In2O3/ZrO2-based materials are emerging as candidates for the next generation of industrial catalysts for direct methanol synthesis. In this research, such catalysts were additively manufactured into two distinct geometries that exhibit different pressure drops and activity profiles, both among themselves and in comparison to extrudates. The monoliths produced were comprehensively characterized using a range of techniques, including gas sorption, X-ray diffraction, micro X-ray fluorescence, and Raman mapping, to verify their phase and chemical composition. Computational fluid dynamics was employed to simulate the gas flow through these structures, corroborating that the variations in the accessible surface area are the reason for changes in their performance. Furthermore, the postreaction characterization provides some insight into the catalysts' degradation mechanisms under hydrogen-rich conditions, identifying the migration of indium oxide to the catalyst surface and pore blocking as possible causes of the loss of activity.

To advance the concept of a circular economy, fungal mycelium-based materials are drawing increased attention as substitutes for nonsustainable materials, such as petroleum-based and animal-derived products, due to their biodegradability, low carbon footprint, and cruelty-free nature. Addressing the challenge of mechanical properties in fungal mycelium products, this study presents a straightforward approach for reinforcing fungal mycelium mats. This is achieved by using two bio-based and biodegradable polymers, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) and polylactic acid (PLA), via material extrusion additive manufacturing (MEX AM), commonly known as 3D printing, to produce fungal mycelium-biopolymer composites. By analyzing the mechanical properties, roughness, and morphology, this study demonstrates significant improvements in ultimate tensile strength with the application of PHBH and even more with PLA, while elasticity is reduced. The study also discusses potential improvements to enhance the quality of the fungal mycelium-biopolymer composites without trading off bio-based and biodegradable features, offering a promising pathway for the development of more durable and sustainable fungal mycelium products.

Humanity is often fascinated by structures and materials developed by Nature. While structural materials such as wood have been widely studied, the structural and mechanical properties of fungi are still largely unknown. One of the structurally interesting fungi is the polypore Fomes fomentarius. The present study deals with the investigation of the light but robust fruiting body of F. fomentarius. The four segments of the fruiting body (crust, trama, hymenium, and mycelial core) were examined. The comprehensive analysis included structural, chemical, and mechanical characterization with particular attention to cell wall composition, such as chitin/chitosan and glucan content, degree of deacetylation, and distribution of trace elements. The hymenium exhibited the best mechanical properties even though having the highest porosity. Our results suggest that this outstanding strength is due to the high proportion of skeletal hyphae and the highest chitin/chitosan content in the cell wall, next to its honeycomb structure. In addition, an increased calcium content was found in the hymenium and crust, and the presence of calcium oxalate crystals was confirmed by SEM-EDX. Interestingly, layers with different densities as well as layers of varying calcium and potassium depletion were found in the crust. Our results show the importance of considering the different structural and compositional characteristics of the segments when developing fungal-inspired materials and products. Moreover, the porous yet robust structure of hymenium is a promising blueprint for the development of advanced smart materials.

Ambient pressure drying (APD) allows for synthesizing aerogels without expensive and sophisticated equipment for achieving supercritical conditions. Since APD does not eliminate the capillary stress that is induced by the liquid/vapour phase boundary, the shrinkage during drying needs to be prevented or reversed. The re-expansion of the silylated silica gels during drying is commonly referred to as the springback effect (SBE). The SBE is not only important for producing aerogels via APD, but is also a fascinating phenomenon, since it is accompanied by a significant volume change unusual for rigid ceramics. Synchrotron X-ray scattering has proven to be especially effective for the investigation of the volume change of these fractal silica structures on different length scales. In this work, we follow the drying, shrinkage, and (partial) re-expansion of various monolithic samples in situ to explore the occurrence of the SBE. For this purpose, various silylation agents, i.e., hexamethyldisilazane, trimethylchlorosilane, and triethylchlorosilane were used to investigate different shrinkage and re-expansion behavior. A scattering model was used to extract additional information of the evolving primary particle size, correlation length, fractal dimension, and other intensity contributions of the silica network and the hexane. While the primary particles pointed towards a relaxation at near molecular size, they were likely not involved in the SBE. However, structures near the size of the correlation length could be essential for the occurrence of this phenomenon. These findings may lead to the origin of this interesting phenomenon, as well as a better understanding of the production of APD aerogels.

Ambient pressure drying (APD) can prospectively reduce the costs of aerogel fabrication and processing. APD relies solely on preventing shrinkage or making it reversible. The latter, i.e., the aerogel re-expansion after drying (so-called springback effect—SBE), needs to be controlled for reproducible aerogel fabrication by APD. This can be achieved by an appropriate surface functionalization of aerogel materials (e.g., SiO2). This work addresses the fabrication of monolithic SiO2 aerogels and xerogels by APD. The effect of several silylation agents, i.e., trimethylchlorosilane, triethylchlorosilane, and hexamethyldisilazane on the SBE is studied in detail, applying several complementary experimental techniques, allowing the evaluation of the macroscopic and microscopic morphology as well as the composition of SiO2 aerogels. Here, we show that some physical properties, e.g., the bulk density, the macroscopic structure, and pore sizes/volumes, were significantly affected by the re-expansion. However, silylation did not necessarily lead to full re-expansion. Therefore, similarities in the molecular composition could not be equated to similarities in the SBE. The influences of steric hindrance and reactivity are discussed. The impact of silylation is crucial in tailoring the SBE and, as a result, the APD of monolithic aerogels.

Different ordered mesoporous silica (OMS) nanoparticles, ranging from regular COK-12 to COK-12 modified in terms of pore shape and size, have been employed as standard drug carriers for the controlled adsorption and release of drug molecules in comparison to well-known OMS SBA-15 and MCM-41. The cytotoxicity analysis demonstrated that regular COK-12 particles were less harmful to mammalian cultured cells, causing lower apoptosis induction than modified COK-12, MCM-41, and SBA-15 particles. Thus, regular COK-12 was further used to prepare a dual antibiotic-loaded drug delivery material, followed by surface functionalization with Staphylococcus aureus-specific aptamers for targeting. The results demonstrated that the joint loading of lysozyme and vancomycin in regular COK-12 improved the ability of the antibiotic treatments to kill methicillin-resistant Staphylococcus strains via aptamer targeting. The minimum inhibitory concentration (MIC) values decreased 4.1-fold and 12-fold compared to the non-targeted use of the antimicrobial agents in homogeneous solutions for vancomycin and lysozyme, respectively, clearly demonstrating the high potential of COK-12 to be used as a carrier in multidrug therapy.

Abstract Hierarchically porous, high‐surface‐area silica materials are excellent candidates for multiple applications like catalysis and environmental remediation. Shaping these materials with additive manufacturing (AM) techniques, like robocasting, could enable their use with the benefit of on‐demand, customized shaping and maximizing performance. Herein, ordered mesoporous silica COK‐12 slurries were robocasted into monoliths, containing different ratios of uncalcined COK‐12 and sodium bentonite (0–25 wt.%). The rheology of the mixed slurries is characterized by lower flow indexes (0.69 vs. 0.32) and higher yield stresses (96 vs. 259 Pa) compared to pure COK‐12 ones. Monoliths were printed in woodpile structures and calcined at 600°C. Micro‐CT measurements showed a linear shrinkage of 25% after calcination. Mechanical characterization showed increased uniaxial strength (0.20 ± 0.07 to 1.0 ± 0.3 MPa) with increasing binder/solids ratio from 13 to 25%. The amorphous, mesoporous structure of COK‐12 was retained. The structures exhibited open porosities of 52 ± 4% and showed higher specific mesopore volumes, and increased average mesopore size (6 vs. 8 nm) compared to COK‐12. Small‐angle x‐ray scattering analysis revealed an increased lattice parameter (10.3 vs. 11.0 nm) and reduced wall thickness (3.1 nm vs. 4.1 nm) of the COK‐12 in the monoliths. These properties indicate suitability for their application as porous supports and adsorbents.

Large, ink-bottle-shaped pores in mesocellular foams (MCFs) are desired for various applications requiring enhanced mass transfer or the immobilization of larger compounds. Hence, the cylindrical pores of COK-12, an ordered mesoporous silica structurally comparable to SBA-15 but synthesized at room-temperature at quasi-neutral pH, are chemically swollen into ink-bottle pores. Therefore, p-xylene is used as a more sustainable swelling agent compared to popular alternatives. Its high boiling point allows for an additional thermal aging step to amplify the mesostructure enlargement without needing additional chemicals. For COK-12, the MCFs obtained at room temperature reach an unprecedented plateau for the modal mesopore cell and window diameter of 19.9 and 5.5 nm, respectively, with an underlying broad pore size distribution and distorted hexagonal lattice up to 14.5 nm, involving hexagonal and spherical structures. The combined chemical and thermal swelling resulted in the selective enlargement of the window diameter to more than 200% and a slightly increased cell diameter, pore size distribution, and hexagonal lattice distortion in comparison to the room temperature synthesis. Such materials are thought to be promising alternatives to SBA-15-based MCFs, often utilizing toxic catalysts during synthesis. The presented results pave the way for enhanced adsorptive, catalytic, and drug delivery performances for COK-12-based materials.

Lab-cultivated mycelia of Fomes fomentarius (FF), grown on a solid lignocellulose medium (FF-SM) and a liquid glucose medium (FF-LM), and naturally grown fruiting bodies (FF-FB) were studied as biosorbents for the removal of organic dyes methylene blue and Congo red (CR). Both the chemical and microstructural differences were revealed using X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, zeta potential analysis, and scanning electron microscopy, illuminating the superiority of FF-LM and FF-SM over FF-FB in dye adsorption. The adsorption process of CR on FF-LM and FF-SM is best described by the Redlich-Peterson model with β constants close to 1, that is, approaching the monolayer Langmuir model, which reach maximum adsorption capacities of 48.8 and 13.4 mg g-1, respectively, in neutral solutions. Adsorption kinetics follow the pseudo-second-order model where chemisorption is the rate-controlling step. While the desorption efficiencies were low, adsorption performances were preserved and even enhanced under simulated dye effluent conditions. The results suggest that F. fomentarius can be considered an attractive biosorbent in industrial wastewater treatment and that its cultivation conditions can be specifically tailored to tune its cell wall composition and adsorption performance.

The springback effect during ambient pressure drying of aerogels is an interesting structural phenomenon, consisting of a severe shrinkage followed by almost complete re-expansion. The drying of gels causes shrinkage, whereas re-expansion is believed to be linked to repelling forces on the nanoscale. A multi-scale structural characterization of this significant volume change is key in controlling aerogel processing and properties. In this work, hydrophobic, monolithic silica aerogels with high specific surface areas were synthesized by modification with trimethylchlorosilane and ambient pressure drying. Here, we report a multi-method approach focusing on in-situ X-ray scattering to observe alterations of the nanostructured material during the drying of surface-modified and unmodified silica gels. Both show a porous fractal nanostructure, which partially collapses during drying and only recovers in surface-modified samples during the springback effect. Distinct changes of the X-ray scattering data were reproducibly associated with the shrinkage, re-expansion and drying of the gel network. Our findings may contribute to tailor aerogels with specific functionality, as the springback effect has a direct influence on properties (e.g., porosity, pore size distribution), which is directly affected by the degree of re-expansion.

Although they are of significant importance for environmental applications, the industrialization of photocatalytic techniques still faces many difficulties, and the most urgent concern is cost control. Natural minerals possess abundant chemical inertia and cost-efficiency, which is suitable for hybridizing with various effective photocatalysts. The use of natural minerals in photocatalytic systems can not only significantly decrease the pure photocatalyst dosage but can also produce a favorable synergistic effect between photocatalyst and mineral substrate. This review article discusses the current progress regarding the use of various mineral classes in photocatalytic applications. Owing to their unique structures, large surface area, and negatively charged surface, silicate minerals could enhance the adsorption capacity, reduce particle aggregation, and promote photogenerated electron-hole pair separation for hybrid photocatalysts. Moreover, controlling the morphology and structure properties of these materials could have a great influence on their light-harvesting ability and photocatalytic activity. Composed of silica and alumina or magnesia, some silicate minerals possess unique orderly organized porous or layered structures, which are proper templates to modify the photocatalyst framework. The non-silicate minerals (referred to carbonate and carbon-based minerals, sulfate, and sulfide minerals and other special minerals) can function not only as catalyst supports but also as photocatalysts after special modification due to their unique chemical formula and impurities. The dye-sensitized minerals, as another natural mineral application in photocatalysis, are proved to be superior photocatalysts for hydrogen evolution and wastewater treatment. This work aims to provide a complete research overview of the mineral-supported photocatalysts and summarizes the common synergistic effects between different mineral substrates and photocatalysts as well as to inspire more possibilities for natural mineral application in photocatalysis.

Mechanically stable structures with interconnected hierarchical porosity combine the benefits of both small and large pores, such as high surface area, pore volume, and good mass transport capabilities. Hence, lightweight micro-/meso-/macroporous monoliths are prepared from ordered mesoporous silica COK-12 by means of spark plasma sintering (SPS, S-sintering) and compared to conventionally (C-) sintered monoliths. A multi-scale model is developed to fit the small angle X-ray scattering data and obtain information on the hexagonal lattice parameters, pore sizes from the macro to the micro range, as well as the dimensions of the silica population. For both sintering techniques, the overall mesoporosity, hexagonal pore ordering, and amorphous character are preserved. The monoliths' porosity (77-49%), mesopore size (6.2-5.2 nm), pore volume (0.50-0.22 g cm-3), and specific surface area (451-180 m2 g-1) decrease with increasing processing temperature and pressure. While the difference in porosity is enhanced, the structural parameters between the C-and S-sintered monoliths are largely converging at 900 °C, except for the mesopore size and lattice parameter, whose dimensions are more extensively preserved in the S-sintered monoliths, however, coming along with larger deviations from the theoretical lattice. Their higher mechanical properties (biaxial strength up to 49 MPa, 724 MPa HV 9.807 N) at comparable porosities and ability to withstand ultrasonic treatment and dead-end filtration up to 7 bar allow S-sintered monoliths to reach a high permeance (2634 L m-2 h-1 bar-1), permeability (1.25 × 10-14 m2), and ability to reduce the chemical oxygen demand by 90% during filtration of a surfactant-stabilized oil in water emulsion, while indicating reasonable resistance towards fouling.

Particulate and gaseous air pollutants pose a threat to human health and contribute to climate change. By today, air filters, stationary and portable, are markedly improved and can often provide innocuous air pollution levels. After introducing the classification and standards on air filters, the influence of the processing route and its parameters on the resulting air filter properties and consequently its performance are discussed. Numerous tools are presented to adjust structural properties such as fiber or pore diameter, specific surface area, surface charge, hydrophilicity, or photocatalytic activity to achieve the desired performance in terms of high filtration efficiencies, sufficient mechanical stability, regeneration eligibility, antimicrobial and optical properties. In particular, inorganic and composite materials as well as nonfibrous structures are covered, which are currently holding an outsider position in an air filter community dominated by polymeric materials and fibrous structures.

Background Recent efforts in fungal biotechnology aim to develop new concepts and technologies that convert renewable plant biomass into innovative biomaterials. Hereby, plant substrates become metabolized by filamentous fungi to transform them into new fungal-based materials. Current research is thus focused on both understanding and optimizing the biology and genetics underlying filamentous fungal growth and on the development of new technologies to produce customized fungal-based materials. Results This manuscript reports the production of stable pastes, composed of Fomes fomentarius mycelium, alginate and water with 71 wt.% mycelium in the solid content, for additive manufacturing of fungal-based composite materials. After printing complex shapes, such as hollow stars with up to 39 mm in height, a combination of freeze-drying and calcium-crosslinking processes allowed the printed shapes to remain stable even in the presence of water. The printed objects show low bulk densities of 0.12 ± 0.01 g/cm 3 with interconnected macropores. Conclusions This work reports for the first time the application of mycelium obtained from the tinder fungus F. fomentarius for an extrusion-based additive manufacturing approach to fabricate customized light-weight 3D objects. The process holds great promise for developing light-weight, stable, and porous fungal-based materials that could replace expanded polystyrene produced from fossil resources.

Microporous organosilicas assembled from polysilsesquioxane (POSS) building blocks are promising materials that are yet to be explored in-depth. Here, we investigate the processing and molecular structure of bispropylurea bridged POSS (POSS-urea), synthesised through the acidic condensation of 1,3-bis(3-(triethoxysilyl)propyl)urea (BTPU). Experimentally, we show that POSS-urea has excellent functionality for molecular recognition toward acetonitrile with an adsorption level of 74 mmol/g, which compares favourably to MOFs and zeolites, with applications in volatile organic compounds (VOC). The acetonitrile adsorption capacity was 132-fold higher relative to adsorption capacity for toluene, which shows the pores are highly selective towards acetonitrile adsorption due to their size and arrangement. Theoretically, our tight-binding density functional and molecular dynamics calculations demonstrated that this BTPU based POSS is microporous with an irregular placement of the pores. Structural studies confirm maximal pore sizes of ∼1 nm, with POSS cages possessing an approximate edge length of ∼3.16 Å.

Large-pore ordered mesoporous silica (OMS) COK-12, analogous to the well-known SBA-15, but synthesized in a more environmentally friendly way and exhibiting a shorter plate-like structure, was grafted with different amounts of graphene oxide (GO) for the first time in an inexpensive and rapid process, that was successfully upscaled. Samples were examined with nitrogen sorption analysis, SAXS, Raman spectroscopy, XPS, and zeta potential analysis. Adsorption experiments with the cationic dye methylene blue (MB) were conducted on the grafted materials and on pure COK-12, taking into account the influence of initial dye concentration (30-600 mg L-1), adsorbent dosage (0.2-14 g L-1), contact time (0.3-300 min), solution pH (4-10), and influence of salts and temperature (0-1 M NaCl, 80 °C) to simulate industrial dye effluent. The adsorption process was found to be represented best by the Langmuir isotherm model, i.e., adsorption is a monolayer process. The calculated maximum adsorption capacities were found to be 20.2 and 197.5 mg g-1 at dosages of 5 and 0.5 g L-1 for pure COK-12 and COK-12 grafted with 50 wt% GO, respectively, at pH 5.65 and MB concentration of 100 mg L-1. Adsorption kinetics were found to follow the pseudo-second order model, i.e., chemisorption is the rate controlling step. The adsorption performances could be well preserved at simulated dye effluent. Desorption was found to be most effective with hydrochloric acid. The COK-12 grafted with GO presented in this work shows superior adsorption properties in comparison to other grafted OMS materials. In addition, grafting with GO remarkably improved the stability of COK-12 in aqueous solution.

The mechanism of multiwalled carbon nano-tube synthesis from methane chemical vapor deposition on a 5% Ni/MnO catalyst is studied at 873 and 1073 K by in situ transmission XRD using synchrotron radiation supported by Rietveld refinement and density functional theory calculations. Upon methane dissociative adsorption at the reaction temperature, the fcc nickel lattice initially expands above the temperature calibration experiment, as carbon dissolves interstitially and subsequently contracts upon graphite precipitation. At 1073 K, carbon dissolution in the fcc lattice of the MnO-supported nickel nanoparticles results in three cubic nickel carbides that occur prior to graphite precipitation. At the two reaction temperatures, the atomic concentration of dissolved carbon exceeds the limit of solubility in nickel films due to the nanoparticle effect. Nudged elastic band calculations display predominant surface diffusion and secondary subsurface bulk diffusion of carbon. Once catalysts are exposed to carbon dioxide, surface and subsurface carbon in nickel is easily oxidized by carbon dioxide and the nickel lattice returns to its original size. The mechanism described above explains the reaction pathway of the dry reforming of methane, confirming that the diffusing carbon species can act as reaction intermediates toward the generation of carbon monoxide, instead of deactivating the catalyst.

Dual-phase membranes for high-temperature carbon dioxide separation have emerged as promising technology to mitigate anthropogenic greenhouse gases emissions, especially as a pre- and post-combustion separation technique in coal burning power plants. To implement these membranes industrially, the carbon dioxide permeability must be improved. In this study, Ce0.8Sm0.2O2−δ (SDC) and Ce0.8Sm0.19Fe0.01O2−δ (FSDC) ceramic powders were used to form the skeleton in dual-phase membranes. The use of MgO as an environmentally friendly pore generator allows control over the membrane porosity and microstructure in order to compare the effect of the membrane’s ceramic phase. The ceramic powders and the resulting membranes were characterized using ICP-OES, HSM, gravimetric analysis, SEM/EDX, and XRD, and the carbon dioxide flux density was quantified using a high-temperature membrane permeation setup. The carbon dioxide permeability slightly increases with the addition of iron in the FSDC membranes compared to the SDC membranes mainly due to the reported scavenging effect of iron with the siliceous impurities, with an additional potential contribution of an increased crystallite size due to viscous flow sintering. The increased permeability of the FSDC system and the proper microstructure control by MgO can be further extended to optimize carbon dioxide permeability in this membrane system.

Ordered mesoporous silica materials such as COK-12, analogous to the well-known SBA-15, are characterized by high surface areas and unique features such as defined pore sizes in the meso-size range and high pore ordering. The aim of this work was to prove the washing step and choice of calcination and aging temperature during the COK-12 synthesis as effective tools in tailoring, markedly improving the specific surface area, pore size, and pore volume. By controlling the aging temperature, the pore size was linearly adjusted between 5.7 and 8.1 nm, while preserving the hexagonal ordering of the pores. The synthesized COK-12 powders possess pore volumes and specific surface areas up to 1.23 cm(3) g(-1) and 860 m(2) g(-1), respectively, which is markedly higher than what has previously been reported about COK-12. The presented results and the environmentally friendly character of the synthesis will make COK-12 more interesting for future adaption to the industrial processes, for example in catalysis, adsorption, or drug delivery.

COK-12 is an ordered mesoporous silica material (OMS) analogous to SBA-15, with hexagonally-packed cylindrical ordered pores of 5.5-6 nm in diameter. The synthesis of COK-12 takes place at room temperature under mild reaction conditions, and in comparison with the most widely known OMS materials syntheses, is more time efficient, inexpensive and environmentally friendly. This work encompasses investigations regarding the production of powder COK-12 in terms of upscaling of the synthesis in batch and continuous mode, as well as direct synthesis and upscaling of granular (monolithic) COK-12. Batch upscaling of the syntheses by a factor of 25 was carried out in a batch reactor at room temperature. In terms of upscaling in continuous mode, the installation and operation of a continuous powder COK-12 production unit was carried out and the influence of the flow rate of the feed streams on the properties of the material was studied. It was demonstrated that batch and continuous upscaling can be carried out, yielding up to 65 g or 330 g/run of powder COK-12, respectively. Upscaling of the direct synthesis of monolithic COK-12 granules was also carried out, yielding up to 60 g of material. (C) 2017 Elsevier Inc. All rights reserved.