Search Results (27)

Layered Ruddlesden–Popper titanates HLnTiO₄ and H₂Ln₂Ti₃O₁₀ (Ln = La, Nd) have been exfoliated into nanosheets in aqueous tetrabutylammonium hydroxide and systematically investigated as hydrogen evolution photocatalysts. The nanosheets were tested both in as-prepared pristine form and after reassembly by two methods (simple filtration and precipitation by hydrochloric acid). The nanosheet-based samples demonstrated by up to 88 times greater photocatalytic performance in comparison with the bulk precursors and, after modification with a Pt cocatalyst, provided apparent quantum efficiency of hydrogen generation up to 14.2% in 1 mol.% aqueous methanol and 3.15% in pure water. It was established that the form in which the nanosheets are used strongly affects the hydrogen production efficiency: the latter typically decreases when moving from the pristine nanosheets to filtered ones and then to those restacked by hydrochloric acid, which is determined by the difference in their physical–chemical characteristics being influenced by the reassembly approach. Full article

The growing demand for efficient energy storage solutions has highlighted the potential of aqueous sodium-ion (Na⁺) batteries, known for their cost-effectiveness and environmental benefits. Despite their promise, challenges such as low specific capacities resulting from proton (H⁺) intercalation issues have limited their effectiveness. This study introduces a novel alkaline electrolyte environment using tetrabutylammonium hydroxide (TBAH) combined with chloride ions (Cl⁻) to improve the Na⁺ storage performance of manganese oxide (MnO₂) cathodes. The optimized electrolyte achieved a remarkable reversible capacity of 101 mAh g⁻¹ for γ-MnO₂ at a current density of 0.1 A g⁻¹, surpassing conventional aqueous solutions. The synergistic effect of TBAH and Cl⁻ not only suppresses H⁺ intercalation, but also prevents the formation of manganese hydroxide passivation layers during cycling. These advancements contribute to a better understanding of electrolyte design for high-performance Na⁺ storage electrodes, marking a significant step forward in aqueous sodium-ion battery technology. Full article

The simultaneous determination of arsenic and mercury species in human urine is critical for clinical diagnostics and therapeutic monitoring because it reduces the costs, time, and consumption of samples. This study proposes a method of utilizing high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for the concurrent analysis of arsenic and mercury species in urine samples. The separation was performed using a Hepu AR 5 μm C₁₈ (250 × 4.6 mm) column, employing a mobile phase composed of 0.1% L-cysteine, 5 mM NH₄H₂PO₄, and 4 mM tetrabutylammonium hydroxide (TBAH). The samples were diluted with water, and matrix interference was reduced through the application of a kinetic energy discrimination (KED) mode. Calibration curves for four arsenic species and three mercury species exhibited strong linearity within the range of 1–20 μg L⁻¹, with correlation coefficients (r) above 0.999. The limits of detection (LOD) ranged from 0.030 to 0.086 μg L⁻¹, while the limits of quantitation (LOQ) were observed to range from 0.10 to 0.29 μg L⁻¹. The spiking recoveries for all species varied from 87.0% to 110.3%, and the intra-day and inter-day relative standard deviations (RSD) were determined to be 1.1–6.0%, and 0.8–9.2%, respectively. These results indicate that the developed method achieves high precision, accuracy, and suitability for clinical applications, offering valuable insights for the diagnosis and treatment of heavy metal exposure. Full article

Water and oil do not mix. This essential statement of the hydrophobic effect explains why oil-in-water (O/W) emulsions are unstable and why energy must be supplied to form such emulsions. Breaking O/W emulsions is an exothermic event. Yet metastable O/W emulsions can be prepared with only water acting as the stabilizer by the adsorption of hydroxide ions formed from the enhanced autolysis of interfacial water. The heat of desorption of the hydroxide ions from the oil–water interface is not directly accessible but is obtained from the difference between the heat of reaction and the sum of the neutralization and interfacial heats when an emulsion is broken by the addition of acid. This experimental value of 28.4 k_BT is in good agreement with the theoretical estimate of 16–20 k_BT made from the fluctuation/correlation model of the hydrophobic force and the value of 14 k_BT obtained recently from surface spectroscopy. Subsequent verification of the force driving ions to hydrophobic surfaces is shown for tetrabutylammonium bromide with a dielectric decrement value of 26 M⁻¹ compared to 20 M⁻¹ for NaOH. The positive cation preferentially adsorbs at the oil–water interface over hydroxide ions in agreement with the predicted model. Full article

In this study, cellulose/Fe₃O₄ hydrogel microbeads were prepared through the sol–gel transition of a solvent-in-oil emulsion using various cellulose-dissolving solvents and soybean oil without surfactants. Particularly, 40% tetrabutylammonium hydroxide (TBAH) and 40% tetrabutylphosphonium hydroxide (TBPH) dissolved cellulose at room temperature and effectively dispersed Fe₃O₄, forming cellulose/Fe₃O₄ microbeads with an average diameter of ~15 µm. Additionally, these solvents co-dissolved cellulose and silk, allowing for the manufacture of cellulose/silk/Fe₃O₄ hydrogel microbeads with altered surface characteristics. Owing to the negatively charged surface characteristics, the adsorption capacity of the cellulose/silk/Fe₃O₄ microbeads for the cationic dye crystal violet was >10 times higher than that of the cellulose/Fe₃O₄ microbeads. When prepared with TBAH, the initial adsorption rate of bovine serum albumin (BSA) on the cellulose/silk/Fe₃O₄ microbeads was 18.1 times higher than that on the cellulose/Fe₃O₄ microbeads. When preparing TBPH, the equilibrium adsorption capacity of the cellulose/silk/Fe₃O₄ microbeads for BSA (1.6 g/g) was 8.5 times higher than that of the cellulose/Fe₃O₄ microbeads. The pH-dependent BSA release from the cellulose/silk/Fe₃O₄ microbeads prepared with TBPH revealed 6.1-fold slower initial desorption rates and 5.2-fold lower desorption amounts at pH 2.2 than those at pH 7.4. Cytotoxicity tests on the cellulose and cellulose/silk composites regenerated with TBAH and TBPH yielded nontoxic results. Therefore, cellulose/silk/Fe₃O₄ microbeads are considered suitable pH-responsive supports for orally administered protein pharmaceuticals. Full article

Nanosheets of layered perovskite-like oxides attract researchers as building blocks for the creation of a wide range of demanded nanomaterials. However, Ruddlesden–Popper phases are difficult to separate into nanosheets quantitatively via the conventional liquid-phase exfoliation procedure in aqueous solutions of bulky organic bases. The present study has considered systematically a relatively novel and efficient approach to a high-yield preparation of concentrated suspensions of perovskite nanosheets. For this, the Ruddlesden–Popper titanates HLnTiO₄ and H₂Ln₂Ti₃O₁₀ (Ln = La, Nd) have been intercalated by n-alkylamines with various chain lengths, exposed to sonication in aqueous tetrabutylammonium hydroxide (TBAOH) and centrifuged to separate the nanosheet-containing supernatant. The experiments included variations of a wide range of conditions, which allowed for the achievement of impressive nanosheet concentrations in suspensions up to 2.1 g/L and yields up to 95%. The latter were found to strongly depend on the length of intercalated n-alkylamines. Despite the less expanded interlayer space, the titanates modified with short-chain amines demonstrated a much higher completeness of liquid-phase exfoliation as compared to those with long-chain ones. It was also shown that the exfoliation efficiency depends more on the sample stirring time in the TBAOH solution than on the sonication duration. Analysis of the titanate nanosheets obtained by means of dynamic light scattering, electron and atomic force microscopy revealed their lateral sizes of 30–250 nm and thickness of 2–4 nm. The investigated exfoliation strategy appears to be convenient for the high-yield production of perovskite nanosheet-based materials for photocatalytic hydrogen production, environmental remediation and other applications. Full article

Herein, a series of novel sulfur-containing functionalized disiloxanes based on a low-cost and commercially available material, i.e., 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and various thiol compounds were prepared by thiol–epoxy click reaction. It was found that both lithium hydroxide (LiOH) and tetrabutylammonium fluoride (TBAF) have high catalytic activity after optimizing the reaction condition, and the reaction can be carried out with high yields, excellent regioselectivity, mild reaction condition, and good tolerance of functional groups. These compounds exhibit excellent nonconventional fluorescence due to the formation of coordination bonds between Si atoms and heteroatoms (e.g., S or N) and can emit blue fluorescence upon ultraviolet (UV) irradiation. These results demonstrate that the thiol–epoxy click reaction could promisingly act as an efficient organosilicon synthetic methodology to construct various organosilicon materials with novel structures and functionality, and thus their application scope will be significantly expanded. Full article

Cu–Mn mixed oxides are well known as active combustion catalysts. The common method for their synthesis is based on co-precipitation, with NaOH as a precipitant, and is burdened with the possibility of introducing undesired Na contamination. This work describes the use of two organic bases, tetrabutylammonium hydroxide and choline hydroxide, as precipitating agents in a novel alkali-free route for Cu–Mn–Al catalyst synthesis. To obtain fine crystalline precursors, which are considered advantageous for the preparation of active catalysts, co-precipitation was carried out in the presence of starch gel. Reference materials prepared with NaOH in the absence of starch were also obtained. Mixed oxides were produced by calcination at 450 °C. The precursors contained MnCO₃ doped with Cu and Al, and an admixture of amorphous phases. Those prepared in the presence of starch were less crystalline and retained biopolymer residues. The combustion of these residues during calcination enhanced the formation of larger amounts of the Cu_1.5Mn_1.5O₄ spinel phase, with better crystallinity in comparison to catalysts prepared from conventionally synthesized precursors. Tests of toluene combustion demonstrated that the catalysts prepared with starch performed better than those obtained in starch-free syntheses, and that the mixed oxides obtained by the alkali-free route were more active than catalysts prepared with NaOH. Catalytic data are discussed in terms of property–performance relationships. Full article

Synthetic Mg-Al hydrotalcites (HT) are environmentally friendly solid bases frequently applied as catalysts in base catalyzed reactions. The most common synthesis method, using NaOH as precipitant, is problematized by the possibility of introducing undesired Na contamination. Alkali-free synthesis is usually performed with NH₃aq, a precipitant which is less efficient in incorporation of Mg into HT lattice. In the present work, organic bases, tetrabutylammonium hydroxide and choline hydroxide, were successfully employed as precipitating agents in a new alkali-free route of Mg-Al HT synthesis. HT solids were also obtained with inorganic bases, NH₃aq and NaOH. Characterization with X-ray diffraction, elemental analysis, scanning electron microscopy, Fourier-transform infrared spectroscopy and thermogravimetry/differential scanning calorimetry, confirmed the formation of nanocrystalline HT compounds with all employed bases. HT prepared with NH₃aq exhibited an Mg deficit, which was detrimental to the catalytic activity in base catalyzed reactions. The effect was attributed to the tendency of Mg²⁺ to form ammine complexes, a conclusion supported by quantum mechanical calculations. HT prepared with NaOH showed the highest crystallinity, which was unfavorable for catalytic application. The addition of starch to the synthesis medium provided a means by which to diminish the crystal size of all HT precipitates. Catalytic tests of the Baeyer–Villiger oxidation of cyclohexanone demonstrated that the highest yields of ε-caprolactone were obtained with fine-crystalline HT catalysts prepared with organic bases in the presence of a starch template. Full article

In the present work, we report the results on exfoliation and coating formation of inorganic–organic hybrids based on the layered perovskite-like bismuth titanate H₂K_0.5Bi_2.5Ti₄O₁₃·H₂O that could be prepared by a simple ion exchange reaction from a Ruddlesden–Popper phase K_2.5Bi_2.5Ti₄O₁₃. The inorganic–organic hybrids were synthesized by intercalation reactions. Exfoliation into nanosheets was performed for the starting hydrated protonated titanate and for the derivatives intercalated by n-alkylamines to study the influence of preliminary intercalation on exfoliation efficiency. The selected precursors were exfoliated in aqueous solutions of tetrabutylammonium hydroxide using facile stirring and ultrasonication. The suspensions of nanosheets obtained were characterized using UV–vis spectrophotometry, dynamic light scattering, inductively coupled plasma spectroscopy, and gravimetry. Nanosheets were coated on preliminarily polyethyleneimine-covered Si substrates using a self-assembly procedure and studied using atomic force and scanning electron microscopy. Full article

Xanthates are by far the most widely used collectors in the froth flotation beneficiation of sulfide ores. However, the xanthate production process suffers from low yield, low productivity, long reaction time and environmental pollution. To address these issues, an effective method was developed for the synthesis of xanthates using phase transfer catalyst. Sodium isobutyl xanthate was synthesized from isobutyl alcohol ((CH₃)₂CHCH₂OH), sodium hydroxide (NaOH) and carbon disulfide (CS₂) with dichloromethane (CH₂Cl₂) as solvent and cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), tetrabutylammonium bromide (TBAB) and tetrabutylammonium chloride (TBAC) as phase transfer catalyst. The compound was characterized by elemental analysis, infrared spectrum, ¹H NMR and ¹³C NMR. The influencing factors on the content and yield of sodium isobutyl xanthate including phase transfer catalyst type, phase transfer catalyst dosage and reaction time were studied by single-factor experiments. The influencing factors on the product purity and yield including reaction temperature, solvent volume, material ratio and rotating speed were studied by orthogonal experiments. The results showed that when the amount of TBAC was 3.0%m_alcohol, the reaction temperature was 35 °C, the solvent volume was 3.5 V_alcohol, the rotating speed was 180 rpm, the reaction time was 4 h and the material ratio was n[(CH₃)₂CHCH₂OH]:n(NaOH):n(CS₂) = 1:1:1.10, the product yield could be up to 86.66% and the product purity reached 82.56%. Full article

This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH₄ + CO₂ hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH₄ + CO₂ hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines. Full article

Chiral tertiary α-hydroxyketones were synthesized with high enantiopurity by asymmetric decarboxylative chlorination and subsequent nucleophilic substitution. We recently reported the asymmetric decarboxylative chlorination of β-ketocarboxylic acids in the presence of a chiral primary amine catalyst to obtain α-chloroketones with high enantiopurity. Here, we found that nucleophilic substitution of the resulting α-chloroketones with tetrabutylammonium hydroxide yielded the corresponding α-hydroxyketones without loss of enantiopurity. The reaction proceeded smoothly even at a tertiary carbon. The proposed method would be useful for the preparation of chiral tertiary alcohols. Full article

Cellulose hydrogels are considered useful biocompatible and biodegradable materials. However, as few cellulose-dissolving solvents can be used to prepare cellulose hydrogel microspheres, the use of unmodified cellulose-based hydrogel microspheres for enzyme immobilization remains limited. Here, we prepared cellulose/Fe₂O₃ hydrogel microspheres as enzyme supports through sol-gel transition using a solvent-in-oil emulsion. Cellulose-dissolving solvents including 1-ethyl-3-methylimidazolium ([Emim][Ac]), an aqueous mixture of NaOH and thiourea, tetrabutylammonium hydroxide, and tetrabutylphosphonium hydroxide were used to prepare regular shaped cellulose/Fe₂O₃ microspheres. The solvent affected microsphere characteristics like crystallinity, hydrophobicity, surface morphology, size distribution, and swelling properties. The immobilization efficiency of the microspheres for lipase was also significantly influenced by the type of cellulose solvent used. In particular, the lipase immobilized on cellulose/Fe₂O₃ microspheres prepared using [Emim][Ac] showed the highest protein loading, and its specific activity was 3.1-fold higher than that of free lipase. The immobilized lipase could be simply recovered by a magnet and continuously reused. Full article

In this study, four ammonium hydroxide ionic liquids (AHILs) with varying alkyl chains were evaluated for their kinetic hydrate inhibition (KHI) impact on pure carbon dioxide (CO₂) and methane (CH₄) gas hydrate systems. The constant cooling technique was used to determine the induction time, the initial rate of hydrate formation, and the amount of gas uptake for CH₄-AHILs and CO₂-AHILs systems at 8.0 and 3.50 MPa, respectively, at 1 wt.% aqueous AHILs solutions. In addition, the effect of hydrate formation sub-cooling temperature on the performance of the AHILs was conducted at experimental temperatures 274.0 and 277.0 K. The tested AHILs kinetically inhibited both CH₄ and CO₂ hydrates at the studied sub-cooling temperatures by delaying the hydrate induction time and reducing the initial rate of hydrate formation and gas uptake. The hydrate inhibition performance of AHILs increases with increasing alkyl chain length, due to the better surface adsorption on the hydrate crystal surface with alkyl chain length enhancement. TPrAOH efficiently inhibited the induction time of both CH₄ and CO₂ hydrate with an average inhibition percentage of 50% and 84%, respectively. Tetramethylammonium Hydroxide (TMAOH) and Tetrabutylammonium Hydroxide (TBAOH) best reduced CH₄ and CO₂ total uptake on average, with TMAOH and Tetraethylammonium Hydroxide (TEAOH) suitably reducing the average initial rate of CH₄ and CO₂ hydrate formation, respectively. The findings in this study could provide a roadmap for the potential use of AHILs as KHI inhibitors, especially in offshore environs. Full article