Evaluation of the CH4/CO2 separation by adsorption on coconut shell activated carbon: Impact of the gas moisture on equilibrium selectivity and adsorption capacity.

Upgrading biogas to biomethane is of great interest to change the energy matrix by feeding the renewable fuel produced from biomass waste into natural gas grids or directly using it to replace fossil fuels. The study aimed to assess the adsorption equilibrium of CH4, CO2, and H2O on a coconut-shell activated carbon (CAC 8X30) to provide data for further studies on its efficiency in upgrading biogas by Pressure Swing Adsorption (PSA). The adsorbent was characterized, and equilibrium parameters were estimated from monocomponent CH4, CO2, and H2O equilibrium isotherms. Binary and ternary equilibrium isotherms were simulated, and the selectivity and adsorption capacity of the CAC 8X30 were calculated in dry and wet conditions and then compared with zeolite 13X as a reference material. Regarding characterization, Nitrogen and Hydrogen Physisorption results indicated that 94 % of the pore volume is concentrated in the region of micropores. The adsorption affinity with CAC 8X30 estimated from monocomponent isotherms was in the order KH20>KCO2>KCH4. IAST-Langmuir model simulations presented good agreement with experimental binary equilibrium data. Further simulations indicated equilibrium selectivity for CO2 over CH4 (e.g., 4.7 at 1 bar and 298 K for a mixture of CH4/CO2, 60/40 vol%), which increased in the presence of moisture, indicating its suitability for upgrading humid biogas. Simulations for zeolite 13X suggested that the material is unsuitable in the presence of water vapor but presents higher selectivity than the CAC 8X30 in dry conditions. Hence, the integration of both materials might be helpful for biogas upgrading.

Dielectric and Ultrasonic Properties of PDMS/TiO2 Nanocomposites.

This work presents the dielectric and ultrasonic properties of polydimethylsiloxane (PDMS) nanocomposites filled with titanium dioxide nanoparticles. The dielectric study was performed over a very broad range of frequencies (20 Hz-3 THz). The dielectric permittivity was almost frequency-independent in all the composites at room temperature over the whole range of measurement frequencies, and the dielectric losses were very low under these conditions (less than 2). The dielectric permittivity strongly increases with the nanoparticle concentration according to the Maxwell-Garnet model. Therefore, the investigated composites are suitable for various flexible electronic applications, particularly in the microwave and terahertz frequency ranges. Dielectric dispersion and increased attenuation of ultrasonic waves were observed at lower temperatures (below 280 K) due to the relaxation of polymer molecules at the PDMS/TiO2 interface and in the polymer matrix. The relaxation time followed the Vogel-Vulcher law, while the freezing temperature increased with the titanium dioxide concentration due to interactions between the polymer molecules and nanoparticles. The significant hysteresis in the ultrasonic properties indicated that titanium dioxide acts as a crystallization center. This is confirmed by the correlation between the hysteresis in the ultrasonic properties and the structure of the composites. The small difference in the activation energy values obtained from the ultrasonic and dielectric investigations is related to the fact that the dielectric dispersion is slightly broader than the Debye-type dielectric dispersion.

Non-reciprocal electromagnetic metasurface based on the nonlinearity of a liquid metamaterial.

In this Letter, we propose the design of a non-reciprocal electromagnetic metasurface, which uses a highly nonlinear liquid metamaterial as a source of non-reciprocity. We show that the proposed metasurface, whose thickness is comparable to the wavelength, can exhibit a difference between the transmission coefficients in the forward and backward directions of up to 0.95. Moreover, the particularly high nonlinearity of the liquid metamaterial enables the radiation power required to induce the nonlinear effects to be considerably reduced compared with natural materials. The feasibility of the proposed metasurface has been verified by numerical simulations.

Glyphosate uses, adverse effects and alternatives: focus on the current scenario in Brazil.

Brazil, a global frontrunner in pesticide consumption and sales, particularly glyphosate, appears to be at odds with other countries that increasingly ban these products in their territories. This study gathers the values of Acceptable Daily Intake and Maximum Residue Limits (MRL) in the European Union for dozens of substances and subsequently contrasts them with the corresponding benchmarks upheld in Brazil concerning its predominant crops. Furthermore, this study delves into the toxicity levels and the potential health ramifications of glyphosate on humans through the ingestion of food containing its residues. The findings from this research underscore a notable surge in glyphosate and pesticide sales and usage within Brazil over the past decade. In stark contrast to its European counterparts, Brazil not only sanctioned the sale and application of 474 new pesticides in 2019, but extended the authorization for glyphosate sales while downgrading its toxicity classification. Finally, this review not only uncovers disparities among research outcomes but also addresses the complexities of replacing glyphosate and introduces environmentally friendlier alternatives that have been subject to evaluation in the existing literature.

Piezoelectric Nanogenerators Based On BaTiO3/PDMS Composites for High-Frequency Applications.

A series of highly flexible and environmentally friendly composites based on polydimethylsiloxane (PDMS) filled with 200 nm size ferroelectric BaTiO3 (BTO) particles at different concentrations (from 7 to 23 vol %) have been fabricated by a simple dispersion method. The dielectric, piezoelectric, and ultrasonic properties have been studied. The ferroelectric state of BTO was confirmed by differential scanning calorimetry and ultrasonic spectroscopy. The addition of BTO into PDMS strongly affects the dielectric properties of the composites. At low temperatures close to 160 K, the PDMS matrix exhibits a dielectric anomaly related to a dynamic glass transition, which shifts to higher temperatures as the BTO content increases due to the strong interaction between polymer chains and nanoparticles. Ultrasonic measurements demonstrate the appearance of a piezoelectric voltage signal on a thin plate of the composite with the highest available filler concentration (23 vol %) under longitudinal stress applied by a 10 MHz ultrasonic wave. As a result, at room temperature, the detected signal is characterized by output voltage and specific stored energy values of 10 mV and 367.3 MeV/m2, respectively, followed by a further increase with cooling to 35 mV at 150 K. The proposed BTO/PDMS composite system is thus a potential candidate for nanogenerators, namely, a simple, flexible, and lead-free device converting high-frequency (10 MHz) mechanical vibrations into electrical voltage.

Towards a surface metric to measure the dustiness of nanomaterial powders.

The relevance of dustiness methods is increasingly recognized in the preliminary exposure evaluation of workers handling nanomaterials in powder form, and should also be transposed to the assessment of environmental risk in the future. The methods currently recommended in the European standards are mainly based on determining a mass-based dustiness index [mg kg-1], whereas surface area is regularly put forward as a more appropriate determinant to assess the pulmonary toxicity of nanoparticles. In this study, we describe an operational methodology leading us to propose a surface metric to determine the dustiness index [m2 kg-1] of nanoparticulate matter. To this end, we demonstrate the equivalence between the external specific surface area of a nanopowder and that of its aerosol with five nanomaterials produced and used on an industrial scale, and covering a range of external specific surface areas from 35 to 230 m2 g-1. Compared to the conventional mass-based dustiness index, the surface-based dustiness index (1) is more discriminating, covering an additional order of magnitude, and (2) has an impact on the powder ranking with potential consequences on the preventive measures to be implemented. Finally, our proposal has the potential to be included in future revisions of European standards for workplace exposure and dustiness measurement, provided that further experimental results on surface-based dustiness indices support these preliminary data.

Influence of Anatomy, Microstructure, and Composition of Natural Fibers on the Performance of Thermal Insulation Panels.

The growing interest in environmentally friendly materials is leading to a re-evaluation of natural fibers for industrial applications in order to meet sustainability and low-cost objectives, especially for thermal insulation of buildings. This paper deals with the chemical and physical characterization of fibers extracted from seagrass (Posidonia oceanica) and alfa grass (Stipa tenacissima) for a possible substitution of synthetic materials for thermal insulation. Hemp (Cannabis sativa), a fiber broadly used, was also studied for comparison. The parameters characterized include porosity, thermal degradation, elemental composition, skeletal and particle density of the fibers as well as investigation of the thermal conductivity of fiber-based panels. Several technologies were involved in investigating these parameters, including mercury intrusion, thermogravimetric analysis, fluorescence spectroscopy, and fluid pycnometry. The fibers showed a degradation temperature between 316 and 340 °C for Posidonia, between 292 and 326 °C for alfa, and between 300 and 336 °C for hemp fibers. A high porosity allied with a reduced pore size was revealed for Posidonia (77%, 0.54 µm) compared to hemp (75%, 0.61 µm) and alfa (57%, 2.1 µm) raw fibers, leading to lower thermal conductivity values for the nonwoven panels based on Posidonia (0.0356-0.0392 W/m.K) compared to alfa (0.0365-0.0397 W/m.K) and hemp (0.0387-0.0427 W/m.K). Bulk density, operating temperature, and humidity conditions have been shown to be determining factors for the thermal performance of the panels.

Electrical Resistivity and Microwave Properties of Carbon Fiber Felt Composites.

We present studies on the microwave properties, electrical resistivity, and low-frequency (10 Hz-20 kHz) noise characteristics in the temperature range of 78 K to 380 K of composite materials made from bisphenol A-based epoxy resin and carbon fiber felts. Two types of carbon fibers were used, derived from polyacrylonitrile or regenerated cellulose. We show that these structures are suitable for electromagnetic shielding applications, especially in the direction parallel to the carbon fibers. The low-frequency voltage fluctuations observed in these materials are of the 1/fα, and the noise intensity is proportional to the square of the voltage. The characteristics of the investigated materials show an instability in the temperature range from 307 K to 332 K. This effect is followed by an increase in resistivity and noise intensity, but it does not change the character of the noise, and this instability vanishes after a few repeated heating and cooling cycles.

A Review of Rigid Polymeric Cellular Foams and Their Greener Tannin-Based Alternatives.

This review focuses on the description of the main processes and materials used for the formulation of rigid polymer foams. Polyurethanes and their derivatives, as well as phenolic systems, are described, and their main components, foaming routes, end of life, and recycling are considered. Due to environmental concerns and the need to find bio-based alternatives for these products, special attention is given to a recent class of polymeric foams: tannin-based foams. In addition to their formulation and foaming procedures, their main structural, thermal, mechanical, and fire resistance properties are described in detail, with emphasis on their advanced applications and recycling routes. These systems have been shown to possess very interesting properties that allow them to be considered as potential substitutes for non-renewable rigid polymeric cellular foams.

Experimental Design Optimization of Acrylate-Tannin Photocurable Resins for 3D Printing of Bio-Based Porous Carbon Architectures.

In this work, porous carbons were prepared by 3D printing formulations based on acrylate-tannin resins. As the properties of these carbons are highly dependent on the composition of the precursor, it is essential to understand this effect to optimise them for a given application. Thus, experimental design was applied, for the first time, to carbon 3D printing. Using a rationalised number of experiments suggested by a Scheffé mixture design, the experimental responses (the carbon yield, compressive strength, and Young's modulus) were modelled and predicted as a function of the relative proportions of the three main resin ingredients (HDDA, PETA, and CN154CG). The results revealed that formulations containing a low proportion of HDDA and moderate amounts of PETA and CN154CG gave the best properties. Thereby, the optimised carbon structures had a compressive strength of over 5.2 MPa and a Young's modulus of about 215 MPa. The reliability of the model was successfully validated through optimisation tests, proving the value of experimental design in developing customisable tannin-based porous carbons manufactured by stereolithography.

Irreversible deformation of hyper-crosslinked polymers after hydrogen adsorption.

Hyper-crosslinked polymers (HCPs) have been produced by the Friedel-Crafts reaction using anthracene, benzene, carbazole or dibenzothiophene as precursors and dimethoxymethane as crosslinker, and the effect of graphene oxide (GO) addition has been studied. The resulting HCPs were highly microporous with BET areas (ABET) between 590 and 1120 m2g-1. The benzene-derived HCP (B1FeM2) and the corresponding composite with GO (B1FM2-GO) exhibited the highest ABET and were selected to study their hydrogen adsorption capacities in the pressure range of 0.1 - 14 MPa at 77 K. The maximum H2 excess uptake was 2.1 and 2.0 wt% for B1FeM2 and B1FeM2-GO, respectively, at 4 MPa and 77 K. The addition of GO reduced the specific surface area but increased the density of the resultant HCP-GO composites, which is beneficial for practical applications and proves that materials giving higher gravimetric storage capacities are not necessarily those that offer higher volumetric capacities. H2 adsorption-desorption cycles up to 14 MPa showed irreversible deformation of both HCP and HCP-GO materials, which calls into question their application for hydrogen adsorption at pressures above 4 MPa.

Comprehensive Analysis of Hierarchical Porous Carbons Using a Dual-Shape 2D-NLDFT Model with an Adjustable Slit-Cylinder Pore Shape Boundary.

A thorough characterization of the textural properties of hierarchical porous carbons (HPCs) is of utmost importance as it provides information that aids in the selection of a suitable material for a given application and in understanding the phenomena observed once the material becomes part of a system. Gas adsorption-desorption isotherms coupled with the application of density functional theory (DFT) models to these isotherms are common tools for the textural characterization of HPCs, for which pore shape is an essential factor for the determination of pore size distributions (PSDs). By analyzing the experimental adsorption data of a series of CO2-activated HPCs with a progressive development of porosity, it is shown that artifacts are found in the derived PSDs when a slit-cylinder pore shape boundary is fixed at 2 nm, which is the case for the original dual-shape nonlocal DFT (2D-NLDFT-HS) and hybrid quenched solid DFT (QSDFT) models. This study presents a new dual-shape 2D-NLDFT-HS (DS-HS) model that, combined with the 2D-NLDFT-HS model for CO2, provides the possibility of analyzing simultaneously N2 and CO2 adsorption-desorption isotherms and adjusting at the same time the limits for the assumed slit and cylindrical pore shapes. Using the DS-HS approach and adjusting the slit-cylinder boundary at 3 nm allowed eliminating PSDs artifacts. The interactive adjustment of the slit-cylindrical pore shape boundary of the DS-HS model represents a major advantage of this approach allowing for a comprehensive analysis of the adsorption data and a more accurate description of the textural properties of HPC materials.

Novel Porous Carbon Material for the Detection of Traces of Volatile Organic Compounds in Indoor Air.

A highly sensitive and selective silicon-based microanalytical prototype was used to identify a few ppb of volatile organic compounds (VOCs) in indoor air. Herein, a new nonactivated tannin-derived carbon synthesized by an environmentally friendly method, DM2C, a MIL-101(Cr) MOF, and a DaY zeolite were selected for the preconcentration of BTEX compounds (i.e., benzene, toluene, ethylbenzene, and xylenes). Integrating a small amount of these nanoporous solids inside a miniaturized preconcentration unit led to excellent preconcentration performance. By taking advantage of the high adsorption-desorption capacities of the DM2C adsorbent, concentrations as low as 23.5, 30.8, 16.7, 25, and 28.8 ppb of benzene, toluene, ethylbenzene, ortho- and para-xylene, respectively, were detected in a short analysis time (∼10 min) even in the presence of 60% relative humidity at 25 °C. The DM2C showed excellent stability over a period of 4 months and more than 500 tests, as well as repeatability, which makes it a very reliable adsorbent for the detection of trace VOCs in indoor air under realistic conditions in the presence of humidity.

A critical review on surface modifications mitigating dairy fouling.

Thermal treatments performed in food processing industries generate fouling. This fouling deposit impairs heat transfer mechanism by creating a thermal resistance, thus leading to regular shutdown of the processes. Therefore, periodic and harsh cleaning-in-place (CIP) procedures are implemented. This CIP involves the use of chemicals and high amounts of water, thus increasing environmental burden. It has been estimated that 80% of production costs are owed to dairy fouling deposit. Since the 1970s, different types of surface modifications have been performed either to prevent fouling deposition (anti-fouling) or to facilitate removal (fouling-release). This review points out the impacts of surface modification on type A dairy fouling and on cleaning behaviors under batch and continuous flow conditions. Both types of anti-fouling and fouling-release coatings are reported as well as the different techniques used to modify stainless steel surface. Finally, methods for testing and characterising the effectiveness of coatings in mitigating dairy fouling are discussed.

Upgrading of pine tannin biochars as electrochemical capacitor electrodes.

Biochar derived from the pyrolysis of pine tannin is a green and available by-product of oil manufacturing that presents interesting features after having been activated by KOH at 650 °C. Different weight ratios of KOH to biochar were used and the resulting activated carbons (ACs) presented highly developed specific surface areas of up to 2190 m2 g-1, well-connected porosity and high oxygen content, leading to enhanced electrochemical performance when used as electrochemical capacitor electrodes in a 1 M H2SO4 aqueous electrolyte. Galvanostatic charge/discharge experiments evidenced that the best material achieved a maximum electrode capacitance of up to 232 F g-1 (at 0.5 A g-1) with a capacitance retention of 70% at 10 A g-1 using commercial mass loadings (i.e., approx. 10 mg cm-2). In addition, long cycling stability with a residual capacitance of 92 to 94% after 10,000 cycles at 5 A g-1 was achieved. These results prove that ACs derived from pine tannin biochars have great potential for their commercial use as electrochemical energy storage devices.

An Evaluation of the Impact of the Amount of Potassium Hydroxide on the Porous Structure Development of Activated Carbons.

This paper presents the results of an evaluation of the impact of the amount of potassium hydroxide on the obtained porous structure of the activated carbons derived from the shells of pistachios, hazelnuts, and pecans by carbonization and subsequent chemical activation with potassium hydroxide by different adsorption methods: Brunauer-Emmett-Teller, Dubinin-Raduskevich, the new numerical clustering-based adsorption analysis, Quenched Solid Density Functional Theory, and 2D-Non-linear Density Functional Theory for Heterogeneous Surfaces, applied to nitrogen adsorption isotherms at -196 °C. Based on the conducted research, a significant potential for the production of activated carbons from waste materials, such as nut shells, has been demonstrated. All the activated carbons obtained in the present study at the activator/char mass ratio R = 4 exhibited the most developed porous structure, and thus very good adsorption properties. However, activated carbons obtained from pecan shells deserve special attention, as they were characterized by the most homogeneous surface among all the samples analyzed, i.e., by a very desirable feature in most adsorption processes. The paper demonstrates the necessity of using different methods to analyze the porous structure of activated carbons in order to obtain a complete picture of the studied texture. This is because only a full spectrum of information allows for correctly selecting the appropriate technology and conditions for the production of activated carbons dedicated to specific industrial applications. As shown in this work, relying only on the simplest methods of adsorption isotherm analysis can lead to erroneous conclusions due to lack of complete information on the analyzed porous structure. This work thus also explains how and why the usual characterizations of the porous structure of activated carbons derived from lignocellulosic biomass should not be taken at face value. On the contrary, it is advisable to cross reference several models to get a precise idea of the adsorbent properties of these materials, and therefore to propose the most suitable production technology, as well as the conditions of the preparation process.

Mechanical and Thermal Behavior of Fibrous Carbon Materials.

The ability of various commercial fibrous carbon materials to withstand stress and conduct heat has been evaluated through experimental and analytical studies. The combined effects of different micro/macro-structural characteristics were discussed and compared. Large differences in mechanical behavior were observed between the different groups or subgroups of fibrous materials, due to the different types of fibers and the mechanical and/or chemical bonds between them. The application of the Mooney-Rivlin model made it possible to determine the elastic modulus of soft felts, with a few exceptions, which were studied in-depth. The possible use of two different mechanical test methods allowed a comparison of the results in terms of elastic modulus obtained under different deformation regimes. The effective thermal conductivity of the same fibrous materials was also studied and found to be much lower than that of a single carbon fiber due to the high porosity, and varied with the bulk density and the fiber organization involving more or less thermal contact resistances. The thermal conductivity of most materials is highly anisotropic, with higher values in the direction of preferential fiber orientation. Finally, the combination of compression and transient thermal conductivity measurement techniques allowed the heat conduction properties of the commercial fibrous carbons to be investigated experimentally when compressed. It was observed that thermal conductivity is strongly affected under compression, especially perpendicular to the main fiber orientation.

Noise and Electrical Characteristics of Composites Filled with Onion-like Carbon Nanoparticles.

Polymer matrix composites filled with carbon nanoparticles are promising materials for many applications, but their properties strongly depend on the particle features, concentration and distribution within the matrix. Here we present a study of the electrical resistivity and the low-frequency voltage fluctuation of composites based on epoxy resin filled with onion-like carbon (OLC) of different sizes (40-250 nm) above the percolation threshold, which should clarify the electrical transport characteristics in these materials. Electrical measurements were performed in the temperature range of 78 to 380 K, and voltage noise analysis was carried out from 10 Hz to 20 kHz. At low temperatures (below 250 K), thermally activated tunneling, variable-range hopping and generation-recombination of charge carriers take place. Above 250 K, the rapid expansion of the matrix with the temperature increases the resistivity, but above ~330 K, the conductivity of the matrix becomes significant. Quasi one-dimensional electrical transport is observed in composites with the smallest particles (40 nm), while in composites with the largest particles (220-250 nm), the dimensionality of the electrical transport is higher. The temperature dependence of the electrical conductivity of composites with smaller particles is more sensitive to matrix expansion.

A Step Forward in Understanding the Hydrogen Adsorption and Compression on Activated Carbons.

Hydrogen adsorption on activated carbons (ACs) is a promising alternative to compression and liquefaction for storing hydrogen. Herein, we have studied hydrogen adsorption on six commercial ACs (CACs) with surface areas ranging from 996 to 2216 m2 g-1 in a temperature range of 77 to 273 K and pressures up to 15 MPa. Excess hydrogen adsorption capacities of 2.3 to 5.8 wt % were obtained at 77 K and 4 MPa. We demonstrated that, contrary to what is normally done, hydrogen capacity is more accurately predicted by the surface area determined by the nonlocal density functional theory method applied to N2 and CO2 adsorption data than by the Brunauer-Emmett-Teller (BET) area. The modified Dubinin-Astakhov (MDA) equation was used to fit the experimental adsorption data, and the relationship between the MDA parameters (nmax, Va, α, and ß) and the textural properties of the CACs was determined for the first time. We concluded that the nmax and Va parameters are related to the BET area, while the α and ß parameters are related to the average micropore size and total pore volume, respectively. α and ß were used to evaluate the enthalpy and entropy of adsorption and we show that these parameters can be used to assess the best carbon for hydrogen storage or compression.

Boron Nitride Nanotube as an Antimicrobial Peptide Carrier: A Theoretical Insight.

INTRODUCTION: Nanotube-based drug delivery systems have received considerable attention because of their large internal volume to encapsulate the drug and the ability to penetrate tissues, cells, and bacteria. In this regard, understanding the interaction between the drug and the nanotube to evaluate the encapsulation behavior of the drug in the nanotube is of crucial importance. METHODS: In this work, the encapsulation process of the cationic antimicrobial peptide named cRW3 in the biocompatible boron nitride nanotube (BNNT) was investigated under the Canonical ensemble (NVT) by molecular dynamics (MD) simulation. RESULTS: The peptide was absorbed into the BNNT by van der Waals (vdW) interaction between cRW3 and the BNNT, in which the vdW interaction decreased during the simulation process and reached the value of -142.7 kcal·mol-1 at 4 ns. DISCUSSION: The increase in the potential mean force profile of the encapsulated peptide during the pulling process of cRW3 out of the nanotube showed that its insertion into the BNNT occurred spontaneously and that the inserted peptide had the desired stability. The energy barrier at the entrance of the BNNT caused a pause of 0.45 ns when half of the peptide was inside the BNNT during the encapsulation process. Therefore, during this period, the peptide experienced the weakest movement and the smallest conformational changes.