customizable pore sizes, and versatile surface functionalities, make them ideal for various biomedical applications. This review aims to provide an overview of the recent advancements in modern COFs for biomedical uses. First, a variety of methods for the synthesis of COFs are outlined, which ensures their suitability for medical use. Next, we delve into innovative biomedical applications, emphasizing their role in disease diagnostics and therapies. Finally, challenges, such as clinical translation, biocompatibility, and controlled drug release, are critically discussed, providing comprehensive insight into the potential of COFs in revolutionizing biomedical technologies. Overall, this review offers a comprehensive overview of COFs' capabilities and future prospects in enhancing biomedical technologies.

Fundamentals and Implication of Point of Zero Charge (PZC) Determination for Activated Carbons in Aqueous Electrolytes.

The point of zero charge (PZC) is a crucial parameter for investigating the charge storage mechanisms in energy storage systems at the molecular level. This paper presents findings from three different electrochemical techniques, compared for the first time: cyclic voltammetry (CV), staircase potentio electrochemical impedance spectroscopy (SPEIS), and step potential electrochemical spectroscopy (SPECS), for two activated carbons (ACs) with 0.1molL-1 aqueous solution of LiNO3, Li2SO4, and KI. The charging process of AC operating in aqueous electrolytes appears as a complex phenomenon - all ionic species take an active part in electric double-layer formation and the ion-mixing zone covers a wide potential region. Therefore, the so-called PZC should not be considered as an absolute one-point potential value, but rather as a range of zero charge (RZC). SPECS technique is found to be a universal and fast method for determining RZC, as applied here together with the EQCM. In most cases, the RZC covers a potential range from ≈100 to ≈200mV and the correlation of the range with the carbon microtexture is clear, highlighting the role of the ion-sieving effect. It is postulated that PZC for porous materials in aqueous electrolytic solutions should be considered instead as RZC.

Progress and Strategies of MOFs in Catalyzing Conversion Processes in Lithium‐Sulfur Batteries

AbstractLithium‐sulfur (Li−S) batteries have attracted considerable attention due to their advantages, such as high specific capacity, high energy density, environmental friendliness, and low cost. However, the severe capacity fading caused by shuttle effect of polysulfide needs to be addressed before the practical application of Li−S batteries. Crystalline porous materials including MOFs have generated great interest in energy storage fields especially batteries, because the ordered porous frameworks can offer a fast‐ionic transportation. Nevertheless, the intrinsic low conductivity of MOFs limits their rapid development in lithium‐sulfur batteries. This review mainly discusses the latest research progress on MOF main materials in Li−S batteries. The working principle of Li−S batteries and the classical “adsorption‐catalysis‐conversion” strategy are briefly introduced. Specifically, three modification methods (non‐metal atom doping, single‐atom, and dual‐atom doping modifications) applied in MOF‐based materials are analyzed and summarized, along with their respective mechanisms and advantages and disadvantages. Ligand doping is an effective strategy that can regulate the structure and properties of MOFs, thereby enhancing their catalytic activity and adsorption capacity towards polysulfides. Through ligand doping, key parameters such as the pore size, surface charge, and active site density of MOFs can be controlled, thereby influencing the adsorption and conversion of polysulfides on MOFs surfaces. Furthermore, crucial insights for the rational design of advanced MOF‐based materials for lithium‐sulfur batteries and the exploration of the main challenges and future directions for their application were also discussed.

Multifunctional Electromagnetic Responsive Porous Materials Synthesized by Freeze Casting: Principles, Progress, and Prospects

AbstractFreeze casting is a solidification technique utilized in the fabrication of porous materials. However, the freeze casting process is quite complex, and significant challenges remain in precisely controlling the pore size and shape of porous structures. This study aims to investigate the customization of multifunctional electromagnetic wave (EMW) absorbers with 3D porous structures via freeze casting. This review initially presents the fundamental principles underlying the freeze casting technique and examines the correlation between internal and external factors during the preparation process and porosity. The emerging trends in constructing novel and intricate macroscopic structures through freeze casting are subsequently outlined. Furthermore, this review focuses on the fabrication of composites with various porous microstructures through freeze casting of low‐dimensional building blocks, and their EMW response and multifunctional properties. By regulating the internal and external influencing mechanisms of freeze casting, porous EMW absorption materials exhibit outstanding advantages such as electromagnetic property manipulation, controllable structure, high porosity, high specific surface area, lightweight, and flexibility. These features broaden their applications in electromagnetic shielding, mechanical property, radar stealth, thermal insulation and fire prevention, flexible sensors, antifreeze ability, etc. In addition, we discuss the challenges and prospects of high‐performance EMW absorbers using freeze casting techniques.

Porous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.

Porphyrin‐based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co‐crystallisation of tetraphenylporphyrin (TPP) with octa(2’,6’‐di‐isopropylphenoxy) phthalocyanine or some of its metal complexes [(dipPhO)8PcM; M = H2, Al‐OH, Ti=O, Mn‐Cl, Fe‐Cl, Co, Ni, Cu, Zn, Ga‐Cl, Ag, In‐Cl or Au‐Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)8PcM, which is driven by the complementary shape and symmetry of the two macrocycles. The (dipPhO)8PcM component directs the crystal structure of the heterodimers to form Phthalocyanine Nanoporous Crystals (PNCs) of similar structure to those formed by (dipPhO)8PcM alone. The incorporation of TPP appears to partially stabilise the PNCs towards the removal of included solvent and for cocrystals containing (dipPhO)8PcCo stability can be enhanced further by the in‐situ addition of 4,4‐bipyridyl to act as a “molecular wall tie”. These stabilised PNC/TPP cocrystals have a Brunauer‐Emmett‐Teller surface area (SABET) of 454 m2 g‐1 and a micropore volume (Vmp) of 0.22 ml g‐1. The reactivity of both macrocycles within the PNC/TPP co‐crystals are demonstrated by in‐situ metal insertion.

Metal-Organic-Framework-Derived CuO-ZnO@CN Hollow Nanoreactors: Precise Structural Control and Efficient Catalytic Performance.

Hollow carbon-nitrogen nanoreactors constitute a class of porous materials that have widespread application owing to their large inner cavities, low densities, core-shell interfaces, and enrichment effects. Direct carbonization of precursors is the simplest and most economical method to prepare porous carbon-nitrogen materials; however, this method requires high temperatures, thus yielding nonoxide structures. In this study, CuO-ZnO@CN (CN: carbon-nitrogen layers) is prepared using the two-step heating of zeolitic imidazolium skeleton-8 (ZIF-8) coated with CuO-ZnO precursors. During carbonization, the ZIF-8 nanoparticles are converted into carbon-nitrogen layers at high temperatures. Next, a heating process based on the autocatalytic effect of Cu can be used to etch the hollow structure prepared by the carbon-nitrogen layers. The CuO-ZnO@CN hollow composites fabricated using this method exhibit excellent catalytic properties for the ethynylation of formaldehyde. The proposed strategy can be used to develop techniques for syntheses of readily reducible carbon oxide claddings and their composites.

Axial mechanical properties of welded orthogonal trapezoidal aluminum honeycomb as filler material for nuclear equipment impact limiter.

Lightweight porous structural materials have excellent energy absorption performance, and their application are gradually appeared. This paper takes the shock-absorbing material of nuclear equipment transportation casks as the starting point, and manufactures an orthogonal trapezoidal aluminum honeycomb by welding (WOTAH). The mechanical properties with different cell thicknesses and cell size ratios under different impact loads are studied through experimental and simulation methods, and the deformation process and energy absorption performance of the materials are obtained. The energy absorption performance of materials under quasi-static loading was investigated using plastic deformation theory and compared with experimental results. Based on the experimental results, the least squares method was used for data fitting to obtain the C-S dynamic constitutive relationship of the material. The equivalent structure was used to replace the honeycomb structure for simulation, and the influence of strain rate effect and structural size on material properties was further studied. Through the above mechanical performance analysis and comparison with wood, it is shown that WOTHA has feasible for the application of nuclear equipment impact limiter.

Chromium Oxide Nanoparticles Anchored in Hydrogel-Derived Three-Dimensional N-Doped Porous Carbon Anode Materials as Lithium-Ion Batteries.

Transition metal oxides (TMOs) have been identified as the most promising anode materials for lithium-ion batteries (LIBs). However, these materials tend to undergo volumetric expansion during battery operation, which disrupts their internal structure and ultimately leads to a degradation of battery performance. Cr2O3/N-doped porous carbon (Cr2O3@NC) composites were successfully synthesized through high-temperature calcination using Cr2O3-containing hydrogels as precursors. The results show that the carbon material not only improves the electron transfer ability of Cr2O3 but also effectively prevents its agglomeration. The Cr2O3@CN composite as a novel anode material for LIBs exhibits a reversible capacity of 936 mAh g-1 after 200 cycles at a current density of 1 A g-1, showcasing excellent cycling and structural stability during cycling. Scanning electron microscopy analysis reveals that the Cr2O3@NC composite remains structurally intact throughout cycling. The innovative approach proposed in this study provides a new direction for the advancement of electrode materials for energy storage technologies.

Numerical Implementation of Electrostatic Solver Within OpenFOAM for Gas Turbine Intake Filtration

Abstract Gas turbines require filtered air to preserve operability, availability, and efficiency. Fouling, corrosion, and erosion severely affect the performance of the axial compressor and it can be in part prevented by filtering the air intake. For this reason, several stages of filters can be used in series to catch pollutant particles gradually smaller and with a high level of capturing efficiency. Traditionally, the separation is obtained using cartridges of porous material, which provide a high level of filtration but at the same time generate a pressure drop increasing over time. Another common type of filter is the inertial one, whose operating principle is based on the inertial force acting on the solid particles to separate them from the mainstream. The capturing efficiency of the inertial filter is not comparable with the porous one and for this reason, it is used upstream as a pre-filter. In recent years, another technique has been developed to filter air flows thanks to an electrostatic field, that is induced inside the flow. The electrostatic force generated is able to attract and separate metallic particles. In the present work, numerical investigations are carried out to simulate the effect of the electrostatic force for gas turbine filtering systems. The computational fluid dynamics tool used is openfoam, whose official release can simulate inertial and porous filtering media, while for electrostatic one is not possible due to the absence of a library able to simulate the electrostatic force that acts on the discrete phase. A new library was developed in order to calculate the electric field, the electric potential, and the charge density of the continuous phase. Simulation results show how the calculation of these quantities allows us to predict the electrostatic force acting on particle flows in the presence of electrostatic fields.

Porous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.

Porphyrin-based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co-crystallisation of tetraphenylporphyrin (TPP) with octa(2',6'-di-isopropylphenoxy) phthalocyanine or some of its metal complexes [(dipPhO)8PcM; M = H2, Al-OH, Ti=O, Mn-Cl, Fe-Cl, Co, Ni, Cu, Zn, Ga-Cl, Ag, In-Cl or Au-Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)8PcM, which is driven by the complementary shape and symmetry of the two macrocycles. The (dipPhO)8PcM component directs the crystal structure of the heterodimers to form Phthalocyanine Nanoporous Crystals (PNCs) of similar structure to those formed by (dipPhO)8PcM alone. The incorporation of TPP appears to partially stabilise the PNCs towards the removal of included solvent and for cocrystals containing (dipPhO)8PcCo stability can be enhanced further by the in-situ addition of 4,4-bipyridyl to act as a "molecular wall tie". These stabilised PNC/TPP cocrystals have a Brunauer-Emmett-Teller surface area (SABET) of 454 m2 g-1 and a micropore volume (Vmp) of 0.22 ml g-1. The reactivity of both macrocycles within the PNC/TPP co-crystals are demonstrated by in-situ metal insertion.

Isoreticular Contraction in Dicopper Paddle-Wheel-Based Metal-Organic Frameworks to Enhance C2H2/CO2 Separation.

Achieving a balance between high selectivity and uptake is a formidable challenge for the purification of acetylene from mixtures with carbon dioxide, particularly when seeking to maximize both C2H2 adsorption capacity and C2H2/CO2 separation selectivity in crystalline porous materials. In this study, leveraging the principles of reticular chemistry, we selected two tetracarboxylate-based linkers and combined them with Cu2+ ions to synthesize two isoreticular dicopper paddle-wheel-based metal-organic frameworks (MOFs): Cu-TPTC (terphenyl-3,3',5,5'-tetracarboxylic acid , H4TPTC) and Cu-ABTC (3,3,5,5-azobenzenetetracarboxylic acid, H4ABTC). The structural and sorption analyses revealed that Cu-ABTC, despite having slightly smaller pores due to the strategic replacement of a phenyl ring with an azo group between two tetratopic ligands, maintains high porosity compared to Cu-TPTC. Furthermore, Cu-ABTC outperforms Cu-TPTC in terms of C2H2 adsorption capacity (196 cm3 g-1 at 298 K and 1 bar) and C2H2/CO2 separation selectivity (16.5~5.6). These findings were corroborated by dynamic breakthrough experiments and computational modeling. This research highlights the potential of the isoreticular contraction strategy in enhancing MOFs for sophisticated gas adsorption and separation processes.

Highly Enantioselective Transportation Across Liquid Membranes Mediated by Porous Covalent Organic Frameworks.

Chiral liquid membrane separation is crucial in pharmaceuticals and chemical synthesis for its simplicity and stability, yet designing membrane carriers that enable efficient enantioseparation remains a challenge. Here, we demonstrated for the first time that chiral porous materials can act as mobile carriers of bulk liquid membranes (BLMs) to enhance enantioselective transport and separation. We design and prepare three 2D chiral covalent organic frameworks (CCOFs) by imine condensations of a chiral dialdehyde with triamines containing ethyl, fluorine and/or isopropyl groups. These isostructural CCOFs feature ABC stacking, excellent water, acid and base tolerance, and chiral amine groups in 1D porous channels, promoting efficient enantioselective transportation of amino acid enantiomers. Among them, the CCOF with both -F and -iPr groups showing superior transport performance. Exfoliating the CCOF into chiral nanosheets creates flexible layers with accessible active sites, enabling nanosheet-mediated liquid membranes to separate chiral drug enantiomers, a feat unattainable with the pristine CCOF. This work establishes CCOFs as a promising platform for chiral BLM separations and will guide the design of high-performance BLMs using porous materials for enantioselective separation.

Polymerization of Sodium 4-Styrenesulfonate Inside Filter Paper via Dielectric Barrier Discharge Plasma

This work explores the polymerization of sodium 4-styrenesulfonate (NaSS) inside filter paper using dielectric barrier discharge (DBD) plasma and its application in the environmental field. The plasma-based technique, performed under mild conditions, solves common problems associated with conventional polymerization inside porous materials. The polymerization process was monitored using Fourier-transform infrared (FTIR) spectroscopy, which confirmed the consumption of double bonds, particularly in NaSS samples containing the optimal concentration of crosslinker divinyl benzene (DVB) (0.25% wt). Our work demonstrates the effectiveness and promise of DBD plasma as a substitute polymerization approach, especially for those in porous materials.