Hierarchical Porous Monoliths Research Articles

Preparation of Hierarchical Porous Monoliths With High Surface Areas by a Solvent Knitting Strategy.

Hierarchical porous hypercrosslinked monoliths (PolyHIPE-HCP) with ultrahigh specific surface areas are prepared via a solvent knitting strategy. Compared to previous work, the solvent knitting strategy is carried out in a relatively low air-controlled atmosphere with gradient heating starting from low temperature while using DCM (Dichloromethane) as both a solvent and a cross-linker, allowing for a slow and controlled cross-linking process, thereby achieving a BET surface area ranging from 514 to 728m2g-1. Scanning electron microscopy (SEM) shows that the knitting process does not affect the presence of macroporous structure in the PolyHIPE. With the introduction of mesopores and micropores, these hierarchical porous monoliths exhibit significant potential for applications in gas adsorption and water treatment. Hence, a universal, simple and low-cost method to synthesize polymeric monoliths with hierarchically porous structure and higher surface area is proposed, which has fascinating prospects in industrialization.

Application of Hierarchically Porous Chitosan Monolith for Enzyme Immobilization.

Enzyme immobilization is a crucial technique for improving the stability of enzymes. Compared with free enzymes, immobilized enzymes offer several advantages in industrial applications. Efficient enzyme immobilization requires a technique that integrates the advantages of physical absorption and covalent binding while addressing the limitations of conventional support materials. This study offers a practical approach for immobilizing α-amylase on a hierarchically porous chitosan (CS) monolith. An optimized CS monolith was fabricated using chemically modified chitin by thermally induced phase separation. By combining physical adsorption and covalent bonding, this technique leverages the amino and hydroxy groups present in CS to facilitate effective enzyme binding and stability. α-Amylase immobilized on the CS monolith demonstrated excellent stability, reusability, and increased activity compared to its soluble counterpart across various pH levels and temperatures. In addition, the CS monolith exhibited a significant potential to immobilize other enzymes, namely, lipase and catalase. Immobilized lipase and catalase exhibited higher loading capacities and enhanced activities than their soluble forms. This versatility highlights the broad applicability of CS monoliths as support materials for various enzymatic processes. This study provides guidelines for fabricating hierarchical porous monolith structures that can provide efficient enzyme utilization in flow systems and potentially enhance the cost-effectiveness of enzymes in industrial applications.

Sol-gel mediated synthesis and characterization of hierarchically porous Fe2O3/SiO2 monolithic catalyst for high temperature sulfuric acid decomposition

To address the issues faced by microparticulate catalysts in fixed bed reactors for high temperature sulfuric acid decomposition viz. channeling and mass transfer, we report the preparation, characterization of Fe2O3/SiO2 hierarchical porous monoliths and testing of its catalytic properties. Monoliths with varying Fe2O3 amounts (5–30 wt%) are synthesized by a modified sol-gel approach and characterized by powder XRD, Mössbauer spectroscopy, SAXS, SEM-EDS and XPS. The Fe2O3(15 wt%)/SiO2 monolith exhibited a SO2 yield of ∼62% at 800 °C. The spent catalyst investigation established the dynamic nature of catalyst surface to accomplish the reaction mechanistic demands.

Hierarchical Porous Monoliths of Steel with Self-Reinforcing Adaptive Properties.

Porous structures offer an attractive approach to reduce the amount of natural resources used while maintaining relatively high mechanical efficiency. However, for some applications the drop in mechanical properties resulting from the introduction of porosity is too high, which has limited the broader utilization of porous materials in industry. Here, it is shown that steel monoliths can be designed to display high mechanical efficiency and reversible self-reinforcing properties when made with porous architectures with up to three hierarchical levels. Ultralight steel structures that can float on water and autonomously adapt their stiffness are manufactured by the thermal reduction and sintering of 3D printed foam templates. Using distinct mechanical testing techniques, image analysis, and finite element simulations, the mechanisms leading to the high mechanical efficiency and self-stiffening ability of the hierarchical porous monoliths are studied. The design and fabrication of mechanically stable porous monoliths using iron as a widely available natural resource is expected to contribute to the future development of functional materials with a more sustainable footprint.

Hierarchical Macro-Mesoporous Silica Monolithic Tablets as a Novel Dose-Structure-Dependent Delivery System for the Release of Confined Dexketoprofen.

This study reports the application of hierarchical porous monoliths as carriers for controlled and dose-adjustable release of model pharmaceutical (dexketoprofen, DEX). The synthesis and detailed characterization of the hierarchical porous scaffolds are provided before and after the adsorption of three doses of DEX─a widely used nonsteroidal anti-inflammatory drug. The drug incorporated in the mesopores of silica was stabilized in an amorphous state, while the presence of macropores provided sufficient space for drug crystallization as we demonstrated via a combination of powder X-ray diffraction, differential scanning calorimetry, and imaging techniques (scanning electron microscopy and EDX analysis). Drug release from silica matrices was tested, and a mechanistic model of this release based on the Fick diffusion equation was proposed. The hierarchical structure of the carrier, due to the presence of micrometric macropores and nanometric mesopores, turned out to be critical for the control of the drug phase and drug release from the monoliths. It was found that at low drug content, the presence of an amorphous component in the pores promoted the rapid release of the drug, while at higher drug contents, the presence of macropores favored the crystallization of DEX, which naturally slowed down its release. Both the hierarchical porous structure and the control of the drug phase (amorphous and/or crystalline) were proven important for adjustable (fast or prolonged) release kinetics, desirable for effective pharmacotherapy and patient compliance. Therefore, the developed materials may serve as a versatile formulation platform for the smart manipulation of drug release kinetics.

Assembly of SBA-15 into hierarchical porous monoliths replicating polymeric scaffolds

This study reports the preparation of highly porous, SBA-15-based monolithic materials with pore sizes spanning over four scales (micro-/meso-/small macro-/large macro-pores). Two approaches were explored. The first one involves the preparation of PMMA scaffolds obtained from chemically-bonded beads and their further infiltration using SBA-15 slurries with suitable viscosity; while the second one directly uses the same amount of PMMA beads dispersed within the slurries. Emphasis was given to the comparison of the textural, structural, and mechanical properties obtained following each approach. Then, application of a thermal consolidation step and its influence over the monoliths properties was investigated, with an optimum observed at 950 °C. The second method systematically allowed reaching higher mechanical resistances (86 vs 32 kPa at 950 °C) for comparable specific surface areas (274 vs 290 m2/g at 950 °C), however at the expense of smaller macropores and lower ordering in the monoliths.

Facile Preparation of Hierarchically Porous Monolith with Optical Activity Based on Helical Substituted Polyacetylene via One-Step Synthesis for Enantioselective Crystallization.

The present study reported the flexible and highly efficient one-step synthesis of chiral hierarchical porous monoliths via cross-linking and polymerization-induced phase separation using substituted acetylene and cross-linker in the presence of porogenic solvent (tetrahydrofuran and methanol) in which the complex doping and complicated procedures were not required. It was demonstrated that hierarchical pore structure with through-pore and high surface area existed in the monoliths, which provides more chiral sites and space for interaction between monolithic materials and the solution. The porous structures and pore size can be adjusted by changing the conditions of phase separation. Moreover, the prepared monoliths exhibited good optical activity, thermal stability and mechanical properties. Therefore, the hierarchically porous monoliths with optical activity were applied in enantioselective crystallization and showed good performance.

A cellulose monolith supported metal/organic framework as a hierarchical porous material for a flow reaction.

A cellulose monolith with immobilized controlled-growth metal organic frameworks (MOFs) is developed. The synthesized hierarchical porous monolith shows great performance as a flow reactor.

Microfluidics for synthesis and morphology control of hierarchical porous covalent organic polymer monolith

The hierarchical porous monoliths are important in enhancing diffusion efficiency and reducing pressure drop in heterogeneous catalysis. Here, a practical way to synthesize hierarchical porous covalent organic polymer (COP) monolith by using droplet microfluidic is proposed. The interconnected macro pores (up to ∼ 130 nm) were created within intrinsic microporous COP structures by the further condensation of COP particles in the confined microdroplets. Concentration, flow rate ratio, catalyst, etc., were screened to figure out the superior condition for producing different hierarchical porous COP monolith in microfluidic. Rod-like and spherical monolith with gradient sizes were controllable synthesized to satisfy the requirements of different packing density for practical applications. Significantly, our homemade single microreactor is able to produce the spherical hierarchical porous COP monolith with a high space-time yield of 413 kg·m−3·day−1 at optimized condition, which provides a promising scale-up method to synthesize COP monoliths for but not limit to industrial heterogeneous catalysis.

Novel Fabrication and Enhanced Photocatalytic MB Degradation of Hierarchical Porous Monoliths of MoO3 Nanoplates

Porous monoliths of MoO3 nanoplates were synthesized from ammonium molybdate (AHM) by freeze-casting and subsequent thermal treatment from 300 to 600 °C. Pure orthorhombic MoO3 phase was obtained at thermal treatment temperature of 400 °C and above. MoO3 monoliths thermally treated at 400 °C displayed bimodal pore structure, including large pore channels replicating the ice crystals and small pores from MoO3 sheets stacking. Transmission electron microscopy (TEM) images revealed that the average thicknesses of MoO3 sheet were 50 and 300 nm in porous monoliths thermally treated at 400 °C. The photocatalytic performance of MoO3 was evaluated through degradation of methylene blue (MB) under visible light radiation and MoO3 synthesized at 400 °C exhibited strong adsorption performance and best photocatalytic activity for photodegradation of MB of 99.7% under visible illumination for 60 min. MoO3 photocatalyst displayed promising cyclic performance, and the decolorization efficiency of MB solution was 98.1% after four cycles.

Assembly of a Metal-Organic Framework into 3 D Hierarchical Porous Monoliths Using a Pickering High Internal Phase Emulsion Template.

3D Hierarchical porous metal-organic framework (MOF) monoliths are prepared by using Pickering high internal phase emulsion (HIPE) template. Pickering HIPEs were stabilized solely by UiO-66 MOF particles with internal phase up to 90 % of the volume. The effects of internal phase type and volume, as well as MOF particle concentration on the stability of resulting Pickering HIPEs were investigated. Furthermore, by adding small amount of polyvinyl alcohol (PVA) as binder or polymerization in the continuous aqueous phase, followed by freeze-drying, two types of MOF-based 3D hierarchical porous monoliths with ultralow density (as low as 12 mg cm(-3) ) were successfully prepared. This Pickering HIPE template approach provides a facile and practical way for assembling of MOFs into complex structures.

Fabrication of Silica Monoliths with Hierarchically Porous Structure from Freeze-Drying

This paper provides a novel route to prepare silica monoliths with hierarchical porous structure via freeze drying. In this method, macroporous silica monoliths were first produced by freeze-drying and calcination. By adjusting the concentration of cetyltrimethylammonium bromide in ethylsilicate, a layer of mesoporous thin film was attached on the macroporous silica monolith. The structural characterization of the hierarchical porous monoliths were studied by field emission scanning electron microscopy, mercury porosimeter and nitrogen adsorption-desorption techniques (BET). It turned out that the pore distribution of the obtained monoliths was ranged from 3.72 nm to 23.21nm and the maximum specific surface area calculated from BET was about 288 m2/g, which indicated the existence of hierarchical structure in the obtained material.