Impact of Compression on the Textural and Structural Properties of CPO-27(Ni).

The employment of metal-organic frameworks in powder form is undesirable from an industrial perspective due to process and safety issues. This work is devoted to evaluating the impact of compression on the textural and structural properties of CPO-27(Ni). For this purpose, CPO-27(Ni) was synthesized under hydrosolvothermal conditions and characterized. Then, the resulting powder was compressed into binderless pellets using variable compression forces ranging from 5-90 kN (37-678 MPa) and characterized by means of nitrogen adsorption/desorption, thermogravimetric analysis and powder X-ray diffraction to evaluate textural, thermal and structural changes. Both textural and structural properties decreased with increasing compression force. Thermal stability was impacted in pellets compressed at forces over 70 kN. CPO-27(Ni) pelletized at 5, 8 and 10 kN, and retained more than 94% of its initial textural properties, while a loss of about one-third of the textural property was observed for the two most compressed samples (70 and 90 kN) compared to the starting powder.

Self-Assembly of Soot Nanoparticles on the Surface of Resistively Heated Carbon Microtubes in Near-Hexagonal Arrays of Micropyramids.

Almost regular hexagonal arrays of microscopic pyramids consisting of soot nanoparticles are formed on the surface of graphitized hollow filaments, which are resistively heated to ∼1800-2400 °C under an Ar atmosphere containing trace amounts of oxygen (∼300 ppm). At higher temperatures (T > 2300 °C, approximately) the soot particles are represented mainly by multishell carbon nano-onions. The height and width of the pyramids are strongly dependent on the temperature of the resistive heating, diminishing from 5 to 10 µm at T ≈ 1800 °C to ∼1 µm at 2300-2400 °C. Quasi-hexagonal arrays of the micropyramids are organized in the convex "craters" on the surface of the microtubes, which grow with the time of the thermal treatment. The pyramids always point normally to the surface of the craters, except at the boundaries between the craters, where the normal direction is not well-defined. The pyramids are soft and can be easily destroyed by touching them but can be hardened by heating them under an oxygen-free atmosphere. The pyramids are observed only on the exterior surface of the microtubes, not on their inner surface. This suggests that the thermophoretic force generated by a strong temperature gradient near the external surface of the tubes may be the cause of the micropyramid formation. Electrostatic charging of the soot nanoparticles due to thermionic emission may also be relevant to this phenomenon. The micropyramids can function as field emission point sources, as demonstrated with the use of a micronanoprobing station, mounted in a scanning electron microscope.

Unveiling the Potential of Corn Cob Biochar: Analysis of Microstructure and Composition with Emphasis on Interaction with NO2.

In the context of sustainable solutions, this study examines the pyrolysis process applied to corn cobs, with the aim of producing biochar and assessing its effectiveness in combating air pollution. In particular, it examines the influence of different pyrolysis temperatures on biochar properties. The results reveal a temperature-dependent trend in biochar yield, which peaks at 400 °C, accompanied by changes in elemental composition indicating increased stability and extended shelf life. In addition, high pyrolysis temperatures, above 400 °C, produce biochars with enlarged surfaces and improved pore structures. Notably, the highest pyrolysis temperature explored in this study is 600 °C, which significantly influences the observed properties of biochars. This study also explores the potential of biochar as an NO2 adsorbent, as identified by chemical interactions revealed by X-ray photoelectron spectroscopy (XPS) analysis. This research presents a promising and sustainable approach to tackling air pollution using corn cob biochar, providing insight into optimized production methods and its potential application as an effective NO2 adsorbent to improve air quality.

Rational Design and Characterisation of Novel Mono- and Bimetallic Antibacterial Linde Type A Zeolite Materials.

The development of antimicrobial devices and surfaces requires the setup of suitable materials, able to store and release active principles. In this context, zeolites, which are microporous aluminosilicate minerals, hold great promise, since they are able to serve as a reservoir for metal-ions with antimicrobial properties. Here, we report on the preparation of Linde Type A zeolites, partially exchanged with combinations of metal-ions (Ag+, Cu2+, Zn2+) at different loadings (0.1-11.9 wt.%). We combine X-ray fluorescence, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction to monitor the metal-ion contents, distribution, and conservation of the zeolite structure after exchange. Then, we evaluate their antimicrobial activity, using agar dilution and optical-density monitoring of Escherichia coli cultures. The results indicate that silver-loaded materials are at least 70-fold more active than the copper-, zinc-, and non-exchanged ones. Moreover, zeolites loaded with lower Ag+ concentrations remain active down to 0.1 wt.%, and their activities are directly proportional to the total Ag content. Sequential exchanges with two metal ions (Ag+ and either Cu2+, Zn2+) display synergetic or antagonist effects, depending on the quantity of the second metal. Altogether, this work shows that, by combining analytical and quantitative methods, it is possible to fine-tune the composition of bi-metal-exchanged zeolites, in order to maximise their antimicrobial potential, opening new ways for the development of next-generation composite zeolite-containing antimicrobial materials, with potential applications for the design of dental or bone implants, as well as biomedical devices and pharmaceutical products.

Size-Dependent Internalization Efficiency of Macrophages from Adsorbed Nanoparticle-Based Monolayers.

Functional coatings based on the assembly of submicrometric or nanoparticles are found in many applications in the biomedical field. However, these nanoparticle-based coatings are particularly fragile since they could be exposed to cells that are able to internalize nanoparticles. Here, we studied the efficiency of RAW 264.7 murine macrophages to internalize physisorbed silica nanoparticles as a function of time and particle size. This cell internalization efficiency was evaluated from the damages induced by the cells in the nanoparticle-based monolayer on the basis of scanning electron microscopy and confocal laser scanning microscopy observations. The internalization efficiency in terms of the percentage of nanoparticles cleared from the substrate is characterized by two size-dependent regimes. Additionally, we highlighted that a delay before internalization occurs, which increases with decreasing adsorbed nanoparticle size. This internalization is characterized by a minimal threshold that corresponds to 35 nm nanoparticles that are not internalized during the 12-h incubation considered in this work.

Does the photocatalytic activity of nanoparticles protect the marine mussel Mytilus galloprovincialis from polycyclic aromatic hydrocarbon toxicity?

In the present study, five NPs (containing ZnO, Au-ZnO, Cu-ZnO, TiO2, and Au-TiO2) were characterized using dynamic light scattering and transmission electron microscopy, in order to observe their behavior under environmental change. The applicability of NPs for degradation of three polycyclic aromatic hydrocarbons (PAHs), including benzo(a)pyrene, fluoranthene, and benzanthracene, using UV irradiation showed the high photocatalytic efficiency of doped NPs for the removal of the study pollutants. To predict the environmental impact and interaction between NPs and PAHs on marine organisms, Mytilus galloprovincialis mussels were exposed to concentrations of each chemical (50 and 100 µg/L) for 14 days. The mussel's response was determined using the oxidative stress biomarker approach. Measured biomarkers in the mussel's digestive gland showed possible oxidative mechanisms in a concentration-dependent manner occurring after exposure to PAHs and NPs separately. Overall, this finding provides an interesting combination to remove PAHs in water, and the incorporation of chemical element into the crystallographic structure of NPs and the combination of two different NPs to form a binary hybrid NPs are promising materials.

Development of novel and ecological keratin/cellulose-based composites for absorption of oils and organic solvents.

Keratin/cellulose cryogels were successfully fabricated using chicken feathers (CF) and cardboard (C) from environmental waste for the first time, to be exploited in oil/solvent absorption. The keratin/cellulose-based composites were obtained by combining the dissolution of CF and C waste in 1-butyl-3-methylimidazolium chloride (Bmim-Cl+) ionic liquid green solvent via regeneration, simply by the freeze-drying method. The characterization analysis of the synthesized keratin/cellulose-based composites was performed using Fourier transform infrared spectrometry, X-ray diffractometry, scanning electron microscopy, and thermogravimetry. The as-prepared cryogel can absorb various oils and organic solvents. Moreover, its sorption capacity can reach up to 6.9-17.7 times the weight of the initial cryogel. This kind of CF/C cryogel revealed good and fast absorption efficiency. It could also be reused by simple absorption/distillation and absorption/desorption methods. Through the kinetic analysis, it was found that the pseudo-second-order model was more appropriate for the keratin/cellulose cryogel oil absorption process. Besides, owing to its low cost, good absorption capacity, and excellent reusability, this cryogel has potential for spill cleanup of oils and organic solvents.

Synthesis of FAU-Type Zeolite Membranes with Antimicrobial Activity.

In this study, a layer of a pure and dense phase of FAU-type zeolite was synthesized directly on the surface of α-Al2O3 plane macroporous support. Before hydrothermal synthesis, a step of cleaning of the support by an anionic detergent was performed, a roughness surface is created, allowing the anchoring of the zeolite nuclei and then their growth, favoring in this sense the formation of a homogeneous zeolite layer. The obtained membranes were fully characterized using X-ray diffraction analysis (XRD), nitrogen sorption, scanning electron microscopy (SEM), and mercury porosimetry. After 24 h of thermal treatment at 75 °C, a homogeneous zeolite layer composed of bipyramidal crystals of FAU-type zeolite is obtained with a thickness of about 2.5 µm. No obvious defects or cracks can be observed. It was found that the increase in heating temperature could lead to the appearance of an impurity phase, GIS-type zeolite. Then the ideal zeolite membrane was exchanged with Ag+ or Zn2+ cations to studies their antimicrobial properties. Zeolites membranes exchanged with Ag+ showed an agar-diffusive bactericidal activity against gram negative Escherichia coli (E. coli) bacteria. Zn2+ exchanged zeolite membrane presented a bacteriostatic activity that is less diffusive in agar. As expected, non-exchanged zeolite membrane (in its Na+ form) have no effect on bacterial activity. This process is particularly interesting for the synthesis of a good quality FAU-type zeolite membranes with antimicrobial properties.

Characterizing the Core-Shell Architecture of Block Copolymer Nanoparticles with Electron Microscopy: A Multi-Technique Approach.

Electron microscopy has proved to be a major tool to study the structure of self-assembled amphiphilic block copolymer particles. These specimens, like supramolecular biological structures, are problematic for electron microscopy because of their poor capacity to scatter electrons and their susceptibility to radiation damage and dehydration. Sub-50 nm core-shell spherical particles made up of poly(hydroxyethyl acrylate)-b-poly(styrene) are prepared via polymerization-induced self-assembly (PISA). For their morphological characterization, we discuss the advantages, limitations, and artefacts of TEM with or without staining, cryo-TEM, and SEM. A number of technical points are addressed such as precisely shaping of particle boundaries, resolving the particle shell, differentiating particle core and shell, and the effect of sample drying and staining. TEM without staining and cryo-TEM largely evaluate the core diameter. Negative staining TEM is more efficient than positive staining TEM to preserve native structure and to visualize the entire particle volume. However, no technique allows for a satisfactory imaging of both core and shell regions. The presence of long protruding chains is manifested by patched structure in cryo-TEM and a significant edge effect in SEM. This manuscript provides a basis for polymer chemists to develop their own specimen preparations and to tackle the interpretation of challenging systems.

Synthesis of Hierarchical Zeolites with Morphology Control: Plain and Hollow Spherical Beads of Silicalite-1 Nanosheets.

Binderless pure silica zeolites (zeosils) spheres and hollow spheres with a diameter of 20 µm composed of silicalite-1 nanosheets particles were prepared by pseudomorphic transformation of spherical silica beads using different temperatures (110, 130, and 150 °C) and treatment times (1-5 days) in order to adapt the local dissolution rate of silica to the crystallization rate of silicalite-1 nanosheets allowing to preserve the initial morphology of the silica beads. Fully crystalline beads of 20 µm were obtained at 110 °C for 5 days, whereas hollow spheres similar in size were synthesized at higher temperatures. The crystallization process seems to begin at the outer surface of the amorphous silica beads and spreads with the time in the interior of the beads leading to a dissolution of the inner amorphous part of the beads to create zeosil hollow spheres for the highest treatment temperatures (130 and 150 °C). The dissolution rate of the inner amorphous part of the beads increases by increasing the hydrothermal treatment temperature from 130 to 150 °C. The silicalite-1 beads synthesized at 110 °C for 5 days showed to be promising for rapid molecular decontamination by adsorbing n-hexane in larger amount than the silicalite-1 conventional big crystals in powder forms.

Free-standing cellulose film containing manganese dioxide nanoparticles and its use in discoloration of indigo carmine dye.

In this study, we report the production of a free-standing film of non-modified cellulose impregnated with 12 wt.% of MnO2 nanoparticles with less than 100 nm in size. The method here described can be applied to the immobilization of different types of nanoparticles. The film was prepared by dissolving microcrystalline cellulose in an ionic liquid followed by its regeneration by adding water to the former solution. Then, the wet film was impregnated with the nanoparticles by dipping it in a MnO2 dispersion. Electron microscopy images revealed manganese dioxide nanoparticles distributed not only at the film surface but also in its interior. The cellulose film impregnated with MnO2 nanoparticles was capable of efficiently discolouring an Indigo Carmine dye solution in 25 min upon ambient light. The film was easily removed from the dye solution and repeatedly reused for at least 10 times without losing its discolouring efficiency.

Diblock Copolymer Core-Shell Nanoparticles as Template for Mesoporous Carbons: Independent Tuning of Pore Size and Pore Wall Thickness.

Latex templating using core-shell particles represents a unique opportunity to design mesoporous carbons with a high level of control on textural properties. This new class of organic colloid templates is synthesized by polymerization-induced self-assembly (PISA) in which a solvophilic poly(hydroxyethyl acrylate) (PHEA) homopolymer is chain extended with a solvophobic polystyrene (PS) via a photomediated reversible-addition-fragmentation-transfer (RAFT) polymerization. The resultant PHEA-b-PS diblock copolymer nanoparticles exhibit a PS core stabilized by a PHEA shell, with two blocks characterized by a low molecular weight dispersity (1.1-1.3) and an adjustable degree of polymerization (DP). The core-shell structured nanoparticles are used as soft template for the formation of mesostructured carbons from phloroglucinol and glyoxylic acid in methanol solution. A micro- and mesostructured cellular foam is obtained having uniform, interconnected, and narrowly distributed mesopores ranging between 15 and 30 nm in diameter, a specific surface area up to 719 m2 g-1, and a total pore volume of (0.4-1.3) cm3 g-1. The mesopore size can be controlled by adjusting the diameter of the PS core (16-29 nm), while the wall thickness can be tailored independently by varying the size of the solvated PHEA shell (5-25 nm). An increase of PHEA block's DP from 25 to 85 gradually extends the stabilizing shell dimension, thus increasing the wall thickness up to 10 nm, and causing the shift from interconnected to isolated mesopores. By comparison, much thinner walls (2-3 nm) are obtained with conventional latex templates such as polystyrene nanoparticles or colloidal silica. Decreasing PHEA DP to 17 induces the formation of copolymer vesicles that can be used as template to create mesoporous carbons with nonspherical mesopores.

Binary Oxides Prepared by Microwave-Assisted Solution Combustion: Synthesis, Characterization and Catalytic Activity.

Three different alumina-based Ni, Cu, Co oxide catalysts with metal loading of 10 wt %, and labeled 10Ni⁻Al, 10Co⁻Al and 10Cu⁻Al, were prepared by microwave-assisted solution combustion. Their morphological, structural and surface properties were deeply investigated by complementary physico-chemical techniques. Finally, the three materials were tested in CO oxidation used as test reaction for comparing their catalytic performance. The 10Cu⁻Al catalyst was constituted of copper oxide phase, while the 10Ni⁻Al and 10Co⁻Al catalysts showed the presence of "spinels" phases on the surface. The well-crystallized copper oxide phase in the 10Cu⁻Al catalyst, obtained by microwave synthesis, allowed for obtaining very high catalytic activity. With a CO conversion of 100% at 225 °C, the copper containing catalyst showed a much higher activity than that usually measured for catalytic materials of similar composition, thus representing a promising alternative for oxidation processes.

The relationship between mineral contents, particle matter and bottom ash distribution during pellet combustion: molar balance and chemometric analysis.

This paper aims to identify the correlation between the mineral contents in agropellets and particle matter and bottom ash characteristics during combustion in domestic boilers. Four agrifood residues with higher mineral contents, namely grape marc (GM), tomato waste (TW), exhausted olive mill solid waste (EOMSW) and olive mill wastewater (OMWW), were selected. Then, seven different pellets were produced from pure residues or their mixture and blending with sawdust. The physico-chemical properties of the produced pellets were analysed using different analytical techniques, and a particular attention was paid to their mineral contents. Combustion tests were performed in 12-kW domestic boiler. The particle matter (PM) emission was characterised through the particle number and mass quantification for different particle size. The bottom ash composition and size distribution were also characterised. Molar balance and chemometric analyses were performed to identify the correlation between the mineral contents and PM and bottom ash characteristics. The performed analyses indicate that K, Na, S and Cl are released partially or completely during combustion tests. In contrast, Ca, Mg, Si, P, Al, Fe and Mn are retained in the bottom ash. The chemometric analyses indicate that, in addition to the operating conditions and the pellet ash contents, K and Si concentrations have a significant effect on the PM emissions as well as on the agglomeration of bottom ash.

Synthesis and crystal structure of IM-6, a new open framework cobalt-gallium phosphate with ten- and twelve-membered pore openings.

A new three-dimensional microporous cobalt-gallium phosphate, named IM-6, has been synthesized under solvothermal conditions with an N-substituted piperazine as organic template. The structure was solved by single-crystal X-ray diffraction (triclinic, P(-)1, a=9.848(20), b=12.470(32), c=12.603(28)A, alpha=63.47(16) degrees, beta=74.56(16) degrees, gamma=76.03(17) degrees). IM-6 exhibits a new framework topology. The inorganic framework is built up of MO(4) (M=Co, Ga) and PO(4) tetrahedra. It displays a two-dimensional interconnected channel system running along the [0(-)11] and [100] directions and delimited by ten- and twelve-membered ring openings, respectively.

Easy access to phosphonothioates.

A new and particularly mild method for the formation of phosphorus-sulfur bonds has been achieved through base-catalyzed addition of thiocyanate to the corresponding H-phosphine oxide, phosphinate, or phosphonate. This reaction procedure offers many advantages: the use as starting material of a stable and not oxygen-sensitive phosphorus(v) species, particularly mild and nonaqueous reaction conditions and workup (a pivotal point for these sensitive phosphonothioates), and, through optimized access to thiocyanates, a wider scope of substrates. This method has been applied to achieve the synthesis of substrate analogues for the study of antibody-catalyzed hydrolysis of acetylcholinesterase inhibitor PhX (11).

Hydrothermal synthesis and characterization of the new layered fluorogallophosphate mu-23.

Mu-23, [(C(6)H(15)N(2))(C(6)H(16)N(2))Ga(5)F(6)(H(2)O)(2)(PO(4))(4)] x 4 H(2)O, the first layered fluorinated gallophosphate with a Ga/P molar ratio of 5:4, was obtained in the presence of fluoride ions with 1,4-dimethylpiperazine as an organic template. It crystallizes in the triclinic space group P1 (no. 2) with unit cell parameters a=8.735(11), b=8.864(5), c=12.636(10) A, alpha=98.36(5), beta=100.18(8), gamma=115.84(7) degrees. The layers consist of GaO(2)F(3)(H(2)O), GaO(4)F(2) octahedra, and GaO(4) and PO(4) tetrahedra; these moieties share their oxygen and some of their fluorine atoms. The connectivity scheme of these different polyhedra leads to the formation of eight-membered rings.