Search Results (73)

To address the challenge of ultra-deep desulfurization in fuels, a series of heteropolyacid-based poly(ionic liquid) catalysts (C4-PIL@PW, C8-PIL@PW, and C16-PIL@PW) were synthesized via radical polymerization and anion exchange methods. The prepared catalysts were characterized via FT-IR, XRD pattern, and Raman spectroscopy. Optimal reaction parameters (e.g., temperature, catalyst dosage, and O/S molar ratio) were systematically investigated, as well as the catalytic mechanism. The typical sample C8-PIL@PW exhibited exceptional oxidative desulfurization (ODS) performance, achieving a sulfur removal of 99.2% for dibenzothiophene (DBT) without any organic solvent as extractant. Remarkably, the sulfur removal could still retain 89% after recycling five times without regeneration. This study provides a sustainable and high-efficiency catalyst for ODS, offering insights into fuel purification strategies. Full article

This work studies the effect of mesostructured silica–zirconia–tungstophosphoric acid (SiO₂-ZrO₂-TPA) composites used as catalysts in the synthesis of nifedipine by the Hantzsch methodology. The selectivity for nifedipine is determined, along with that of secondary products that may form depending on the reaction conditions. The materials were synthesized via the sol–gel method and characterized by N₂ adsorption–desorption isotherms, infrared spectroscopy (FT-IR), ³¹P solid-state nuclear magnetic resonance (NMR-MAS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), and potentiometric titration. The characterization results from the XPS spectra showed that as the Si/Zr ratio drops, the Si-O-Si signal size decreases, while the Zr-O signal size increases. Characterization by titration indicated that an increase in the total acidity of the material, resulting from support modification with tungstophosphoric acid (H₃PW₁₂O₄₀, TPA), enhances the reaction yield. The catalytic activity in the solvent-free Hantzsch reaction was evaluated under thermal heating and microwave irradiation. The experiments conducted at 80 °C achieved a maximum yield of 57% after 4 h of reaction using the Si20Zr80TPA30 catalyst (50 mg), while by microwave heating, the yield significantly improved, reaching 77% in only 1 h of reaction. This catalyst exhibited stability and reusability without significant loss of activity up to the third cycle. Depending on the type of material and the reaction conditions, it is possible to modify the selectivity of the reaction, obtaining a 1,2-dihydropyridine isomeric to nifedipine. Reaction intermediates and other minor secondary products that may be formed in the process were also evaluated. Full article

In this study, a statistical analysis of results reported in the literature was conducted through a 2ⁿ experimental design on the synthesis of bifunctional catalysts used in the production of lighter fuels, aiming for optimization while considering factors such as support (bentonite and vermiculite), acidity modifier (zirconium and cerium), metal (tungsten and molybdenum), metal content (5% and 10%), promoter (nickel and cobalt), and heteropolyacids (tungstophosphoric acid and molybdophosphoric acid), identifying their influence on textural properties and catalytic performance. Regarding the textural properties, vermiculite proved to be the most favorable support due to its high porosity. It was also established that the implemented metals impart positive characteristics to the catalysts due to their various properties; however, incorporating large amounts led to an adverse effect by clogging the pores. Catalytic performance was analyzed in isomerization and cracking reactions, which were enhanced by the use of cerium due to the presence of Brønsted acid sites and molybdenum for its stability. In this way, the statistical analysis conducted in this study was crucial for identifying the influence of key factors on the textural properties and catalytic performance of bifunctional catalysts. Using a 2ⁿ experimental design allowed for a systematic evaluation of variables reported in the literature, such as support, acidity modifiers, metals, metal content, promoters, and heteropolyacids. Full article

The use of tomato plant residues (i.e., stems, leaves, etc.) as a substrate for catalytic pyrolysis of biomass was investigated. A comprehensive study was conducted to investigate the impact of catalysts on the performance of different pyrolysis fractions (i.e., gas, biosolid, waxes, and bioliquid) as well as the distribution of products within the bioliquid. The catalysts employed in this study were derived from two distinct types of zirconia. The first type was synthesized by a conventional sol-gel method, while the second type was prepared with a modified method aimed at improving the presence of mesopores. This modification involved the incorporation of Pluronic 123. These materials were designated ZrO₂ and ZrO₂P25, respectively. Both types of zirconia were used as supports for tungstophosphoric acid (H₃PW₁₂O₄₀, TPA), a heteropolyacid with a Keggin structure, in the preparation of catalysts with strong acid sites. The results demonstrated that the bioliquid yield of the non-catalytic fast pyrolysis of tomato plant waste was approximately 23% and that the obtained bioliquid contained a wide variety of molecules, which were detected and quantified by GC-MS. In the presence of the catalysts, both the bioliquid yield and the distribution of bioliquid products were substantially modified. Furthermore, the possible sugar degradation pathways leading to the formation of the molecules present in the pyrolytic bioliquids were thoroughly examined. The results obtained from this study indicate that the physicochemical characteristics of the catalysts, specifically their pore size and acidity, have a significant impact on the selectivity of the catalytic processes towards valuable molecules, including anhydro-sugars and furanic derivatives such as furfural and furfuryl alcohol. Full article

In this work, tin and zinc salts of silicotungstic and phosphotungstic acids were synthesized, characterized, and tested as catalysts for esterification reactions of glycerol with acetic acid (HOAc) to produce glycerol esters such as monoacetyl glycerol (MAG), which are used as additives in the pharmaceutical and food industries and in the manufacturing of explosives, or, in the case of di- or triacetyl glycerol (DAG and TAG), green bioadditives for diesel or gasoline. The activity of metal-exchanged salts (Zn, Sn) in H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀ heteropolyacids was evaluated in esterification reactions at room temperature. Among the catalysts tested, Sn_2/3PW₁₂O₄₀ was the most active and selective toward the glycerol esters. The process’s selectivity can be controlled by changes to reaction conditions. The maximum selectivitiesy of DAG and TAG were 60% and 30%, respectively, using a 1:3 molar ratio of glycerol/HOAc and a Sn_3/2PW₁₂O₄₀/673 K catalyst load of 0.4 mol%. Under these conditions, a glycerol conversion rate of 95% was observed and selectivity towards DAG and TAG was observed at 60% and 30%, respectively. The results were achieved after an 8 h reaction at a temperature of 333 K. The Sn_3/2PW₁₂O₄₀/673 K catalyst demonstrated the highest efficiency, which was attributed to its higher degree of acidity. Full article

In the present work, the epoxidation of fatty acid methyl esters (biodiesel or FAMEs) with an iodine number of 96.4 g/100 g and containing approximately 11% palmitic acid, 4% stearic acid, 51% oleic acid, 25% linoleic acid, and 5% linolenic acid was studied with an aqueous H₂O₂ solution and different quaternary phosphonium salts (QPSs) combined with the phosphotungstic heteropolyacid (HPA) H₃PW₁₂O₄₀ in a biphasic system. The effect of the molar ratio of H₂O₂:C=C on the epoxidation of FAMEs was investigated. The effect of the molar ratio of H₂O₂:C=C on the epoxy number (EN) and iodine number (IN) was measured. Multiple regression analysis methods were used to determine the regression model describing the influence of the various independent variables. In the results obtained, it was found that the highest yields were obtained for [P6][Phosf]. The optimum conditions for the epoxidation process with the systems used were a time range of 30 ± 4 min and a H₂O₂/double bond molar ratio in the range of 1.8 ± 0.2. The formation of epoxidised fatty acid methyl esters (E-FAMEs) was confirmed by FT-IR, ¹H NMR and ¹³C NMR analyses. In the FT-IR spectrum of the E-FAMEs, epoxy ring vibration signals were identified at 826 cm⁻¹. In the ¹H NMR spectrum, signals appeared in the range of 3.25–3.00 ppm, corresponding to epoxy ring formation in biodiesel, and in the range of 60–55 ppm in the ¹³C NMR spectrum. Full article

This paper describes the methodology of the preparation and analyses of the structure and anticorrosion properties of silane coatings modified with poly(3,4-ethylenedioxythiophene) (PEDOT) with phosphododecamolybdic acid (PMo₁₂). Protective coatings, consisting of vinyltrimethoxysilane (VTMS), PEDOT powder with PMo₁₂ admixture (at different concentrations), and ethanol, were deposited on X20Cr13 and 41Cr4 steels by immersion. The physicochemical properties of these silane coatings (e.g., surface morphology, thickness, roughness, and adhesion to the substrate) were elucidated using a digital microscope, a Fourier transform infrared spectrophotometer with attenuated total reflectance, and various electrochemical diagnostic techniques. Protective properties were assessed in acidified sulfate solutions with and without chloride ions (pH 2). Experimental results have shown that this coating displayed the effective protection of steel against general and pitting corrosion, stabilized the corrosion potential in the passive state, and provided barrier protection. Full article

The industrial processes used to produce paper and cellulose generate many lignocellulosic residues. These residues are usually burned to produce heat to supply the energy demands of other processes, increasing greenhouse gas emissions and resulting in a high environmental impact. Instead of burning these lignocellulosic residues, they can be converted into saccharides, which are feedstock for high-value products and biofuels. Keggin heteropolyacids are efficient catalysts for obtaining saccharides from cellulose and hemicellulose and converting them into bioproducts or biofuel. Furfural, 5-hydroxymethylfurfural, levulinic acid, and alkyl levulinates are important platform molecules obtained from saccharides and raw materials in the biorefinery processes used to produce fine chemicals and biofuels. This review discusses the significant progress achieved in the development of the processes based on heteropolyacid-catalyzed reactions to convert biomass and their residues into furfural, 5-hydroxymethylfurfural, levulinic acid, and alkyl levulinates in homogeneous and heterogeneous reaction conditions. The different modifications that can be performed to a Keggin HPA structure, such as the replacement of the central atom (P or Si) with B or Al, the doping of the heteropolyanion with metal cations, and a proton exchange with metal or organic cations, as well as their impact on the catalytic activity of HPAs, are detailed and discussed herein. Full article

The combustion of fuel with high sulfur concentrations produces a large number of sulfur oxides (SO_x), which have a range of negative effects on human health and life. The preparation of catalysts with excellent performance in the oxidative desulfurization (ODS) process is highly effective for reducing SO_x production. In this paper, cross-linked polyvinylimidazole (VE) was successfully created using a simple ontology aggregation method, after which a catalyst of polyvinylimidazolyl heteropolyacid clusters (VE-HPA) was prepared by adding heteropolyacid clusters. Polyvinylimidazolyl-phosphotungstic acid (VE-HPW) showed an outstanding desulfurization performance, and the desulfurization efficiency reached 99.68% in 60 min at 50 °C with H₂O₂ as an oxidant. Additionally, the catalyst exhibited recyclability nine consecutive times and remained stable, with a removal rate of 98.60%. The reaction mechanism was eventually proposed with the assistance of the free radical capture experiment and GC-MS analysis. Full article

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H₃PW₁₂O₄₀, HPW) supported on TiO₂ combined with a Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. In this work, different types of TiO₂ were used as a support to study the effect of changes in the structure of the TiO₂ support on the acidity and dispersion of HPW. Various TiO₂ supports with different structural and surface characteristics have been studied and the results indicate that: (i) the crystallinity and crystallite size of the primary particles of the HPW units depend on the TiO₂ support; (ii) the pore size distribution of the TiO₂ support affects the surface segregation of the heteropolyacids; and (iii) changes in the supported HPW acid catalysts do not significantly alter the crystal structure of the CuO and ZnO phases after contact with CZA in bifunctional catalysts. The activity results indicate that the variation in the intrinsic activity of the Cu-ZnO_x centers in the bifunctional catalysts for direct DME synthesis is minimal due to the limited alteration of the crystal structure of the centers. Full article

Among the different polyoxometalate compounds, Keggin heteropolyacids have been extensively used as catalysts in several acid-catalyzed reactions, due to their strong strength of Bronsted acidity. These metal–oxygen clusters have a highly versatile structure that allows their conversion to derivatives, which are catalysts that are much more efficient than their precursors, with a greater catalytic activity in a plethora of reactions of industrial interest. Particularly, due to the inevitable exhaustion of fossil sources, reactions to valorize biomass have attracted significant attention, since it is a precious renewable raw material that can provide fine chemicals or fuels, minimizing our dependence on petroproducts. Biorefinery processes can produce platform molecules to achieve this goal. In this review, the recent advances achieved in the development of routes to converting biomass feedstocks to levulinic acid and furfural, which are valuable ingredients in biorefinery processes, using Keggin heteropolyacid catalysts were assessed. Full article

In this work, a series of vanadium-substituted phosphomolybdic acids were synthesized and tested as the catalysts for the synthesis of solketal, a green fuel bioadditive, from the condensation reaction of glycerol with acetone. The objective was to demonstrate that an easily synthesizable solid catalyst can efficiently promote glycerol condensation with acetone at room temperature. The activity of pristine heteropolyacid (i.e., H₃PMo₁₂O₄₀) and its vanadium-substituted cesium salts (Cs_3+nPMo_12-nV_nO₄₀; n = 0–3) was evaluated in condensation reactions carried out at room temperature. Among the catalysts tested, Cs₄PMo₁₁VO₄₀ was the most active and selective towards a five-member ring solketal isomer (dioxolane). A high yield of solketal (i.e., 95% conversion and 95% selectivity to solketal) was achieved in glycerol condensation with acetone at room temperature within a short reaction time (2 h). The influence of the main reaction parameters, such as the acetone–glycerol molar ratio, catalyst load, and reaction temperatures, was investigated. The greatest activity of the Cs₄PMo₁₁VO₄₀ catalyst was correlated to its greatest acidity. Full article

The composites of heteropolyacids (H₃PW₁₂, H₃PMo₁₂) incorporated into amine-functionalized silica materials were used for the first time as heterogeneous catalysts in the valorization of glycerol (a major waste from the biodiesel industry) through acetalization reaction with acetone. The polyoxotungstate catalyst H₃PW₁₂@AptesSBA-15 exhibited higher catalytic efficiency than the phosphomolybdate, achieving 97% conversion and 97% of solketal selectivity, after 60 min at 25 °C, or 91% glycerol conversion and the same selectivity, after 5 min, performing the reaction at 60 °C. A correlation between catalytic performance and catalyst acidity is presented here. Furthermore, the stability of the solid catalyst was investigated and discussed. Full article

A novel photochromic heteropolyacid-based composite film consisting of phosphomolybdic acid (PMoA), ZnO, and polyvinylpyrrolidone (PVP) was fabricated by a sol–gel process. The microstructure and photochromic properties of the PMoA/ZnO/PVP were characterized via Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible spectroscopy (UV-Vis). The FTIR spectra showed that the basic structures of ZnO and PVP, and the Keggin structure of PMoA in the PMoA/ZnO/PVP composite film, had not been destroyed during the preparation. The TEM images demonstrated that ZnO presented a rod-like structure, while PMoA was spherical, and many PMoA balls adhered to the surface of the ZnO rods. The XPS spectra of Mo 3d indicated that the valency of Mo atoms in the PMoA/ZnO/PVP was changed by visible light exposure. After visible light irradiation, the PMoA/ZnO/PVP varied from slight yellow to blue, while undergoing an opposite color change upon heating. The discoloration mechanism of the PMoA/ZnO/PVP was consistent with the photoelectron transfer mechanism. Full article

The esterification of oleic acid was applied in order to screen the suitability of a series of phosphotungstic-based Wells-Dawson types of compounds as potential catalysts in the heterogeneous transesterification of sunflower waste cooking oil. This test reaction indicated that the phosphotungstic Wells-Dawson heteropolyacid H₆P₂W₁₈O₆₂·xH₂O, dispersed on titania oxide in a loading of 15 mg per m² of oxide support (named 42% HPA/TiO₂) and possessing exclusively Brønsted acid sites, was the most promising among the screened materials. In addition, the application of a nonlinear analysis methodology to find a surface that fits the specific activity of the oleic acid esterification with methanol at various temperatures, weights of catalyst, molar ratios of substrates, and stirring speeds, and also considering the active phase desorption out of the catalyst’s surface, allowed determining the optimum operative conditions that were applied in the transesterification of the waste cooking oil afterwards. The transesterification of the waste cooking oil at 60 °C and 1:9 WCO: methanol molar ratio in a batch reactor under stirring at 650 rpm for 3 h, catalyzed with 0.25 wt% of 42% HPA/TiO₂ (20.0 g of oil and 49.6 mg of catalyst), presents 74.6% of conversion of glycerides and 74.4% yield towards fatty acid methyl esters. The catalyst was recovered and reused several times, maintaining a fairly constant catalytic performance. Full article