Search Results (407)

The paper describes the conversion of carbon dioxide into methanol in a chemical reactor under standard operating conditions. Electro-analytical techniques, cyclic voltammetry, and chrono-amperometry characterize the process. The electrochemical redox reaction develops using various catalyzers to evaluate the performance of the carbon dioxide conversion into methanol process under variable chemical conditions. The results of the applied technique showed an incomplete redox reaction with an electronic change of z = 2.84 on average, below the ideal number, z = 6, that may be due to methanol decomposition (reverse reaction) because the system operates with a reaction constant above the equilibrium value. The methanol production may improve by draining the methanol/water solution from the chemical reactor to reduce the methanol concentration in the electrochemical cell, shifting the forward reaction towards the formation of methanol, increasing the electron change number, which approaches the ideal value, and improving the methanol production efficiency. The draining process shows a significant increase in methanol formation, which depends on the draining flow rate and the catalyzer type. A simulation process shows that if we operate in optimum conditions, with no methanol decomposition through a reverse reaction, the redox reaction fulfills the ideal condition of maximum electronic change. The experimental tests validate the simulation results, showing a relevant increase in the electron change number with values up to z = 4.2 for optimum draining flow rate conditions (0.2 L/s). The experimental results show a relative increase factor of 4.7 in methanol production, meaning we can produce more than four times more methanol compared with no draining techniques. The data analysis shows that the draining flow rate has a threshold of 0.2 L/s, beyond which the extent of the reaction reverses, reducing the methanol formation due to a chemical reaction disequilibrium. The paper concludes that using the draining method, the methanol production mass rate increases significantly from an average value of 20.9 kg/h for non-draining use, considering all catalyzer types, to a range between 91.9 kg/h and 104.3 kg/h, depending on the flow rate. Averaging all values for different flow rates and comparing with the non-draining case, we obtain an absolute methanol production mass rate of 77 kg/h, meaning an incremental percentage of 469.1%, more than four times the initial production. Although the proposed methodology looks promising, applying this procedure on an industrial scale may suffer from restrictions since the chemical reactions intervening in the methanol formation do not perform linearly. According to experimental tests, the best option among the six catalyzers used for methanol production is the plain copper, with copper oxides (Cu₂O, CuO) and copper Sulphur (CuS) as feasible alternatives. Full article

The efficiency of membrane reactors for steam reforming of hydrocarbons depends critically on the performance and selectivity of hydrogen-permeable membranes. In this work, a strategy for controlling the catalytic and gas-transport characteristics of Pd-Ag-Ru membranes by modifying the surface and controlling the morphology of nanostructured coatings was developed. It was found that as the process temperatures approached ~200 °C and the membrane thickness decreased, a transition to limitation of the hydrogen transfer process by surface stages was observed. Surface modification with pyramidal nanoparticles resulted in a significant increase in the hydrogen flux by up to 1.5 times compared to membranes with spiked nanoparticles and up to 2 times compared to membranes with spherical nanoparticles. The maximum difference in fluxes of up to 12 times was achieved compared to uncoated membranes. The achieved result is due to a significant increase in the active surface area associated with a systematic change in the morphology of the coatings. This aspect was a key factor in improving the catalytic activity of the material, reducing the energy barrier of sorption and accelerating the stages of hydrogen transfer through the developed membranes. Thus, modification with shape-controlled nanoparticle coatings presents an effective strategy for overcoming the limitations of the permeability of palladium-based membranes under conditions of small thickness and low temperatures. The use of the developed membranes in steam reforming reactors of alcohols can provide increased energy efficiency, conversion and purity of hydrogen. Full article

In this study, MnO₂-CNTs composite support was prepared by citric acid reduction method, and then, Pt nanoparticles were loaded on the surface by ethylene glycol reduction method to obtain a series of Pt/xMnO₂-CNTs catalysts. Structural characterization (TEM, XRD, HRTEM) showed that Pt nanoparticles were uniformly dispersed on the surface of the catalyst with an average particle size of 3.6 nm. Electrochemical tests show that when the content of MnO₂ is 20 wt.%, the Pt/_20wt.%MnO₂-CNTs catalyst has the best methanol oxidation performance, and its mass activity and long-term stability are 4.0 times and 5.41 times that of commercial Pt/C, respectively. The in situ FTIR results showed that MnO₂ promoted the dissociation of water through synergistic effect, generated abundant OH species, accelerated the oxidation of CO intermediates, and inhibited the poisoning of Pt sites. In this study, it is clear that the excellent performance of Pt/xMnO₂-CNTs is due to multiple synergistic effects. Modified carbon nanotubes facilitate proton conduction, Pt nanoparticles effectively activate methanol, and MnO₂ modulates reaction intermediates via its bifunctional mechanism. This comprehensive mechanism understanding provides a theoretical basis for the design of high-performance catalysts for direct methanol fuel cells. Full article

Hydrolates are aromatic aqueous solutions saturated with volatile water-soluble compounds of essential oil. Despite their potential, hydrolates remain less explored than essential oils. In this work, the hydrolate of Pelargonium odoratissimum (L.) L’Hér. has been analyzed by multiple analytical techniques in order to describe its chemical composition. Headspace (HS-) and Direct Immersion-Solid Phase Microextraction-Gas Chromatography/Mass spectrometry (DI-SPME-GC/MS) and Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) were employed to reveal the VOC emission from the hydrolate. Further, a direct injection of the pure hydrolate and of the hydrolate after extraction with hexane was performed by Large-Volume Injection Gas Chromatography/Mass Spectrometry (LVI-GC/MS) and GC/MS. The results obtained by HS- and DI-SPME-GC/MS highlighted a nearly overlapping chemical profile with linalool, isomenthone, and α-terpineol as the main volatiles. On the other hand, analysis of the hydrolate by GC/MS after solvent extraction revealed a lower overall number of compounds but allowed the detection of thujone and cis-linalool oxide. In comparison, LVI-GC/MS was the technique that allowed the identification of a higher number of volatiles with citronellol, linalool, and α-terpineol as the principal compounds. Finally, PTR-ToF-MS was a fundamental approach to quantify and evaluate total terpene emissions from this complex matrix starting from low-molecular-weight compounds such as acetylene, methanol, acetaldehyde, acetone, and ethanol, which were the most abundant. Among the detected compounds, dimethyl sulfide and small amounts of dimethyl-furan and 2-butylfuran were also identified. Overall, the findings showed that the hydrolate was rich in monoterpene compounds while sesquiterpene compounds were missing. A very low intensity relating to sesquiterpenes was recorded only by PTR-ToF-MS technique. Full article

The large-scale implementation of direct methanol fuel cells (DMFCs) is significantly impeded by sluggish methanol oxidation reaction (MOR) kinetics, degradation of Pt electrocatalysts, and significant carbon support corrosion in commercial Pt/C. Herein, we design a mesoporous hollow TiO₂@carbon core–shell composite (MH-TiO₂@C) as a support for Pt nanoparticles to serve as an efficient MOR electrocatalyst. Pt/MH-TiO₂@C demonstrates exceptional MOR activity in alkaline electrolyte, exhibiting a mass activity 2.56-fold higher than commercial Pt/C. Furthermore, Pt/MH-TiO₂@C displays remarkable durability compared to Pt/C. Following chronoamperometry tests, the mass activity of Pt/MH-TiO₂@C decreased by 30.92%, substantially lower than the 52.31% loss observed for commercial Pt/C. The superior MOR activity and durability originate from the inherent structural stability of the MH-TiO₂@C composite, strong metal-support interaction between Pt and TiO₂, and enhanced resistance to intermediate poisoning. This work presents a feasible strategy for developing efficient and durable Pt-based electrocatalysts, accelerating the commercialization of DMFCs. Full article

This work aims to present tes-thermo, a Python library developed to solve thermodynamic equilibrium problems using the Gibbs energy minimization approach. The library is a variant of TeS v.3, a standalone executable developed for the same purpose. The tool formulates the chemical equilibrium problem of combined phases as a nonlinear programming problem, implemented using Pyomo (Python Optimization Modeling Objects) and solved with IPOPT (Interior Point OPTimizer). To validate the tool and demonstrate its robustness, the supercritical water gasification (SCWG) of methanol and ethanol was investigated. The Peng–Robinson equation of state was employed to account for non-idealities in the gas phase. Experimental and simulated data from the literature were used for validation, and, in both cases, the results were satisfactory, with root mean square errors consistently below 0.23. The SCWG processes studied revealed that hydrogen production is favored by increasing temperature and decreasing pressure. For both methanol and ethanol, increasing the carbonaceous substrate fraction in the feed promotes hydrogen formation; however, it also leads to reduced hydrogen relative yield due to the enhanced formation of methane and carbon monoxide under these conditions. Consequently, although hydrogen production increases, the hydrogen molar fraction in the dry gas stream tends to decrease with the higher substrate content. As expected, the SCWG of methanol produces more hydrogen and less carbon monoxide compared to ethanol under similar conditions. This behavior is consistent with the higher carbon content in ethanol, which favors reactions leading to carbon oxides. In summary, tes-thermo proves to be a robust and reliable tool for conducting research and studies on topics related to thermodynamic equilibrium. Full article

The methanol oxidation reaction (MOR) of direct methanol fuel cells (DMFCs) is limited by the slow kinetic process and high reaction energy barrier, significantly restricting the commercial application of DMFCs. Therefore, developing MOR catalysts with high activity and stability is very important. In this paper, oxygen-functionalised activated carbon (FAC) with controllable oxygen-containing functional groups was prepared by adjusting the volume ratio of H₂SO₃/HNO₃ mixed acid, and Pd/AC and Pd/FAC catalysts were synthesised via the hydrazine hydrate reduction method. A series of characterisation techniques and electrochemical performance tests were used to study the catalyst. The results showed that when V(H₂SO₃):V(HNO₃) = 2:3, more defects were generated on the surface of the AC, and more oxygen-containing functional groups represented by C=O and C–OH were attached to the surface of the support, which increased the anchor sites of Pd and improved the dispersion of Pd nanoparticles (Pd NPs) on the support. At the same time, the mass–specific activity of Pd/FAC for MOR was 2320 mA·mg_Pd, which is 1.5 times that of Pd/AC, and the stability was also improved to a certain extent. In situ infrared spectroscopy further confirmed that oxygen functionalisation treatment promoted the formation and transformation of *COOH intermediates, accelerated the transformation of CO_L into CO_B, reduced the poisoning of CO_ads species adsorbed to the catalyst, optimised the reaction path and improved the catalytic kinetic performance. Full article

This work addresses for the first time the effect of anode serpentine channel depth on Methanol Electrolysis Cells (MECs) and Direct Methanol Fuel Cells (DMFCs) for improving performance of both devices. Anode plates with serpentine flow fields of 0.5 mm, 1.0 mm and 1.5 mm depths are designed and tested in single-cells to compare their behaviour. Performance was evaluated through methanol crossover, polarization and power density curves. Results suggest shallower channels enhance mass transfer efficiency reducing MEC energy consumption for hydrogen production at 40 mA∙cm⁻² by 4.2%, but increasing methanol crossover by 30.3%. The findings of this study indicate 1.0 mm is the best depth among those studied for a MEC with 16 cm² of active area, while 0.5 mm is the best for a DMFC with the same area with an increase in peak power density of 14.2%. The difference in results for both devices is attributed to higher CO₂ production in the MEC due to its higher current density operation. This increased CO₂ production alters anode two-phase flow, partially hindering the methanol oxidation reaction with shallower channels. These findings underscore the critical role of channel depth in the efficiency of both MEC and DMFC single-cells. Full article

Biodiesel, a renewable and environmentally friendly alternative to fossil fuels, has attracted significant attention due to its potential to reduce greenhouse gas emissions. However, high production costs and complex processing remain challenges. Heterogeneous catalysts have shown promise in overcoming these barriers by offering benefits, such as easy separation, reusability, low-cost raw materials, and the ability to reduce reaction times and energy consumption. This review evaluates key classes of heterogeneous catalysts, such as metal oxides, ion exchange resins, and zeolites, and their performance in transesterification and esterification processes. It highlights the importance of catalyst preparation methods, textural properties, including surface area, pore volume, and pore size, activation techniques, and critical operational parameters, like the methanol-to-oil ratio, temperature, time, catalyst loading, and reusability. The analysis reveals that catalysts supported on high surface area materials often achieve higher biodiesel yields, while metal oxides derived from natural sources provide cost-effective and sustainable options. Challenges, such as catalyst deactivation, sensitivity to feedstock composition, and variability in performance, are discussed. Overall, the findings underscore the potential of heterogeneous catalysts to enhance biodiesel production efficiency, although further optimization and standardized evaluation protocols are necessary for their broader industrial application. Full article

The procedure for the generation of azirinyl-substituted nitrile oxides by the reaction of 2-(diazoacetyl)-2H-azirines with tert-butyl nitrite while preserving the azirine ring has been developed. The [3+2] cycloaddition of azirinyl-substituted nitrile oxides to terminal acetylenes produced azirinyl(isoxazolyl)ketones with various substituents in position 3 of azirine and position 5 of isoxazole fragments in a 51–91% yield at room temperature in DCM. DFT calculations and experimental data are consistent with the assumption that the formation of azirinyl-substituted nitrile oxides is accelerated by the acid catalyst. Cycloadducts of nitrile oxides with aryl/hetarylacetylenes and DMAD can be obtained by catalysis with boron trifluoride etherate, which significantly expands the scope of application of the reaction. Expansion of the azirine ring of the prepared cycloadducts allows obtaining a wide range of structurally diverse functionalized isoxazole-containing heterocyclic hybrids. LED light induces isomerization of the azirinecarbonyl moiety of the azirinyl(isoxazolyl)ketones, resulting in the formation of a set of 3,5’-biisoxazoles in a 40–71% yield, while the catalytic reaction of the azirine moiety with 1,3-diketones opens the way to pyrrole- and isoxazole-containing hybrids. 2-(Isoxazole-3-ylcarbonyl)-3-arylazirines were also easily isomerized to 3-(oxazol-5-yl)isoxazoles in methanol in the presence of excess potassium carbonate at room temperature. Full article

A novel metal–organic framework based on zinc ions, designated as Zn-URJC-12, has been synthesized and applied for the first time in the cycloaddition reaction between carbon dioxide and epoxides. This MOF is constructed from two different organic linkers: 5-aminoisophthalic acid and 4,4′-biphenyldicarboxylic acid. The framework features –NH₂ functional groups coordinated to Zn(II) centers, as confirmed by single-crystal X-ray diffraction analysis. Zn-URJC-12 demonstrates exceptional chemical stability in polar organic solvents, such as methanol, while maintaining thermal stability up to 250 °C. The material exhibits high catalytic efficiency in the cycloaddition of CO₂ with epoxides, achieving yields of 100% and 76% for propylene oxide and allyl glycidyl ether, respectively. Additionally, Zn-URJC-12 maintains its structural integrity and catalytic performance during five successive reaction cycles. These findings underscore Zn-URJC-12 as a promising heterogeneous catalyst for the valorization of CO₂ into cyclic carbonates. Full article

Chymotrypsin inhibitors were initially considered mainly as anti-nutritional factors. However, the potential for their use as therapeutics has been recognized, particularly in the control of cancer, neurodegenerative diseases, and inflammatory processes. The search for new, effective, and safe chymotrypsin inhibitors has become important not only for food and feed safety reasons, but also in the search for new compounds with potential for use in the pharmaceutical industry. Oxidative stress is also an integral etiological factor in the development of the aforementioned pathological conditions. Antioxidants supplied with food can have an impact on reducing the probability of developing these diseases. Herbaceous plants are a valuable reservoir of biologically active chemical compounds, which can show both inhibitory effects against a number of enzymatic reactions and have antioxidant activity. The compounds found within them are also often characterized by higher bioavailability and safety than their synthetic analogs. In the present study, phytochemical characterization of plant materials Galium aparine L., Galium verum L., Solidago virgaurea L. and Solidago canadensis L. was performed, in order to search for new, potential substances with chymotrypsin inhibitor and antioxidant properties. Antioxidant and inhibitory activities against chymotrypsin were determined using effect-directed HPTLC. The total content of phenolic compounds and flavonoids and antioxidant activity were also determined in UV-Vis spectrophotometric tests. Both plant species showed antioxidant and chymotrypsin inhibitory activity. Among the methanol and methanol:water extracts, the extracts from Solidago sp. showed stronger inhibitory and antioxidant activity. However, in the case of dichloromethane extracts, Galium aparine inhibited chymotrypsin activity in a stronger manner than Solidago sp. The results indicate the application potential of compounds obtained from these plants as chymotrypsin inhibitors and antioxidant agents. Full article

In this study, the chemical compositions of PM_2.5 (particulate matter < 2.5 μm) and the molecular compositions of methanol-soluble organic carbon (MSOC) in suburban Shanghai during summer were measured to investigate the molecular characteristics of organic aerosol (OA) under high humidity. Diurnal variation analysis reveals the influence of relative humidity (RH) on secondary organic aerosol (SOA) components. Organosulfates (OSs), particularly nitrooxy-OSs, exhibit a positive correlation with increasing humidity rather than atmospheric oxidants in this high-humidity site. This suggests that high RH can promote the formation of OSs, possibly through enhancing particle surface area and volume, and creating a favorable environment for aqueous-phase or heterogeneous reactions in the particle phase. A considerable proportion of CHOS compounds may be derived from anthropogenic aliphatic hydrocarbon derivatives. These compounds exhibit slightly elevated daytime concentrations due to increased emissions of long-chain aliphatics from sources such as diesel combustion, as well as photochemically enhanced oxidation to OSs. In contrast, CHONS compounds increased at night, driven by high-humidity liquid-phase oxidation. Terpenoid derivatives accounted for 13.4% of MSOC and contributed over 40% to nighttime CHONS. These findings highlight humidity’s important role in driving daytime and nighttime processing of anthropogenic and biogenic precursors to form SOA, even under low SO₂ and NO_x conditions. Full article

As one of the key processes of photosynthesis, carbon fixation and reduction is one of the most important biochemical reactions on planet Earth. Yet, reducing oxidized carbon elements through directly harnessing solar energy by using water-soluble, simple enzymes continues to be challenging. Here, CO₂ and bicarbonate were found to be transformed into methanol by fluorescent protein mRuby by using light as the single energy input. The binding of substrates to mRuby chromophore was supported by crystallography and light spectrometry. Gas chromatography showed the generation of methanol in mRuby-bicarbonate aqueous solution upon sunlight illumination. Atomic-resolution serial structures of mRuby showed snapshots of the step-by-step reduction of bicarbonate and CO₂. The amino, imino, or carboxylate group of residues near the chromophore was within hydrogen bonding distances of the substrates, respectively. A decrease in fluorescence was observed upon binding of bicarbonate, and the energy liberated from fluorescence was presumably utilized for methanol production. This research represents an exciting example of sunlight-driven photobiocatalysis by water-soluble small proteins. The new, green, and sustainable mechanisms uncovered here indicated great promises to harness solar energy straightforwardly, for, i.e., fuel production and green chemistry. Full article

The hydrogen economy, associated with electrochemical water splitting, represents a promising pathway to mitigate reliance on fossil fuels. However, the efficiency of this process is constrained by the sluggish oxygen evolution reaction (OER) at the anode, with low commercial interests of the produced oxygen. As a promising solution, OER can be replaced with the methanol oxidation reaction (MOR), which not only accelerates the hydrogen evolution reaction (HER) but also yields valuable formate as a product, depending on the nature of the anode electrocatalysts. In this context, nickel selenides have emerged as highly efficient and cost-effective electrocatalysts due to their rich compositional diversity, tunable electronic structures, and superior conductivity. Additionally, nickel selenides exist in multiple stoichiometric and nonstoichiometric phases, and also in the engineering versatility for optimizing catalytic MOR performance. This review comprehensively presents the design principles of electrocatalysts, provides a strategy for the optimization of performance, and discusses the mechanistic understanding of nickel selenide-based electrocatalysts for coupled HER and MOR systems, particularly focusing on the MOR. By bridging fundamental insights with practical applications, it additionally highlights the latest advancements in their catalytic MOR performance, offering insights into their potential for future energy and chemical applications. Full article