Porous Materials Research Articles

Ionic Porous Aromatic Frameworks Embedding Polyoxometalates for Heterogeneous Catalysis.

Porous aromatic frameworks (PAFs) are promising functional porous solids known for their feasible amenability and extraordinary stability. When the frameworkmodified by ionic functional groups, the given ionic PAFs (iPAFs) exhibited charged channels for adsorption, separation and catalysis. However, the surface areas of ionic porous frameworks are usually lower than the neutral ones, and their synthesis limited by specific strategies and complex modifying processes. To overcome these problems, we proposed an intuitive route to construct ionic porous framework with high specific surface area, through a multivariable synthesis strategy. Herein, multivariate ionic porous aromatic framework (MTV-iPAFs) material named PAF-270 was synthesized from readily available building units with ionic functional groups. PAF-270 exhibited hierarchical structure with the highest specific surface area among reported imidazolium functionalized PAFs. Leveraging its physical and chemical properties, we explored its availability for polyoxometalates loading and heterogeneous catalysis. PAF-270 exhibited high adsorption capacity up to 50% for both H3O40PW12 (HPW) and (NH4)5H6PV8Mo4O40 (V8). HPW@PAF-270 and V8@PAF-270 exhibited excellent catalytic abilities for oleic acid esterification and extractive oxidative desulfurization, respectively. Due to the stability of PAFs, these materials also showed remarkable resistance to temperature and pH changes. These results highlight the potential application of MTV-iPAFs as functional porous materials.

Effect of Boron-Doping on Gate-Opening CO2 Adsorption in Zinc-Benzimidazolate Coordination Networks.

Flexible metal-organic frameworks (MOFs) have attracted much attention as selective gas adsorption and storage. This report describes boron doping in zeolitic imidazolate framework-7 (B-ZIF-7), which exhibits reversible phase transition during CO2 adsorption/desorption. We have successfully prepared B-ZIF-7 coordination networks using boron-bridged benzimidazolate (B(bim)4-) as organic ligands. Powder X-ray diffraction (PXRD) measurements and infrared spectroscopy revealed that B-ZIF-7 has a crystal structure similar to that of ZIF-7 while containing boron bridging in the coordination network. Since B-ZIF-7 forms a cationic coordination network, the guest anions are encapsulated within the pore. CO2 adsorption/desorption measurements at 300 K showed that B-ZIF-7(NO3), which contains nitrate ions (NO3-) as guest anions in its pores, exhibits a S-shaped CO2 adsorption/desorption isotherm, which is characteristic of gate-opening type MOFs. Compared with ZIF-7, B-ZIF-7(NO3) has superior CO2 adsorption capacity in the low-pressure and superior CO2 storage capacity. The CO2 adsorption and desorption behavior of B-ZIF-7(NO3) was analyzed by in situ temperature-controlled PXRD measurements and thermogravimetric analysis under a CO2 atmosphere, and a reversible phase transition was observed. We have also successfully prepared B-ZIF-7(Cl) and B-ZIF-7(OTf) (OTf = CF3SO3-) with different guest anions. The CO2 adsorption/desorption behaviors of B-ZIF-7(Cl) and B-ZIF-7(OTf) were significantly different from those of B-ZIF-7(NO3) and ZIF-7. B-ZIF-7(Cl) showed gate opening at a higher pressure than ZIF-7, and B-ZIF-7(OTf) did not show S-shaped CO2 adsorption isotherm and showed adsorption behavior in micropores. These results indicate that the CO2 adsorption behavior of B-ZIF-7 depends on the interaction between the guest anions and CO2 molecules or the cationic framework and the bulkiness of the guest anions. Boron doping in a coordination network with boron-bridged imidazolate ligands is a promising strategy to increase the gas adsorption capability of porous materials.

Controlling the Uptake and Release of Semiochemicals in Channel-type Metal-Organic Frameworks through Pore Expansion.

Semiochemicals can be used to manipulate insect behaviour for sustainable pest management strategies, but their high volatility is a major issue for their practical implementation. Inclusion of these molecules within porous materials is a potential solution to this issue, as it can allow for a slower and more controlled release. In this work, we demonstrate that a series of Zr(IV) and Al(III) metal-organic frameworks (MOFs) with channel-type pores enable controlled release of three semiochemicals over 100 days by pore size design, with the uptake and rate of release highly dependent on the pore size. Insight from Grand Canonical Monte Carlo simulations indicates that this is due to weaker MOF-guest interactions per guest molecule as the pore size increases. These MOFs are all stable post-release and can be reloaded to show near-identical re-release profiles. These results provide valuable insight on the diffusion behaviour of volatile guests in MOFs, and for the further development of porous materials for sustainable agriculture applications.

Pore Space Characteristics and Morphology of Highly Porous Sc2O3 Ceramic Materials Synthesized

Pore Space Characteristics and Morphology of Highly Porous Sc2O3 Ceramic Materials Synthesized

Engineering Porosity and Functionality in a Robust Twofold Interpenetrated Bismuth-Based MOF: Toward a Porous, Stable, and Photoactive Material.

Defect engineering in metal-organic frameworks (MOFs) has gained worldwide research traction, as it offers tools to tune the properties of MOFs. Herein, we report a novel 2-fold interpenetrated Bi-based MOF made of a tritopic flexible organic linker, followed by missing-linker defect engineering. This procedure creates a gradually augmented micro- and mesoporosity in the parent (originally nonporous) network. The resulting MOFs can tolerate a remarkable extent of linker vacancy (with absence of up to 60% of linkers per Bi node) created by altering the crystal-growth rate as a function of synthesis temperature and duration. Owing to the enhanced porosity and availability of the uncoordinated Lewis acidic Bi sites, the defect-engineered MOFs manifested improved surface areas, augmented CO2 and water vapor uptake, and catalytic activity. Parallel to this, the impact of defect engineering on the optoelectronic properties of these MOFs has also been studied, offering avenues for new applications.

Efficient Template-Catalyzed In Situ Polymerization for Carbon Xerogels with Large Specific Surface Area and High Adsorption.

The limited specific surface area (SSA), long preparation period, and high cost are significant challenges for carbon xerogels (CXs). To overcome these limitations, we propose an approach to prepare tannin-resorcinol-formaldehyde-based CXs through template-catalyzed in situ polymerization. ZnCl2 acts as a catalyst and significantly accelerates the polymerization reaction through the coordination of Zn2+ to the carbonyl group in formaldehyde, while atmospheric drying instead of special drying and without solvent exchange reduces the preparation period to 24 h. In addition, ZnCl2 acts as an activator for the formation of many pores. Plant-derived tannins not only reduce the preparation cost but also regulate the pore structure. The resulted CXs with hierarchical porous structures show an optimal SSA of 1308 m2/g, high adsorption capabilities (for cationic, nitrosoaniline dyes, metal, and nonmetallic ions, especially for methylene blue with 454.93 mg/g), low shrinkage down to 10%, and reusability with 92.9% retention after 5 cycles. This work provides a promising and cost-effective method for the large-scale preparation of porous carbon materials with large SSA, offering potential applications in adsorption, energy storage, and catalysis.

Active learning graph neural networks for partial charge prediction of metal-organic frameworks via dropout Monte Carlo

Metal-organic frameworks (MOF) are an attractive class of porous materials due to their immense design space, allowing for application-tailored properties. Properties of interest, such as gas sorption, can be predicted in silico with molecular mechanics simulations. However, the accuracy is limited by the available empirical force field and partial charge estimation scheme. In this work, we train a graph neural network for partial charge prediction via active learning based on Dropout Monte Carlo. We show that active learning significantly reduces the required amount of labeled MOFs to reach a target accuracy. The obtained model generalizes well to different distributions of MOFs and Zeolites. In addition, the uncertainty predictions of Dropout Monte Carlo enable reliable estimation of the mean absolute error for unseen MOFs. This work paves the way towards accurate molecular modeling of MOFs via next-generation potentials with machine learning predicted partial charges, supporting in-silico material design.

Microstructural design of rigid porous materials using a Bayesian optimization method

Microstructural design of rigid porous materials using a Bayesian optimization method

Heat-Annealed Zinc Oxide on Flexible Carbon Nanotube Paper and Exposed to Gradient Light to Enhance Its Photoelectric Response

Buckypaper (BP), a flexible and porous material, exhibits photovoltaic properties when exposed to light. In this study, we employed radio frequency (RF) sputtering of zinc oxide (ZnO) followed by rapid thermal annealing to enhance the photovoltaic response of BP. We investigated the impact of various sputtering parameters, such as the gas flow ratio of argon to oxygen and deposition time, on the morphology, composition, resistivity, and photovoltaic characteristics of ZnO-modified BP. Additionally, the photovoltaic performance of the samples under different illumination modes and wavelengths was compared. It was found that optimal sputtering conditions—argon to oxygen flow ratio of 1:2, deposition time of 20 min, and power of 100 watts—resulted in a ZnO film thickness of approximately 45 nanometers. After annealing at 400 °C for 10 min, the ZnO-modified BP demonstrated a significant increase in photocurrent and photovoltage, along with a reduction in resistivity, compared to unmodified BP. Moreover, under gradient illumination, the ZnO-modified BP exhibited a photovoltage enhancement of 14.70-fold and a photocurrent increase of 13.86-fold, compared to uniform illumination. Under blue light, it showed a higher photovoltaic response than under other colors. The enhancement in photovoltaic response is attributed to the formation of a Schottky junction between ZnO and BP, an increased carrier concentration gradient, and an expanded light absorption spectrum. Our results validate that ZnO sputtering followed by annealing is an effective method for modifying BP for photovoltaic applications such as solar cells and photodetectors.

3D-printed porous tantalum artificial bone scaffolds: fabrication, properties, and applications.

Porous tantalum scaffolds offer a high degree of biocompatibility and have a low friction coefficient. In addition, their biomimetic porous structure and mechanical properties, which closely resemble human bone tissue, make them a popular area of research in the field of bone defect repair. With the rapid advancement of additive manufacturing, 3D-printed porous tantalum scaffolds have increasingly emerged in recent years, offering exceptional design flexibility, as well as facilitating the fabrication of intricate geometries and complex pore structures that similar to human anatomy. This review provides a comprehensive description of the techniques, procedures, and specific parameters involved in the 3D printing of porous tantalum scaffolds. Concurrently, the review provides a summary of the mechanical properties, osteogenesis and antibacterial properties of porous tantalum scaffolds. The use of surface modification techniques and the drug carriers can enhance the characteristics of porous tantalum scaffolds. Accordingly, the review discusses the application of these porous tantalum materials in clinical settings. Multiple studies have demonstrated that 3D-printed porous tantalum scaffolds exhibit exceptional corrosion resistance, biocompatibility, and osteogenic properties. As a result, they are considered highly suitable biomaterials for repairing bone defects. Despite the rapid development of 3D-printed porous tantalum scaffolds, they still encounter challenges and issues when used as bone defect implants in clinical applications. Ultimately, a concise overview of the primary challenges faced by 3D-printed porous tantalum scaffolds is offered, and corresponding insights to promote further exploration and advancement in this domain are presented.

Study on the Coupled Heat Transfer of Conduction, Convection, and Radiation in Foam Concrete Based on a Microstructure Numerical Model

Foam concrete is a typical cement-based porous material; its special microstructure endows it with excellent properties, such as light weight, energy efficiency, thermal insulation, and fire resistance. Therefore, it is widely used as a thermal insulation material for buildings. The heat transfer modes of foam concrete include conduction, convection, and radiation. However, previous studies considered conduction to be the dominant mode, often neglecting the effects of convection and radiation. In this study, a stochastic numerical model of the foam concrete microstructure is established based on the statistical parameters of the pore structure. With this model, the heat transfer mechanism of foam concrete is analyzed at the mesoscopic level, and the equivalent thermal conductivity is calculated. By comparing four different working conditions, the influence of conduction, convection, and radiation on the heat transfer of foam concrete is analyzed, and the specific contribution rates of conduction, convection, and radiation are calculated. The results show that the convection effect is weak due to the pore size being smaller than 1 ; so, the influence of convection can be neglected in the heat transfer analysis of foam concrete. The contribution of radiation increases with the decrease in foam concrete density and the increase in temperature difference. When the temperature difference is 40 and the density is 300 , the contribution of radiation exceeds 20. Therefore, for low-density and high-temperature difference situations, the influence of radiation cannot be ignored. The heat transfer in foam concrete is mainly through conduction, but with the decrease in density and the increase in temperature difference, the contribution of conduction shows a downward trend. Nevertheless, the contribution of conduction is still much larger than that of radiation and convection.

Novel cobalt-incorporated two dimensional covalent organic frameworks for supercapacitor applications

Covalent-organic frameworks (COFs), are a promising new class of crystalline porous organic materials with confined structures either in 2D or 3D domains. The current study focuses on using a solvothermal approach consisting of sealed pyrex tubes to synthesize two-dimensional TBP-COF and TBP-COF that have been doped with cobalt (Co) (TBP-Co@COF). The results of the experimentally acquired X-ray diffraction study were compared with those from simulations, and it was discovered that both are in good agreement. A thorough theoretical analysis of the layer packing in AA stacking (P1) and AB stacking (P1) modes using the Materials Studio revealed that AA stacking is more stable than the AB stacking (P1) structure. The formation of imine linkage and incorporation of Co into the COF are indicated by the result of XPS. Unaggregated dispersion of Co particles can be seen on the square and rectangular sheets of TBP-COF in TEM and SEM images. Both materials are fabricated as electrode materials and evaluated for their supercapacitor applications. The TBP-Co@COF shows an enhanced specific capacitance (CSp) of 975F/g compared to the TBP-COF (827F/g) at 2 mV/s scan rate. TBP-Co@COF exhibit an energy density (ED) of 69 Wh/kg even at a high power density (PD) of 75000 W/kg and also retains 79 % of its initial capacitance up to 2000 cycles. TBP-COF and TBP-Co@COF were fabricated for an asymmetric supercapacitor device (ASD) and found to exhibit a CSp of 191F/g at a scan rate of 2 mV/s.

Rational solvent selection for the preparation of industrial monolithic supported liquid-phase (SLP) olefin hydroformylation catalyst

Heterogenisation of the hydroformylation (HyFo) process converting C4 olefins and syngas (CO/H2) to n-pentanal can substantially reduce its carbon footprint by simplifying downstream processing. Current upscaling efforts include constructing a pilot plant containing a Rh-diphosphite-stabiliser supported liquid-phase (SLP) catalyst. The air-sensitive nature of the catalyst requires in-situ impregnation of the porous support material with the liquid phase components (Rh-precursor, ligand, stabiliser) entailing the use of large quantities of an organic solvent. Environment, health, and safety (EHS) as well as regulatory aspects prompt the search for an alternative to dichloromethane (DCM), which was used as standard solvent for lab-scale studies. To obtain alternatives to DCM, the replacement solvent methyl tert-butyl ether (MTBE) and in-silico screening of more than 5000 solvent candidates has been performed covering boiling points and solubility predictions by COSMO-RS as well as carcinogenicity- and mutagenicity predictions by quantitative structure–activity relationship (QSAR) models. The final list of solvent candidates contained unsaturated compounds (alkenes, alkynes) in addition to ether- and ester-functionalised solvents, which are typically recommended as DCM replacements. Sufficiently high solubilities of ligand and stabiliser to prepare the desired SLP catalyst were experimentally determined in the following solvents: methyl propionate (MP), dimethoxymethane (DMM), MTBE, tetrahydrofuran (THF) and DCM for benchmarking, and a monolithic SLP catalyst prepared with MTBE demonstrated to perform equally well in the HyFo reaction of 1-butene as the benchmark catalyst prepared using DCM solvent. Overall, the study demonstrates a practical approach for selecting solvents with a greener profile for making catalyst systems applicable for large-scale production.

Oscillatory instability of magneto-convection during the melting of non-Newtonian ferromagnetic nano-enhanced phase change materials at low Rayleigh number

This work complements mechanism of the oscillatory instability of magneto-convection in the process of melting heat transfer controlled by magnetic field at low Rayleigh number (Ra), aiming to provide a theoretical basis for improving the stability of energy storage system and melting manufacturing process. A latent heat storage cavity unit exposed in uniform magnetic field is designed to reveal the magnetic-controlled heat transfer in solid–liquid phase change process. The volume average method is used to describe porous media composite nano-enhanced phase change materials in latent heat unit. Special attentions are paid to the key parameters of Magnetic number (Mn) and Ra, and coupling flow heat transfer mechanism of magnetic force and natural convection effect is numerically studied. The evolution stages of different flow patterns are divided according to the Kelvin force, vorticity, velocity, flow field and isotherm distributions of characteristic points. Main results show that the magnetic field-modulated phase change process at low Ra can be divided into three stages, of which the second stage is characterized by periodic oscillations. Increasing Mn at fixed Ra accelerates the second stage of oscillatory convection heat transfer coming earlier and promotes melting. When Mn increase to 5 × 106, the full melting time is reduced to the greatest extent, resulting in 11.6 % reduction in heat storage but 17.4 % increase in heat storage efficiency. Three mechanisms of magnetic forced convection coupled with natural convection are found during the increase of Ra: synergistic (Ra < 2 × 103), antagonistic (2 × 103≤ Ra < 1 × 104), and natural convection-dominated (Ra = 1 × 104). Finally, the mode distribution map of Ra-Mn regulation is obtained, in which the unstable transformation mechanism of steady-state, periodic oscillation and chaotic oscillation heat transfer in the melting process under the control of magnetic field is described.

Capacitance performance of N/O co-doped hierarchical porous carbon nanosheets synthesized via "one stone for three birds" strategy

The enrichment of heteroatom doping and optimization of pore structure are considered crucial strategies for enhancing the capacitive performance of carbon materials. In this study, utilizing potassium folate as the precursor, we propose a green, simple, and scalable self-activation, self-template, self-doping method to fabricate N/O co-doped porous carbon material. The optimized sample exhibits a specific surface area of 1852 m2 g−1, providing abundant active sites. In a three-electrode system, the specific capacitance of KFA-800 reaches 274.2Fg−1 at 0.2Ag−1 in 6M KOH electrolyte. Symmetric supercapacitors prepared with KFA-800 as the electrode show a specific capacitance of 129.2Fg−1 at 0.1Ag−1. The maximum energy density of symmetric supercapacitor was 17.9Whkg−1 at the power density of 100Wkg−1. After 50,000 cycles at 10Ag−1, it retained 90.91% of the initial capacitance. This work provides a novel approach for the preparation of folate derived porous carbon materials, expanding their applications in energy storage devices.

Free-standing ultra-thin carbon nanofiber films with controllable thickness for lithium ion batteries

Thin and porous anode materials enable short ion migration distances and high-rate performance. However, the current freestanding anode materials are too thick (typically around 100 μm) for high-rate lithium ion batteries (LIBs). Here, we have developed a facile and scalable process to synthesize ultra-thin (<400 nm) freestanding films. In comparison to other chemical and physical deposition methods that yield thin films (<500 nm), our freestanding films do not require the substrate material, achieving a 100% loading of active material. Our ultra-thin carbon nanofiber films exhibit an exceptional specific capacity of 599 mAh/g even after 10,000 cycles at a current density of 10 A/g. Compared to thick carbon nanofiber films, the utilization of ultra-thin carbon nanofiber films as anode materials exhibits a remarkable enhancement of more than tenfold in cycling performance

Shape engineering for improved gas separation: Computation-driven insights on harnessing platonic particles in mixed-matrix membranes

Recently, there has been a growing focus on the significance of mixed matrix membranes (MMMs) in the domain of gas separation processes. It is well known that, the integration of structurally diverse porous materials into a polymeric matrix intensifies the influence of filler structural sensitivity during the performance evaluation of MMMs. In this study, a computational approach utilizing voxel-based finite element method (FEM) was employed for a systematic investigation of the impact of Platonic shapes used as fillers on the criteria that dictate the design of optimal membranes. The assessment of single gas transport in MMMs containing randomly distributed fillers has confirmed that filler particles with varying sphericity, but the same volume, can significantly influence the effective permeability of MMMs. A reduction in filler particle sphericity, such as in the case of a tetrahedral structure compared to a spherical one, results in a substantial enhancement of effective permeability, primarily due to the introduction of more interconnected pathways. This effect becomes increasingly pronounced at higher filler loading fractions and filler-to-polymer ratios. Furthermore, binary gas transport assessments of MMMs established that filler particle shapes have a considerable influence over the optimal filler-matrix combination, particularly in the context of phase gas transport compatibility, aimed at achieving maximal selectivity in gas mixtures. Filler particles with lower sphericity yield a higher maximum selectivity; however, this is achieved with a partially higher filler-to-polymer permeability for faster gas flow compared to spherical filler particles. This research offers valuable insights for the strategic enhancement of permeability and selectivity in MMMs through the integration of structurally diverse porous materials.

Functionalization of β-Cyclodextrin Metal-Organic Frameworks with Gelatin and Glutamine for Drug Delivery of Curcumin to Cancerous Cells

Beta-cyclodextrin Metal-Organic Framework (β-CD-MOF) is a unique class of porous materials that merges the inherent properties of cyclodextrins with the structural advantages of metal-organic frameworks (MOFs). When combined with the concept of MOFs, which are crystalline structures composed of metal ions or clusters linked by organic ligands, the resulting β-CD-MOF holds immense potential for various applications, especially in the field of drug delivery. In this study, biocompatible metal-organic frameworks (MOFs) synthesized using β-Cyclodextrin (β-CD) and potassium enabled drug delivery of curcumin (CCM) to cancerous cells. Functionalizing β-CD-MOF with L-glutamine (glutamine-β-CD-MOF) enhanced cancer cell-specific targeting due to glutamine's essential role in cancer cell proliferation and energy pathways. Amino group functionalization provided further functionalization opportunities. Gelatin coating (gelatin@β-CD-MOF) facilitated controlled drug release in an acidic medium. High drug loading capacities (52.38-55.63%) were achieved for β-CD-MOF@CCM and glutamine-β-CD-MOF@CCM, leveraging the high porosity and affinity of amine and phenol groups of curcumin. The MTT assay highlighted the specificity and differentiation of glutamine-β-CD-MOF in targeting cancerous over normal cells. These functionalized β-CD MOFs efficiently encapsulate curcumin, ensuring controlled drug release and enhanced therapeutic efficacy, particularly in cancer therapy.

Preparation of porous materials by ultrasound-intensified acid leaching of high-carbon component in coal gasification fine slag

Preparation of porous materials by ultrasound-intensified acid leaching of high-carbon component in coal gasification fine slag

Core‐Shell Zeolite with Confined Nickel Particles as Prominent Catalyst for the Hydrogenation of Maleic Anhydride

Transformation of maleic anhydride (MA) into succinic anhydride (SA) through the development of high‐performance catalysts is an appealing approach from a sustainable development perspective. Herein, a core‐shell catalyst with silicate‐1 supported and MCM‐41 encapsulated nickel was prepared, which exhibited extraordinarily high MA conversion (99.8%) and SA selectivity (99.9%). Detailed structural characterizations and catalytic evaluation demonstrated that the core‐shell catalyst derived from the liquid deposition method is a hierarchically porous material with tunable shell thicknesses, possessing strong interaction between Ni particles and the supports. Key to this success is the MCM‐41 shell that covered the defects such as silanol nests on the surface of the silicate‐1 zeolite, diminishing both the surface and intra‐particle diffusion barriers, thus the specially‐designed catalyst achieved high activity under rather mild conditions (100 °C, 3.0 MPa), which is 59% higher than the conventional silicate‐1 supported Ni catalyst. Furthermore, the mesoporous MCM‐41 shell plays a crucial role in minimizing the leaching and sintering of Ni particles, thereby bolstering catalytic stability. Overall, the research provides a new approach for the rational design to optimize the performance of hydrogenation catalysts and introduces a novel idea to enhance the activity and stability of Ni‐supported catalysts.