Paraffin-type phase change materials (PCMs) were entrapped using poly(methyl methacrylate) (PMMA) by suspension polymerisation for heat storing purposes at room temperature. To reduce the supercooling of the entrapped RT25HC paraffin, organic PCMs with different melting points were used as nucleating agents, i.e. RT35HC (melting point: 35 °C), MOL62-66 (melting point: 62–66 °C) paraffin and hydrogenated beef tallow (HBT) (melting point: 55–61 °C). Morphology, particle size distribution and degree of supercooling were investigated, and special attention has been paid to thorough thermal analysis. The prepared particles were compared with commercially available Micronal DS5038X microcapsules. The different rotational phases and solid–solid transitions have been analysed. The heat content of the characteristic transitions of different paraffins occurred at temperatures well below their melting points, and hence, it does not affect their applicability. However, knowledge of the rotational phase transition of mixtures and microencapsulated products near the main peak of the DSC curves is important from a practical point of view, since the formation of mixtures and subsequent microencapsulation together resulted in a substantial loss of heat capacity. HBT as, a novel, renewable and inexpensive nucleating agent was explored and found to be an effective compound to minimise the supercooling of microencapsulated paraffin. Avoiding supercooling is necessary to exploit the latent heat capacity of the capsules under real operating conditions.

γ-Al2O3-supported Ni- and bimetallic Ni-based catalysts modified with Zn, Cu, or In were investigated in hydrogen uptake and release cycle of the toluene (TOL)/methylcyclohexane (MCH) LOHC pair. The results demonstrate that strong metal–support interactions dominate the structure of the supported bimetallic systems, leading to highly dispersed Ni–O–Al interfacial species rather than bulk alloy phases. Cu and Zn preserved sufficiently large contiguous Ni ensembles required for reversible hydrogenation–dehydrogenation, while suppressing hydrogenolysis and coke formation. In induced extensive fragmentation of Ni ensembles, generating isolated Ni sites that favored selective dehydrogenation and enhanced resistance to carbon deposition. NiIn and NiZn/γ-Al2O3 exhibited the best overall balance of activity, selectivity and stability, achieving MCH conversion over 80% with >90% toluene selectivity at atmospheric and at elevated hydrogen pressures, respectively. The beneficial effect of hydrogen pressure was attributed to hydrogen-assisted desorption of strongly adsorbed intermediates, which suppressed coke formation and catalyst deactivation.

To mitigate the environmental impacts of harmful chemical substances, tannin has emerged as an eco-friendly corrosion inhibitor in acidic media. The condensed tannin was extracted from Acacia Mollissima and characterized using IR, XRD, and SEM. This paper explores the corrosion inhibition effect of tannin on mild steel in 1 M HCl using corrosion potential (Ecorr), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) across temperatures ranging from 303 to 343 K. Results demonstrate that tannin effectively inhibits corrosion in HCl, with its efficiency increasing with concentration but decreasing with temperature. Additionally, this research aims to extract thermal and kinetic data from tannin sourced from Acacia Mollissima, employing thermogravimetric analysis across four heating rates. Thus, the mass loss' second derivative DDTG was used to determine the characteristic decomposition temperatures precisely and to compare the thermal stability. The kinetic parameters, including activation energy and pre-exponential factor, were obtained using four isoconversional model-free methods proposed by Kissinger, Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), and Friedman. The energy required for degradation is higher at the final stages, indicating the presence of stable oxides at high temperatures. Using the Kissinger technique, the activation energy and pre-exponential factor were determined to be 301 kJ/mol and 6.9537 × 1025 min−1, respectively. In contrast, the average activation energy for free model approaches is 87.48, 82.66, and 82.97 kJ/mol when utilizing the FWO, KAS, and Friedman methods. Then, the most probable reaction functions were determined using the Coats-Redfern method, resulting in significantly improved calculation performance across the entire conversion range.

The thermal decomposition kinetics of biomass-derived tannins, particularly from Acacia Mollissima, are a significant factor for advancing both health and sustainability in materials science. In this study, tannins extracted from Acacia Mollissima underwent rigorous characterization using Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results confirmed that these tannins are of the condensed type. Subsequently, the condensed tannins were subjected to thermal decomposition analysis using a thermogravimetric analyzer (TGA) at four distinct heating rates: 10, 15, 20, and 25 K/min. The thermal behavior revealed four distinct stages of mass loss, accompanied by activation energies of 63.35, 257.01, 202.69, and 442.34 kJ/mol, respectively, indicating their significant potential for energy recovery and biochar production. Model-based kinetic approaches (Fn/DFn) demonstrated superior performance compared to model-free methods, achieving a correlation coefficient (R2) of 0.99979. The first stage of mass loss is attributed to moisture evaporation, followed by the degradation of crucial biological components, including decarboxylation, glycosidic bond breakdown, and aromatic ring degradation, ultimately producing valuable high-carbon residues. Kinetic analyses were conducted with NETZSCH Kinetics Neo software to compare model-fitting (model-based) and isoconversional (model-free) methods, such as Vyazovkin (Vya), Friedman (Fr), and numerical optimization (NOA). The optimal statistical performance in model-based analysis was achieved with a four-independent parallel reactions framework aligning with nth order kinetics, characterized respectively by the equations f(alpha) = (1 - alpha) n and f(alpha) = 0.5/alpha x (1-alpha)n, elucidating the transition from biomass to bioenergy. This work highlights the relevance of accurate kinetic modeling in optimizing biomass utilization pathways, contributing to the field of biomass energy and sustainable materials.

Meteorites arriving on Earth possess indigenous organic, isotopic, mineralogic, and magnetic properties that reveal conditions and processes from their formation. However, these properties can rapidly change when exposed to the Earth's environment. Asteroids, which formed nearly 4.5 billion years ago, inhabit the ultrahigh vacuum of interplanetary space, with a pressure of around 1.3 × 10 −11 Pa, equivalent to only a few tens of atoms per cubic centimeter. Fragments of these asteroids, which land on Earth as meteorites, immediately adsorb atmospheric gases into their pore spaces, which can subsequently adsorb into and onto the minerals. In this study, we show that adsorption of atmospheric water can significantly increase the mass of the smectite‐rich Tarda (C2‐ung) meteorite, with mass gains reaching around 30 wt% at 100% relative humidity (RH) and between 5 and 10 wt% under typical laboratory conditions (up to ~50% RH). In contrast, the serpentine‐rich Aguas Zarcas meteorite gains approximately 11 wt% at 100% RH and around 2 wt% at ~50% RH. This water adsorption leads to observable mass fluctuations in clay‐rich carbonaceous chondrites (CCs), especially those with high smectite content, which undergo a “breathing‐like” process. This process involves the uptake and release of water, influenced by atmospheric humidity. Although this mass change is reversible in the short term, prolonged “breathing” can alter the mineral composition and physical properties of these materials, complicating our understanding of their origins and evolution. For instance, gypsum forms in Tarda after 10 min of exposure to 100% RH at room temperature, while the Aguas Zarcas meteorite forms significant gypsum within 24 h under similar conditions. In addition, mass changes for Tarda are measured with thermal gravimetry in a He atmosphere, by heating the sample at 100°C in a high vacuum, and after curation under an ultradry atmosphere. These experiments show that samples exposed to the atmosphere rapidly adsorb significant water that is not removed by curation under dry N 2 . Our findings indicate that this “breathing” process can profoundly and rapidly affect the properties of astromaterials, including samples returned from asteroids Ryugu and Bennu. Maintaining these materials in a stable, low‐humidity environment can help prevent such changes and preserve their indigenous properties.

The lifetime of polymer electrolyte membrane fuel cells (PEMFCs) is significantly influenced by the degradation of their catalysts. A composite-type electrocatalyst support with the formula Ti(1−x)MoxO2-C (x: 0–0.2, C: carbon) has been found to provide higher stability for the Pt active metal than carbon alone. Non-traditional carbon materials such as graphene nanoplatelets (GNPs) and graphite oxide (GO) offer new possibilities for supports. This work aims to explore whether it is possible to combine the advantageous properties of GNP and GO in composite-supported Pt electrocatalysts. Composites prepared using the modified sol–gel method and Pt catalysts supported on them were characterized by physicochemical methods. Electrochemical behavior in terms of CO tolerance, activity and stability was studied. Although GO transformed into a mainly graphitic material during composite synthesis, its addition still increased the functional group content of the carbonaceous backbone. The electrical conductivity was significantly higher when GNPs-GO mixtures were used as the starting carbon material compared to the use of pure GNPs. Increased CO oxidation activity was achieved due to the incorporated Mo. Stability of the composite-supported Pt catalyst was significantly higher than that of commercial Pt/C. Increased stability of the GNPs-GO-derived catalyst compared to the GNP-derived one was obtained.

The replacement of persistent plastics with chemically recyclable and environmentally benign alternatives has become an urgent issue for our society. Although an increasing number of degradable polymers are available, many of them are facing with common challenges, that do not always allow for efficient direct replacements for durable plastics such as polyethylene. In this work, we present a new methodology for synthesizing cleavable units containing elastomers and thermoplastics by Ring-Opening Insertion Metathesis Polymerization (ROIMP) of cyclopentene (CP) with unsaturated polyester and polycarbonate oligomers. In the first step, diallyl ester oligomers were synthesized through acyclic diene metathesis (ADMET) polymerization, cyclopentene was then co-polymerized with the oligomers via ROIMP giving longchain polypentenamer (PP) dyads separated by easily cleavable singular ester or carbonate functionalities. Hydrolysis of the formed cleavable PP elastomer resulted in the formation of low molecular weight telechelic, OH-end-functionalized PP oligomers. Hydrogenation of the synthesized elastomers using Wilkinson's catalyst produced saturated long-chain hydrocarbon polymers with randomly distributed, cleavable subunits.

The replacement of persistent plastics with chemically recyclable and environmentally benign alternatives is an urgent environmental challenge. Although an increasing number of degradable polymers are now available, many face limitations that prevent their efficient direct substitution for durable plastics, such as polyethylene. Here, we present a methodology for the synthesis of polyolefin copolymers containing cleavable units via Ring-Opening Insertion Metathesis Polymerization (ROIMP) of cyclopentene (CP) with unsaturated polyester and polycarbonate oligomers. In the first step, diallyl ester oligomers were prepared through acyclic diene metathesis (ADMET) polymerization followed by copolymerization with CP via ROIMP to yield long-chain polypentenamer (PPe) dyads separated by singular, easily cleavable ester or carbonate functionalities. Hydrolysis of the resulting cleavable PPe elastomers produced low-molecular-weight, telechelic OH-end-functionalized PPe oligomers. Subsequent hydrogenation using Wilkinson's catalyst afforded saturated long-chain hydrocarbon polymers with randomly distributed cleavable subunits. The scalability of this approach was demonstrated for the ROIMP of CP with oligo-diallyl succinate (oligo-DAS).

Potassium ferrate(VI) (K2FeO4) as a particularly strong oxidant represents an effective and environmentally friendly waste water treatment material. When produced by anodic oxidation in highly alkaline aqueous solution, the K2FeO4 product is separated and sealed in inert plastic bags with the retention of some liquid phase with high pH. This method proved to be excellent for long-term storage at moderately low temperature (5 °C) for industrial applications. It is still imperative to check the ferrate(VI) content of the product whenever it is to be used. Fe-57 Mössbauer spectroscopy is an excellent tool for checking the ratio of ferrate(VI) to the degradation product iron(III) in a sample. For this purpose, normally the spectral areas of the corresponding subspectra are considered; however, this approximation neglects the possible differences in the corresponding Mössbauer–Lamb factors. In this work, we have successfully determined the Mössbauer–Lamb factors for the ferrate(VI) and for the most common iron(III) degradation products observed. We have found superparamagnetic behavior and low-temperature phase transformation for another iron(III) degradation product that made the determination of the Mössbauer–Lamb factors impossible in that case. The identities of a total of three different iron(III) degradation products have been confirmed.

Porosity affects key astromaterial processes from disruption in our atmosphere and impact with the ground, to the comminution of boulders by thermal and impact processes and slope mechanics on asteroid surfaces, to access and utilization of in-situ resources. Whereas the bulk porosity of clay-rich meteorites is well established, the magnitude of their surface area and nano-scale porosity is poorly known. Here we use N2 BET gas adsorption to measure the specific surface area and nanoscale pore distribution in several clay-rich meteorites. Two recent falls Tarda (C2-ung) and Aguas Zarcas (CM2) have specific surface areas of 72.5 and 16.5 m2/g, respectively. However, the specific surface area of Tarda ranges from 33.7 to 81.6 m2/g depending on outgassing conditions. The Tarda surface area is dominated by an interconnected network of ~ 3-nm-sized pores, whereas Aguas Zarcas shows a lower density of ~ 3 nm pores and broader size distribution around 40 nm. In contrast, Ivuna and Orgueil (CI1) have surface areas of ~ 15 to 18 m2/g: the low values compared to Tarda are likely due to the neoformation of pore-blocking minerals during atmospheric exposure. These data suggest that returned samples from asteroids Ryugu and Bennu, which are mineralogically and texturally similar to Tarda, also have interconnected nano-scale porosity with high surface area.

A unique compound (compound 1) with structural features including an unprecedented tridentate-bridging coordination mode of permanganate ions and an eight-coordinated (rhombohedral) κ1-chlorido and tridentate permanganato ligand in a potassium complex containing coordination polymer (CoIII(NH3)6]n[(K(κ1-Cl)2(μ2,2′,2″-(κ3-O,O′,O″-MnO4)2)n∞) with isolated regular octahedral hexamminecobalt(III) cation was synthesized with a yield of >90%. The structure was found to be stabilized by mono and bifurcated N-H∙∙∙Cl and N-H∙∙∙O (bridging and non-bridging) hydrogen bonds. Detailed spectroscopic (IR, far-IR, and Raman) studies and correlation analysis were performed to assign all vibrational modes. The existence of a resonance Raman effect of compound 1 was also observed. The thermal decomposition products at 500 °C were found to be tetragonal nano-CoMn2O4 spinel with 19–25 nm crystallite size and KCl. The decomposition intermediates formed in toluene at 110 °C showed the presence of a potassium- and chloride-containing intermediates combined into KCl during aqueous leaching, together with the formation of cobalt(II) nitrate hexahydrate. This means that the CoIII–CoII redox reaction and the complete decomposition of the permanganate ions occurred in the first decomposition step, with a partial oxidation of ammonia into nitrate ions.

Mesoporous materials containing heteroelements have a huge potential for use as catalysts, exchangers, and adsorbents due to their tunable nanometer-sized pores and exceptionally large internal surfaces accessible to bulky organic molecules. In the present work, ordered mesoporous silica containing Ni atoms as active sites was synthesized by a new low-temperature method of condensation of silica precursors on a micellar template from aqueous solutions in the presence of nickel salt. The homogeneity of the resulting product was achieved by introducing ammonia and ammonium salt as a buffer to maintain a constant pH value. The obtained materials were characterized by nitrogen sorption, X-ray and neutron diffraction, scanning electron microscopy, infrared spectroscopy, and thermal analysis. Their morphology consists of polydisperse spherical particles 50–300 nm in size, with a hexagonally ordered channel structure, high specific surface area (ABET = 900–1200 m2/g), large pore volume (Vp = 0.70–0.90 cm3/g), average mesopore diameter of about 3 nm, and narrow pore size distribution. Adsorption tests for methylene blue show sorption capacities reaching 39–42 mg/g at alkaline pH. The advantages of producing nickel silicates by this method, in contrast to precipitation from silicon alkoxides, are the low cost of reagents, fire safety, room-temperature processing, and the absence of specific problems associated with the use of ethanol as a solvent, as well as the absence of the inevitable capture of organic matter in the precipitation process.

Hydrated dipalmitoylphosphatidylcholine (DPPC) and lyso-palmitoylphosphatidylcholine (Lyso-PPC, abbreviated as LPC) mixtures form vesicles composed from periodically or randomly arranged layers and micelle-like nanoparticles, as revealed by a wide range of thermodynamical, structural, and morphological characterization methods. Based on five different experimental methods, we have reconstructed the phase diagram of the system. The micelle-like objects are strongly anisotropic and are identified as bicelles. Even a small amount of LPC induces drastic changes in the thermotropic phase behaviour of DPPC. Here, an interdigitated gel (L-beta I) structure, coexisting with the other gel phases, forms at moderate LPC concentration. Bicelles and L-beta I structured vesicles appear in the equimolar LPC ratio range (0.4 <= X-LPC <= 0.6). Two complex phase transition regimes are detectable. Between 36-40 degrees C, bicelles are pre-melted while domains of L-beta I structure are "crystallized" through local endothermic and exothermic transitions, respectively. Then, around 42 degrees C the chains of both the L-beta I and bicelles melt completely. Above the equimolar LPC ratio range (X-LPC > 0.6) the chain melting in the L-beta I structure vanishes, while this transition still exists in the chain region of bicelles. This wealth of structural forms, due to the weak first order transition characteristics, is highly sensitive for perturbations and interactions induced by e.g. the presence of membrane proteins.

Levocetirizine dihydrochloride is an effective antiallergenic drug applied mostly orally; however, developing a topical formulation for localized treatment could be beneficial. To achieve this, a modified formulation technique is necessary to enhance bioavailability efficiency and minimize possible side effects. Therefore, levocetirizine particles were prepared by immobilization on mesoporous silica material. Both the dihydrochloride form and its free base of levocetirizine were fixed on a silica-type Syloid support. Immobilization of the active ingredient levocetirizine in a free base form on a Syloid support by mixing in a dichloromethane solution provides better surface coverage (65.5%) than immobilization in the dihydrochloride form in water or methanol (24.5% for both). The successful binding of levocetirizine was confirmed by X-ray photoelectron spectroscopy and infrared measurements. The active ingredient in the form of hydrochloride is more likely to be in the pores, while the free base is bound to the surface in larger quantities. The time-dependent levocetirizine release showed that the liberation of the active ingredient from the Syloid is slower than the dissolution of the starting active ingredient itself, so it may be suitable for exerting a more reliable and prolonged local effect. A gel containing a Syloid-fixed levocetirizine free base was tested in vivo in a croton oil-induced ear edema mouse model. When compared to a reference gel, the half-dose formulation containing levocetirizine free base demonstrated a similar efficacy to Fenistil gel, indicating that the new formulation may offer superior effectiveness at lower doses.

The adsorption of surfaces exposed to sunlight results in increased temperatures that can cause physical damage and an increase in energy consumption. Infrared reflective coatings can keep objects cooler and have significant benefits in a wide variety of application by reflecting infrared light and decreasing heat, reducing operating costs, improving energy efficiency in buildings and vehicles, and extending an objects’ lifespan. The main aim of our research was to develop coatings in a RAL7016 Anthracite grey color with minimum heat adsorption in the infrared wavelength range. This was achieved using a combination of infrared transparent and infrared reflective pigment built-in coatings applied on two primers: white and black. Infrared reflectivity or transparency, as well as surface temperature, was investigated as a function of the composition and concentration of pigments. These coatings were characterized by chromatic parameters, by total solar and infrared solar reflectance in the UV, visible, and infrared wavelength range, and by heat reflection. Among the coatings developed, two produced very effective controls for infrared reflectance and transparency, and they could control heat reflectance, resulting in a significant decrease in surface temperature.

Latent heat storage by phase change materials (PCMs) has become an important research area due to the need of energy saving especially in the building sector. Environmental considerations require the intensified use of bio-originated materials instead of agents gained from mineral oil. Due to its melting point in the range of room temperature, the coconut oil is an available bio-originated PCM with low cost and high heat capacity. In this study, the main process parameters of coconut oil PCM-loaded calcium alginate microcapsules with double-layered shell were optimised. Viscosity of alginate solution, contact time, concentrations of alginate and calcium ions played important role in the process optimisation and waste reduction. In a thermal cycling test, it was confirmed that the microcapsules did not leak the PCM after 200 heating and cooling cycles.

Ikaite formation and its transformation to calcite occurs via distinct amorphous calcium carbonates (referred to as I and II) that differ in their morphology, particle size, water content and stability.

[κ2-O,O′-Carbonatotetraamminecobalt(III)] iodide, or [Co(NH3)4CO3]I, named in this paper as compound 1, was prepared and characterized comprehensively with spectroscopic (IR, Raman and UV) and single-crystal X-ray diffraction methods. Compound 1 was orthorhombic, and isomorphous with the analogous bromide. The four ammonia ligands and the carbonate anion were coordinated to the central cobalt cation in a distorted octahedral geometry. The carbonate ion formed a four-membered symmetric planar chelate ring. The complex cations were bound to each other by N-H···O hydrogen bonds and formed zigzag sheets via an extended 2D hydrogen bond network. The complex cations and iodide ions were arranged into ion pairs and each cation bound its iodide pair through three hydrogen bonds. The thermal decomposition started with the oxidation of the iodide ion by CoIII in the solid phase resulting in [Co(NH3)4CO3] and I2. This intermediate CoII-complex in situ decomposed into Co3O4 and C-N bond containing intermediates. In inert atmosphere, CO or C-N bond containing compounds, and also, due to the in situ decomposition of CoCO3 intermediate, Co3O4 was formed. The quasi-intramolecular solid-phase redox reaction of [Co(NH3)4CO3] might have resulted in the formation of C-N bond containing compounds with substoichiometric release of ammonia and CO2 from compound 1. The C-N bond containing intermediates reduced Co3O4 into CoO and Co, whereas in oxygen-containing atmosphere, the end-product was Co3O4, even at 200 °C, and the endothermic ligand loss reaction coincided with the consecutive exothermic oxidation processes.

Thermal processing of Zr-loaded ion-exchangers is a facile route to synthetize (ZrO2, ZrC)@C composites. In the present paper, furnace and RF-thermal plasma processing of ZrOCl2 loaded thiourea-functionalized styrene-divinylbenzene copolymer was investigated and led to composites containing ZrO2 and ZrC. Different ZrO2@C composites were formed between 1000 and 1400 °C in 2 h, whereas the composite containing ZrC was created at 1400 °C in 8 h. The ratio of ZrO2/ZrC, the prevailing ZrO2 modifications, and the crystallite sizes strongly depend on the synthesis conditions. The ZrC-containing composites formed only at 1400 °C in 8 h and by the plasma treatment of the ZrO2@C sample prepared in the furnace, resulting in 8 and 16% ZrC content, with 44 and 41 nm ZrC crystallite sizes, respectively. The ZrO2-containing composites (tetragonal, monoclinic, and cubic modifications with 65–88 nm ZrO2 crystallite sizes and 15–43 m2/g BET surface areas) formed in a tube furnace between 1000 and 1400 °C in 2 h. All ZrO2@C composites had both amorphous carbon and graphite, and their ratio is temperature dependent. The carbonaceous compounds were characterized by Raman spectroscopy with analysis of the G and D band intensities. XPS studies showed the surface oxidation of ZrC.

Lignin is known to have great potential for use as a renewable feedstock in a variety of industrial applications, including energy and chemicals. Furthermore, to ensure an efficient valorization of lignin, the efficiency of the isolation procedure and the knowledge of its properties are crucial. In the present study, we extracted lignin from date seeds using the Klason method. The extracted lignin was characterized by FT-IR spectrometry, XRD and SEM-EDX analysis. The thermal behavior of date seeds lignin has been investigated using TGA and DSC. Several isoconversional and model-fitting methods were employed to derive the kinetic parameters. A comparison between these procedures was carried out. Based on the results of activation energy (Ea) and pre-exponential factor (A) determined using Kissinger’s equation for date seeds lignin decomposition, some thermodynamic parameters (ΔS#, ΔH# and ΔG#) were determined. Following a broad endothermic stage, a large exothermic peak was observed in the DSC plots, attesting to the overall exothermicity of the lignin pyrolysis. From the derivative curve of DSC plots, the glass transition temperature Tg of the studied lignin was determined. High values of Tg, ranging from 102.62 to 127.28 °C, significantly affected by the heating rate, were found.