Understanding how water interacts with nanopores of carbonaceous electrodes is crucial for energy storage and conversion applications. A high surface area of carbonaceous materials does not necessarily need to translate to a high electrolyte-solid interface area. Herein, we study the interaction of water with nanoporous CN materials to explain their very low specific capacitance in aqueous electrolytes despite their high surface area.
View Article and Find Full Text PDFLiquid porosimetry experiments reveal a peculiar trend of the intrusion pressure of water in hydrophobic Cu(3,3',5,5'-tetraethyl-4,4'-bipyrazolate) MOF. At lower temperature (T) range, the intrusion pressure (P) increases with T. For higher T values, P first reaches a maximum and then decreases.
View Article and Find Full Text PDFFluids under extreme confinement show characteristics significantly different from those of their bulk counterpart. This work focuses on water confined within the complex cavities of highly hydrophobic metal-organic frameworks (MOFs) at high pressures. A combination of high-pressure intrusion-extrusion experiments with molecular dynamic simulations and synchrotron data reveals that supercritical transition for MOF-confined water takes place at a much lower temperature than in bulk water, ∼250 K below the reference values.
View Article and Find Full Text PDFACS Appl Mater Interfaces
February 2024
ACS Appl Mater Interfaces
January 2024
Wetting of a solid by a liquid is relevant for a broad range of natural and technological processes. This process is complex and involves the generation of heat, which is still poorly understood especially in nanoconfined systems. In this article, scanning transitiometry was used to measure and evaluate the pressure-driven heat of intrusion of water into solid ZIF-8 powder within the temperature range of 278.
View Article and Find Full Text PDFThis study explores task-specific ionic liquids (TSILs) in smart floor systems, highlighting their strong electrical rectification abilities and previously established wood preservative properties. Two types of TSILs, featuring a "sweet" anion and a terpene-based cation, were used to treat selected wood samples, allowing for a comparison of their physical and electrical performance with untreated and commercially treated counterparts. Drop shape analysis and scanning electron microscopy were employed to evaluate the surface treatment before and after coating.
View Article and Find Full Text PDFMolecular engineering is a unique methodology to take advantage of the electrochemical characteristics of materials that are used in energy-harvesting devices. Particularly in triboelectric nanogenerator (TENG) studies, molecular grafting on dielectric metal oxide surfaces can be regarded as a feasible way to alter the surface charge density that directly affects the charge potential of triboelectric layers. Herein, we develop a feasible methodology to synthesize organic-inorganic hybrid structures with tunable triboelectric features.
View Article and Find Full Text PDFZeolitic Imidazolate Frameworks (ZIF) find application in storage and dissipation of mechanical energy. Their distinctive properties linked to their (sub)nanometer size and hydrophobicity allow for water intrusion only under high hydrostatic pressure. Here we focus on the popular ZIF-8 material investigating the intrusion mechanism in its nanoscale cages, which is the key to its rational exploitation in target applications.
View Article and Find Full Text PDFRecent interest in the antioxidant capacity of foods and beverages is based on the established medical knowledge that antioxidants play an essential role in counteracting the damaging effects of free radicals, preventing human neurodegenerative diseases, cardiovascular disorders, and even cancer. At the same time, there is no "the method" that uniquely defines the antioxidant capacity of substances; moreover, the question of interrelation between results obtained by different experimental techniques is still open. In this work, we consider the trolox equivalent antioxidant capacity (TEAC) values obtained by electron paramagnetic resonance (EPR) spectroscopy and ultraviolet-visible (UV-vis) spectroscopy using the classic objects for such studies as an example: red, rosé, and white wine samples.
View Article and Find Full Text PDFACS Appl Mater Interfaces
July 2022
Controlling the pressure at which liquids intrude (wet) and extrude (dry) a nanopore is of paramount importance for a broad range of applications, such as energy conversion, catalysis, chromatography, separation, ionic channels, and many more. To tune these characteristics, one typically acts on the chemical nature of the system or pore size. In this work, we propose an alternative route for controlling both intrusion and extrusion pressures proper arrangement of the grains of the nanoporous material.
View Article and Find Full Text PDFNegative compressibility (NC) is a phenomenon when an object expands/shrinks in at least one of its dimensions upon compression/decompression. NC is very rare and is of great interest for a number of applications. In this work a gigantic (more than one order of magnitude higher compared to the reported values) NC effect was recorded during intrusion-extrusion of a non-wetting liquid into a flexible porous structure.
View Article and Find Full Text PDFEfficient and compact energy conversion is at the heart of the sustainable development of humanity. In this work it is demonstrated that hydrophobic flexible nanoporous materials can be used for thermal-to-mechanical energy conversion when coupled with water. In particular, a reversible nonhysteretic wetting-drying (contraction-expansion) cycle provoked by periodic temperature fluctuations was realized for water and a superhydrophobic nanoporous Cu(tebpz) MOF (tebpz = 3,3',5,5'-tetraethyl-4,4'-bipyrazolate).
View Article and Find Full Text PDFOn-demand access to renewable and environmentally friendly energy sources is critical to address current and future energy needs. To achieve this, the development of new mechanisms of efficient thermal energy storage (TES) is important to improve the overall energy storage capacity. Demonstrated here is the ideal concept that the thermal effect of developing a solid-liquid interface between a non-wetting liquid and hydrophobic nanoporous material can store heat to supplement current TES technologies.
View Article and Find Full Text PDFMaterials or systems demonstrating negative linear compressibility (NLC), whose size increases (decreases) in at least one of their dimensions upon compression (decompression) are very rare. Materials demonstrating this effect in all their dimensions, negative volumetric compressibility (NVC), are exceptional. Here, by liquid porosimetry and neutron diffraction, we show that one can achieve exceptional NLC and NVC values by nonwetting liquid intrusion in flexible porous media, namely in the ZIF-8 metal-organic framework (MOF).
View Article and Find Full Text PDFMolecular dynamics simulations have been performed on liquid dibromomethane at thermodynamic states corresponding to temperature in the range 268-328 K and pressure varying from 1 bar to 3000 bar. The interaction model is a simple effective two-body pair potential with atom-atom Coulomb and Lennard-Jones interactions and molecules are rigid. Thermodynamic properties have been studied, including the isobaric thermal expansion coefficient, the isothermal compressibility, the heat capacities and the speed of sound.
View Article and Find Full Text PDFPresented here is a comprehensive study on the antioxidant properties of various alcoholic beverages: beers, wines, tinctures, and strong spirits, including whisky, brandy, cognac, vodkas, and liquors. The Trolox equivalent antioxidant capacity (TEAC) of each of these various alcoholic beverages is determined using an electron paramagnetic resonance (EPR) method, which is based on a semiempirical correlation. Moreover, the EC parameter was determined on the basis of the dependences of the TEAC values obtained by this mathematical equation.
View Article and Find Full Text PDFIn this article, the effect of a porous material's flexibility on the dynamic reversibility of a nonwetting liquid intrusion was explored experimentally. For this purpose, high-pressure water intrusion together with high-pressure in situ small-angle neutron scattering were applied for superhydrophobic grafted silica and two metal-organic frameworks (MOFs) with different flexibility [ZIF-8 and Cu(tebpz) (tebpz = 3,3',5,5'tetraethyl-4,4'-bipyrazolate)]. These results established the relation between the pressurization rate, water intrusion-extrusion hysteresis, and porous materials' flexibility.
View Article and Find Full Text PDFIn this work, we argue that the volumetric properties of liquids cannot be reproduced by a single isothermal equation of state derived by the compressibility route for the whole pressure region extended up to a GPa pressure but require the consideration of two states associated with qualitatively different molecular packing properties. This is confirmed by examples of polar and non-polar substances within the range of temperatures from 203.15 K to 491.
View Article and Find Full Text PDFA correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.
View Article and Find Full Text PDFDuring this work, we demonstrate, for the first time, that the volumetric properties of pure ionic liquids could be truly predicted as a function of temperature from 219 K to 473 K and pressure up to 300 MPa. This has been achieved by using only density and isothermal compressibility data at atmospheric pressure through the Fluctuation Theory-based Tait-like Equation of State (FT-EoS). The experimental density data of 80 different ionic liquids, described in the literature by several research groups as a function of temperature and pressure, was then used to provide comparisons.
View Article and Find Full Text PDFThis paper presents the first experimental evidence of pronounced electrification effects upon reversible cycle of forced water intrusion-extrusion in nanoporous hydrophobic materials. Recorded generation of electricity combined with high-pressure calorimetric measurements improves the energy balance of {nanoporous solid + nonwetting liquid} systems by compensating mechanical and thermal energy hysteresis in the cycle. Revealed phenomena provide a novel way of "mechanical to electrical" and/or "thermal to electrical" energy transformation with unprecedented efficiency and additionally open a perspective to increase the efficiency of numerous energy applications based on such systems taking advantage of electricity generation during operational cycle.
View Article and Find Full Text PDFA complete review of the literature data on the speed of sound and ultrasound absorption in pure ionic liquids (ILs) is presented. Apart of the analysis of data published to date, the significance of the speed of sound in ILs is regarded. An analysis of experimental methods described in the literature to determine the speed of sound in ILs as a function of temperature and pressure is reported, and the relevance of ultrasound absorption in acoustic investigations is discussed.
View Article and Find Full Text PDFForty-two hydrocarbon-degrading bacterial strains were isolated from the soil heavily contaminated with petroleum hydrocarbons. Forty-one strains were identified based on their whole-cell fatty acid profiles using the MIDI-MIS method. Thirty-three of them belong to species Rhodococcus erythropolis, while the others to the genera Rahnella (4), Serratia (3) and Proteus (1).
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