Search Results (33)

This work targets a knowledge gap in the high-pressure decomposition of methanol, complementing prior moderate-pressure diamond anvil studies below 4 GPa and hyperbaric-pressure laser chemical vapour deposition (HP-LCVD) experiments below 0.01 GPa. Localised decomposition of methanol into various carbon allotropes was investigated at pressures of up to 15 GPa. Diamond anvil cell (DAC) pressures were monitored in real-time using ruby fluorescence and a high-resolution spectrometer. Selective saser reactive synthesis within diamond anvil cells (LRS-DAC) was achieved using a 20-micron 1/e² laser beam focus—one order of magnitude smaller than the diamond anvil chamber dimensions. Confocal Raman spectroscopy and electron microscopy were employed to investigate the deposit’s local microstructure. Various carbon allotropes were synthesised selectively, including single-crystal diamond, nanocrystalline diamond, multi-walled carbon nanotubes (MWCNTs), single-walled carbon nanotubes (SWCNTs), and amorphous carbons. At least two unknown Raman signatures were observed and unlikely to be harmonics or combinations of ordinary Raman peaks, the closest known Raman spectra being that of catechol and polycatechol. Potential side reactions are proposed, where polymerisation and/or ring-formation may occur during high-pressure moderate-temperature (HPMT) conditions. Full article

The large-scale implementation of 2D material-based membranes is hindered by mechanical stability and mass transport control challenges. This work describes the fabrication, characterisation, and testing of self-standing graphene oxide (GO) membranes cross-linked with oxides such as Fe₂O₃, Al₂O₃, CaSO₄, Nb₂O₅, and a carbide, SiC. These cross-linking agents enhance the mechanical stability of the membranes and modulate their mass transport properties. The membranes were prepared by casting aqueous suspensions of GO and SiC or oxide powders onto substrates, followed by drying and detachment to yield self-standing films. This method enabled precise control over membrane thickness and the formation of laminated microstructures with interlayer spacings ranging from 0.8 to 1.2 nm. The resulting self-standing membranes, with areas between 0.002 m² and 0.090 m² and thicknesses from 0.6 μm to 20 μm, exhibit excellent flexibility and retain their chemical and physical integrity during prolonged testing in direct contact with ethanol/water and methanol/water mixtures in both liquid and vapour phases, with stability demonstrated over 24 h and up to three months. Gas permeation and chemical characterisation tests evidence their suitability for gas separation applications. The interactions promoted by the oxides and carbide with the functional groups of GO confer great stability and unique mass transport properties—the Nb₂O₅ cross-linked membranes present distinct performance characteristics—creating the potential for scalable advancements in cross-linked 2D material membranes for separation technologies. Full article

The most commonly used homogeneous catalyst for fatty acid esterification is a corrosive sulphuric acid. However, this requires costly investment in non-corrosive equipment, presents a safety risk, is time consuming, and increases effluent generation. In this study, inorganic 3D heteroborane cluster strong acids are employed for the first time as homogeneous catalysts. Three novel isomeric tetrachlorido and tetrabromido derivatives of 3,3′-commo-bis[undecahydrido-closo-1,2-dicarba-3-cobaltadodecaborate](1−) [1⁻] were synthesised and fully characterised using a range of analytical techniques, including NMR, TLC, HPLC, MS, UV-Vis, melting point (MP), CHN analyses, and XRD. Ultimately, H₃O[8,8′-Cl₂-1⁻] was identified as the most efficient, reusable, and non-corrosive homogeneous catalyst for the esterification of four fatty acids. The reactions are conducted in an excess of alcohol at reflux. The effective absorption of water vapour provided by the molecular sieves maximises acid conversion. The hydrophobic dye Sudan black B was employed as an acid-base indicator to facilitate a comparison of the H₀ acidity function of sulphuric acid and halogenated heteroboranoic acids when dissolved together in methanol. The ²³Na NMR analysis demonstrated that the application of dry methanol resulted in the displacement of Na⁺ ions from zeolite, which subsequently exchanged the H₃O⁺ ions of the acid. This process led to a gradual reduction in the efficiency of the catalysts, particularly with repeated use. The solution to this issue is to regenerate the catalyst on the ion exchanger following each reaction. In contrast to the published methods, our new approach meets 10 of 12 green chemistry principles. Full article

Freeform carbon fibres were 3D-printed from CH₃OH:H₂O mixtures using hyperbaric-pressure laser chemical vapour deposition (HP-LCVD). The experiment overlapped a region of known diamond growth, with the objective of depositing diamond-like carbon without the use of plasmas or hot filaments. A high-pressure regime was investigated for the first time through the precursor’s critical point. Seventy-two C-fibres were grown from 13 different CH₃OH:H₂O mixtures at total pressures between 7.8 and 180 bar. Maximum steady-state axial growth rates of 14 µm/s were observed. Growth near the critical point was suppressed, ostensibly due to thermal diffusion and selective etching. In addition to nanostructured graphite, various carbon allotropes were synthesised at/within the outer surface of the fibres, including diamond-like carbon, graphite polyhedral crystal, and tubular graphite cones. Several allotropes were oversized compared to structures previously reported. Raman spectral pressure–temperature (P-T) maps and a pictorial P-T phase diagram were compiled over a broad range of process conditions. Trends in the Raman I_D/I_G and I_2D/I_G intensity ratios were observed and regions of optimal growth for specific allotropes were identified. It is intended that this work provide a basis for others in optimising the growth of specific carbon allotropes from methanol using HP-LCVD and similar CVD processes. Full article

Reactions of copper(II) sulfate with 2,2′-bipyridine (bpy) and l-serine (l-Hser) were investigated using different solution-based and mechanochemical methods. Four new ternary coordination compounds were obtained by solution-based synthesis, and three of them additionally via the liquid-assisted mechanochemical method: α-[Cu(l-Ser)(H₂O)(bpy)]₂SO₄ (1a-α), β-[Cu(l-Ser)(H₂O)(bpy)]₂SO₄ (1a-β), [Cu(l-Ser)(H₂O)(bpy)]₂SO₄·6H₂O (1a∙6H₂O), and [Cu(l-Ser)(bpy)(CH₃OH)]₂SO₄·2CH₃OH (1b∙3CH₃OH). The compounds were characterized by single-crystal and powder X-ray diffraction, infrared spectroscopy, and thermal analysis. Structural studies revealed two polymorphs (1a-α and 1a-β) and two solvatomorphs (1a∙6H₂O and 1b∙3CH₃OH). To investigate the stability of the compounds, crystalline samples were exposed to different conditions of relative humidity (RH) and an atmosphere of methanol vapours. Successful solid-state transformation of 1a∙6H₂O into 1a-α was established at lower RH values, and vice versa at higher RH values, while both compounds partially transitioned to 1a-β in the atmosphere of methanol vapours. Compound 1b∙3CH₃OH decomposed spontaneously into 1a-α by standing in the air. All of the investigated structural transformations were underpinned with proposed mechanisms. Additionally, 1a-α showed moderate in vitro antiproliferative activity toward a human breast cancer cell line (MCF-7), a human colon cancer cell line (HCT116), and a human lung cancer cell line (H460). Full article

Heat pumps have the potential for several applications across various industrial sectors, showcasing significant promise, especially in sectors such as pulp and paper, food and beverage, chemical, non-metallic minerals, and machinery. Envisioning the near future, there is confidence that heat pumps can achieve temperatures above 200 °C, offering substantial potential for utilization in these sectors. Nevertheless, a crucial aspect for the advancement of high-temperature heat pumps is the selection of the fluid. Fluid selection involves considerations of both thermodynamic efficiency and environmental impact, requiring fluids with zero ODP, negligible GWP, and no PFAS. Moreover, it is essential to consider the risks to human health associated with a specific fluid. Despite extensive research, particularly in the realm of vapour compression heat pumps, choosing the most suitable working fluid for these applications is a complex undertaking. Therefore, this paper conducts a theoretical analysis to evaluate potential fluids with suitable thermodynamic properties for high-temperature heat pumps (HTHPs). The comparative results gleaned from this study provide valuable insights for the comprehensive analysis of fluids, showing promise within temperature ranges dictated by specific applications. The metrics employed in the comparison emphasise the merits of fluids in terms of the overall performance, dimensions, and operating ranges of applicable compressor, heat exchange capacity, transport properties, and safety. One noteworthy finding from the analysis is that maintaining a constant HTHP lift (at 40 K) results in having the highest COP across all fluids when the condensing temperature ranges between 85% and 90% of their respective critical temperatures. According to the results of the analysis, natural fluids, including water and alcohols like ethanol or methanol, emerge as particularly compelling candidates. Full article

In this work, we report on the synthesis of four morphologies of ZnO, namely, nanoparticles, nanorods, nanosheets, and nanoflowers, from a single precursor Zn(CH₃COO)₂·2H₂O under different reaction conditions. The synthesised nanostructured materials were characterised using powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Raman spectroscopy, UV–Vis, XPS analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and nitrogen sorption at 77 K. The XRD, FTIR, and Raman analyses did not reveal any significant differences among the nanostructures, but differences in the electronic properties were noted among the different morphologies. The TEM and SEM analyses confirmed the four different morphologies of the ZnO nanostructures. The textural characteristics revealed that the specific surface areas were different, being 1.3, 6.7, 12.7, and 26.8 m²/g for the nanoflowers, nanoparticles, nanorods, and nanosheets, respectively. The ZnO nanostructures were then mixed with carbon nanoparticles (CNPs) and cellulose acetate (CA) to make nanocomposites that were then used as sensing materials in solid-state sensors to detect methanol, ethanol, and isopropanol vapour at room temperature. The sensors’ responses were recorded in relative resistance. When detecting methanol, 6 out of 12 sensors were responsive, and the most sensitive sensor was the composite with a mass ratio of 1:1:1 of ZnO nanorods:CNPs:CA with a sensitivity of 0.7740 Ω ppm⁻¹. Regarding the detection of ethanol vapour, 9 of the 12 sensors were responsive, and the 3:1:1 mass ratio with ZnO nanoparticles was the most sensitive at 4.3204 Ω ppm⁻¹. Meanwhile, with isopropanol, 5 out of the 12 sensors were active and, with a sensitivity of 3.4539 Ω ppm⁻¹, the ZnO nanoparticles in a 3:1:1 mass ratio were the most sensitive. Overall, the response of the sensors depended on the morphology of the nanostructured ZnO materials, the mass ratio of the sensing materials in the composites, and the type of analyte. The sensing mechanism was governed by the surface reaction on the sensing materials rather than pores hindering the analyte molecules from reaching the active site, since the pore size is larger than the kinetic diameter of the analyte molecules. Generally, the sensors responded well to the ethanol analyte, rather than methanol and isopropanol. This is due to ethanol molecules displaying a more enhanced electron-donating ability. Full article

The paper deals with a new method of drying cellulose insulation, which uses methanol vapour present in nitrogen as a drying medium. Compared to the insulation drying methods currently used in the industry, the method presented in the article has the following advantages: there is no cellulose depolymerization because there is no need to heat the insulation, there is no need to use large-size and energy-intensive dryers because the whole process takes place in the tank of the transformer. Important parameters of the drying process, such as methanol concentration in the nitrogen, flow rate, and process duration, were determined in four separate experiments. For the purposes of these experiments, a special system was constructed to control and measure the flow of drying medium. Controlling the flow rate of the carrier gas (nitrogen) made it possible to obtain different concentrations of methanol in nitrogen. Such values of concentration and flow rate were determined that allow drying of pressboard and paper in less than 144 h to a level lower than 1%. Full article

Determination of relative volatilities of flavour compounds in hydro-alcoholic solutions is usually performed by time-consuming and costly standard methods such as the Gillespie dynamic recirculation method. This study tested a quick and easy method with a simple distillation apparatus for measuring empirical relative volatilities. A total of 17 representative flavour compounds of apple and pear brandies were selected and investigated for their relative volatilities. This also included so far unpublished relative volatilities of one alcohol (2-butanol), one aldehyde (hexanal), one ketone (β-damascenone), and three esters (ethyl butyrate, butyl acetate, ethyl 2-methylbutyrate). Relative volatilities of three alcohols (methanol, isobutanol, and isoamyl alcohol), one ester (ethyl acetate), one aldehyde (acetaldehyde), and one acetal (1,1-diethoxyethane) were compared to reference data. All compounds, except for 1,1-diethoxyethane, showed a high correlation with the reference data. Vapour–liquid equilibrium for an ethanol–water mixture showed a high correlation with the reference data (r > 0.9). In accordance with the high correlation levels, we suggest that the simple distillation apparatus is a fast and simple alternative to the standard method. Full article

In this study, multi-walled carbon nanotubes (MWCNTs) were prepared by chemical vapour deposition (CVD) using acetylene as a carbon source over an iron catalyst. As-prepared MWCNTs were used to support modern mono-copper, palladium, and bimetallic palladium-copper catalysts, and their feasibility for hydrogen production was tested during steam reforming of methanol (SRM) and methanol decomposition (DM). The structural characteristics of the MWCNTs were evaluated using the SEM and XRD methods. The physicochemical properties of the monometallic and bimetallic catalysts were analysed using the TPR and XRD methods. The promotion effect of palladium on methanol conversion rate and H₂ productivity in the case of the copper catalysts was demonstrated. The enhanced activity of the Cu/MWCNTs after palladium promotion was due to the formation of Pd-Cu alloy compound. Full article

Chondrichthyan fishes, which comprise sharks, rays, and chimaeras, are one of the most threatened groups of vertebrates. Given this situation, one possible strategy for the protection of these species could be the use of ex situ conservation projects. However, to develop sustainable ex situ conservation programs, captive breeding techniques, such as sperm extraction and its preservation, should be used. Two main obstacles must be overcome to develop these techniques: first, the lack of knowledge and the scarce previous work focused on the conservation of gametes from these animals; secondly, the peculiarities of the reproductive anatomy of each particular species. Through a detailed description of their reproductive anatomy, we have been able to develope the best techniques to obtain viable sperm from 17 species. Extraction has been performed in both live and dead animals, using cannulation, abdominal massage, and dissection. Exceptionally, we have even been able to recover viable sperm from the reproductive tract of females. Moreover, we have formulated artificial seminal plasma that can be used as an extender to maintain sperm motility for 36 days at 4 °C. By supplementing this extender with different combinations of cryoprotectants, i.e., methanol, dimethyl sulfoxide (DMSO), and fresh egg yolk, we were able to successfully cryopreserve (for the first time in most of these species) the sperm of 14 chondrichthyan species. Sperm samples were frozen inside a styrofoam box using the vapour of liquid nitrogen and were preserved in liquid nitrogen. The sperm quality was assessed by studying the motility and membrane integrity post thawing, demonstrating its effectiveness in the 14 species tested. In rays, the use of 10% DMSO or 10% methanol rendered post-thawing motility values higher than 40%. In sharks and the chimaera species, the best post-thawing motility values were obtained with a combination of 5% DMSO, 5% methanol and 10% egg yolk, which induced mean values close to 35%. All this information broadens our knowledge on the reproductive techniques that can be applied to chondrichthyans, laying the foundations for the first cryobanks for their sperm. Full article

The surface properties of coal, interactions with gaseous and vapour media, and knowledge of the pore structure are important in terms of preparation, use, and utilisation of coal. This publication combines new unpublished data with analyses included in earlier publications by the research team to expand and systematise information on the sorption of water vapour, methanol vapour, and the saturated and unsaturated hydrocarbons hexane, 1-hexene, heptane, 1-heptene, octane on coals of different ranks. The study showed that the affinity of coal for water and methanol is related to the content of oxygen in the coal rather than the rank of the coal. Water sorption is a multilayer phenomenon, while methanol sorption is a monolayer phenomenon. The water monolayer is greater than that of methanol for low-rank coal, but for the higher-rank coals it is the opposite. The sorption capacity of the applied hydrocarbons depends on the presence or absence of a double bond and the size of the molecule. It increases in the order: n-octane < n-heptane/n-hexane < 1-heptene < 1-hexene. The effect of a double bond is dominant over the influence of the length and shape of the molecule. Full article

Bismuth-based perovskites are potentially a promising alternative for lead-free perovskites. During bond formation, however, trivalent ions on ${\mathrm{Cs}}_3{\mathrm{Bi}}_2{\mathrm{I}}_9$with CsI/BiI₃ ratio of 1.5/1 form 0D-neutral charged compounds with higher bandgap (>2.0 eV) and poor absorption capacity. Mixed 0/2-dimensional structures are potentially suitable substitutes due to their low bandgap. So far, the reported CsI/BiI₃ ratios for 0D/2D structures are 1:1, 1:2 and 1:3. Herein, a new ratio of 1/1.5 is reported. Caesium bismuth iodide at a ratio of CsI/BiI₃ of 1/1.5 was synthesised using a one-step processing method with/without solvent vapour annealing. During solvent annealing, a 1/4 (v/v) mixture of DMF/methanol was used as a solvent. The crystal structure formed at a ratio of 1/1.5 is more similar to 1.5/1 than to 1/3. The XRD pattern revealed additional characteristics peaks at 009, 012, 209 and 300, indicating the growth of another phase. The formed heterogeneous mixed 0D/2D structure has an extended light absorption capacity greater than 720 nm. Solvent vapour annealing improved film morphology by enhancing grain size and packing density. When cells with and without solvent vapour annealing are compared, the power conversion efficiency of caesium bismuth iodide increases from 0.26% without solvent annealing to 0.98% with solvent vapour annealing. This study establishes a new route for future research on crystal configuration, nomenclature, film and morphology, quality tailoring and applications toward the goal of lead-free perovskite solar cells. Full article

Diamond is a very interesting material with a wide range of properties, making it highly applicable, for example, in power electronics, chemo- and biosensors, tools’ coatings, and heaters. Due to the high demand for this innovative material based on the properties it is already expected to have, it is important to obtain homogeneous diamond layers for specific applications. Doping is often chosen to modify the properties of layers. However, there is an alternative way to achieve this goal and it is shown in this publication. The presented research results reveal that the change in methanol content during the Hot Filament Chemical Vapour Deposition (HF CVD) process is a sufficient factor to tune the properties of deposited layers. This was confirmed by analysing the properties of the obtained layers, which were determined using Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and an atomic force microscope (AFM), and the results were correlated with those of X-ray photoelectron spectroscopy (XPS). The results showed that the increasing of the concentration of methanol resulted in a slight decrease in the sp³ phase content. At the same time, the concentration of the -H, -OH, and =O groups increased with the increasing of the methanol concentration. This affirmed that by changing the content of methanol, it is possible to obtain layers with different properties. Full article

In search a hydrogen source, we synthesized TiO₂-Cu-graphene composite photocatalyst for hydrogen evolution. The catalyst is a new and unique material as it consists of copper-decorated TiO₂ particles covered tightly in graphene and obtained in a fluidized bed reactor. Both, reduction of copper from Cu(CH₃COO) at the surface of TiO₂ particles and covering of TiO₂-Cu in graphene thin layer by Chemical Vapour Deposition (CVD) were performed subsequently in the flow reactor by manipulating the gas composition. Obtained photocatalysts were tested in regard to hydrogen generation from photo-induced water conversion with methanol as sacrificial agent. The hydrogen generation rate for the most active sample reached 2296.27 µmol H₂ h⁻¹ g_cat⁻¹. Combining experimental and computational approaches enabled to define the optimum combination of the synthesis parameters resulting in the highest photocatalytic activity for water splitting for green hydrogen production. The results indicate that the major factor affecting hydrogen production is temperature of the TiO₂-Cu-graphene composite synthesis which in turn is inversely correlated to photoactivity. Full article