Search Results (1,491)

In this study, Cu(II) complexes containing the bidentate ligand N,N-dimethylethylendiamine (dmen), i.e., [Cu^II(dmen)₂(CH₃COO)₂], [Cu^II(dmen)₂(NO₃)₂], and [Cu^II(dmen)₂Cl₂], were developed to explore molecular catalysis for the oxygen reduction reaction (ORR). Cyclic voltammetry and UV–vis spectroelectrochemical and electrochemical impedance spectroscopy experiments were performed in the absence and presence of oxygen. The UV–vis spectroscopy results suggested that the aforementioned Cu(II) complexes present an octahedral geometry in the solid state; meanwhile, they show a square pyramidal geometry in an aqueous solution. It is proposed that the chemical species [Cu^I(dmen)₂H₂O]⁺ reacts with O₂, exhibiting an outer-sphere electron transfer mechanism. The same UV–vis spectroelectrochemical response obtained with and without O₂ indicated a direct electron transfer from Cu(II) to Cu(I), with the regeneration of catalyst and the absence of other intermediate species. Among the reported compounds, [Cu(dmen)₂(NO₃)₂] exhibited the highest catalytic rate (TOF = 1.3 × 10⁴ s⁻¹). The impedance spectroscopy results showed that the resistance charge transfer (R_ct) of the redox pair Cu^II|Cu^I decreased in the presence of O₂ from 36.391 kΩ to 5.54 kΩ. For a better understanding of the effect of aliphatic amines on the ORR, a comparison with the complex [Cu(1,10-phen)₂NO₃]NO₃ is also presented. Full article

Micron-sized near-spherical α-Al₂O₃ powders are widely used as thermal fillers due to their high thermal conductivity, high packing density, good flowability, and low cost. During the high-temperature calcination, the resulting α-Al₂O₃ powders often exhibit an aggregated worm-like morphology owing to limitations in solid-state mass transfer. Researchers have employed various mineralizers to regulate the morphology of α-Al₂O₃ powders; however, the preparation of micron-sized highly spherical α-Al₂O₃ powders via solid-state calcination is still a great challenge. In this work, micron-sized near-spherical α-Al₂O₃ powders were synthesized through high-temperature calcination using hydratable alumina (ρ-Al₂O₃) as precursor with water-soluble mineralizer ammonium fluoroborate (NH₄BF₄). ρ-Al₂O₃ can undergo a hydration reaction with water to form AlO(OH) and Al(OH)₃ intermediates, serving as an excellent precursor. With the addition of 0.1 wt% NH₄BF₄, the product exhibits an optimal near-spherical morphology. Excessive addition (>0.2wt%), however, significantly promotes the transformation of α-Al₂O₃ from a near-spherical to a plate-like structure. Further studies reveal that the introduction of NH₄BF₄ not only modulates the crystal morphology but also effectively reduces the content of sodium impurities in the powder through a high-temperature volatilization mechanism, thereby enhancing the thermal conductivity of the powder. It is shown that the thermal conductivity of the micron-sized α-Al₂O₃/ epoxy resin composites reaches 1.329 ± 0.009 W/(m·K), which is 7.4 times that of pure epoxy resin. Full article

This study evaluates the impact of mineralogy, elemental composition, and reaction pathways on hydrogen (H₂) generation in seven ultramafic and mafic (basaltic) rocks. Experiments were conducted under typical low-temperature hydrothermal conditions (150 °C) and captured early and evolving stages of fluid–rock interaction. Pre- and post-interactions, the solid phase was analyzed using X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS), while Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to determine the composition of the aqueous fluids. Results show that not all geologic H₂-generating reactions involving ultramafic and mafic rocks result in the formation of serpentine, brucite, or magnetite. Our observations suggest that while mineral transformation is significant and may be the predominant mechanism, there is also the contribution of surface-mediated electron transfer and redox cycling processes. The outcome suggests continuous H₂ production beyond mineral phase changes, indicating active reaction pathways. Particularly, in addition to transition metal sites, some ultramafic rock minerals may promote redox reactions, thereby facilitating ongoing H₂ production beyond their direct hydration. Fluid–rock interactions also regenerate reactive surfaces, such as clinochlore, zeolite, and augite, enabling sustained H₂ production, even without serpentine formation. Variation in reaction rates depends on mineralogy and reaction kinetics rather than being solely controlled by Fe oxidation states. These findings suggest that ultramafic and mafic rocks may serve as dynamic, self-sustaining systems for generating H₂. The potential involvement of transition metal sites (e.g., Ni, Mo, Mn, Cr, Cu) within the rock matrix may accelerate H₂ production, requiring further investigation. This perspective shifts the focus from serpentine formation as the primary driver of H₂ production to a more complex mechanism where mineral surfaces play a significant role. Understanding these processes will be valuable for refining experimental approaches, improving kinetic models of H₂ generation, and informing the site selection and design of engineered H₂ generation systems in ultramafic and mafic formations. Full article

Gossypol, a polyphenolic naphthalene derivative and yellow polyphenolic pigment found in cotton seed glands, presents notable environmental, animal, and human health hazards. To screen for yeast strains capable of utilizing gossypol and to investigate their removal efficiency and mechanisms. Yeast strains capable of utilizing gossypol as the exclusive carbon source were isolated from cotton field soil. The identification of these strains involved assessment of colony morphology, physiological and biochemical characteristics, and phylogenetic analysis utilizing 26S rDNA gene sequences. Safety evaluations included hemolytic and antibiotic susceptibility tests. The growth responses of the selected strains to varying temperatures and pH levels were determined. Using cotton meal as the solid fermentation substrate, the effects of single factors on gossypol removal by the strains were determined. The intracellular and extracellular localization as well as the nature of the gossypol-removing active components in the strains were characterized, followed by an investigation into the molecular mechanism of gossypol removal using LC-MS analysis. A total of 17 gossypol-utilizing strains were isolated from cotton field soil samples, with strain ZYS-3 demonstrating superior removal capability. Strain ZYS-3 was identified as Meyerozyma guilliermondii, exhibiting no hemolytic activity and susceptibility to nine commonly used antifungal agents. The optimal growth parameters for this strain were determined to be a temperature of 30 °C and a pH of 5.0. In solid-state fermentation using cotton meal at 30 °C with initial fermentation conditions (10% corn flour added as an external carbon source, 40% moisture content, and 6% inoculum concentration) for 3 days, strain ZYS-3 achieved a gossypol removal rate of 73.57%. Subsequent optimization of the fermentation process, including the addition of 10% corn flour as an external carbon source, adjustment of moisture content to 55%, and inoculum concentration to 10%, resulted in an increased gossypol removal rate of 89.77% after 3 days of fermentation, representing a 16.2% enhancement over the initial conditions. Assessment of gossypol removal activity revealed that strain ZYS-3 predominantly removes gossypol through the secretion of extracellular enzymes targeting specific active groups (phenolic hydroxyl groups and aldehyde groups) within the gossypol molecule. These enzymes facilitate oxidation and elimination reactions, leading to the opening of the naphthalene ring and subsequent removal of gossypol. Full article

Nanocrystalline CoWO₄ sampled were synthesized using a simple mechanochemical approach and a solid-state reaction, respectively. The formation of nanocrystalline CoWO₄ was characterized by X-ray diffraction (XRD) and infrared spectroscopy (IR). The optical properties of the obtained samples were explored by diffuse reflectance UV–visible (DRS) and photoluminescence (PL) techniques. A milling speed of 850 rpm led to the direct synthesis of monoclinic CoWO₄ with a short reaction time (1 h). The complete reaction did not occur in the solid-state synthesis. The obtained samples had monoclinic crystal systems with different lattice parameters. The average crystallite sizes of CoWO₄ were in the range of 20 to 180 nm. The TEM investigation showed that the morphology of the CoWO₄ particles differed depending on the preparation conditions. The values of the determined optical bandgap of CoWO₄ were the range of 1.89 to 2.18 eV, according to diffusion reflectance spectroscopy in the ultraviolet-to-visible range. Broader blue–green emission spectra with peaks at 430 nm were observed for samples prepared via both routes. The CIE color coordinates of the CoWO₄ samples lay in the blue and purple regions. The quantum yields of the CoWO₄ samples synthesized after 1 h and 5 h milling times at 850 rom were 0.34 and 0.67%, respectively. This study proposes an affordable mechanochemical approach for blue–green phosphors that could possibly be used in various light-emitting diodes (LEDs). Full article

The development of a straightforward strategy for preparing organic fluorescent materials, fine-tuning white-light emission, and subsequently constructing white light-emitting diodes (LEDs) is of great significance. Herein, we report on the modulation of white-light emission and the fabrication of white LEDs using polyhedral oligomeric silsesquioxane (POSS)-based fluorescent hybrid porous polymers (HPPs) through simple physical blending. Two HPPs, namely HPP-1 and HPP-2, which emit blue and red light, respectively, were synthesized via the efficient Heck reactions of octavinylsilsesquioxane with 4,4′-dibromobiphenyl and 1,3,6,8-tetrabromopyrene. By physically doping of HPP-1 and HPP-2 in variable ratios in solvent suspensions, it was discovered that white-light emission is significantly influenced by the concentrations of the materials and the excitation wavelength. Similar findings were also observed in the solid-state physical doping. An ideal white light emission with a CIE coordinate of (0.33, 0.33) can be achieved when excited at 380 nm with a mass ratio of HPP-1 to HPP-2 of 1:2. Finally, the two HPPs were dispersed in polysiloxane matrices, and a white LED with a CIE coordinate of (0.42, 0.36) was obtained. The LED exhibited a color rendering index of up to 90 and a correlated color temperature of 2858 K, realizing warm white light emission. This simple and convenient white-light regulation strategy holds great promise for application in the development of novel white LEDs based on organic fluorescent porous materials. Full article

The reaction system of nanocrystalline iron carburization and carbon deposit formation as an example of a parallel chemical reaction was studied. The main measurement procedure was the Chemical Potential Programmed Reaction method, according to which the course of a chemical reaction in this particular case was controlled by the methane–hydrogen mixtures of precisely selected variable composition. The measurements were performed in a tubular differential flow reactor with thermogravimetric measurement and analysis of the gas phase composition at a temperature of 650 °C under atmospheric pressure. In the current research, by measuring the mass of the solid sample at changing carburizing potential and after balancing the reacting system, the reaction rates of parallel iron carburization and carbon deposit formation were precisely determined using the model of the reaction of a nanocrystalline substance with the gas phase in states close to chemical equilibrium. The reaction rate constants for those reactions were estimated as well based on model equations. Full article

Lithium (Li) ion sieve is considered to have great potential in the selective extraction of Li⁺ from complex Li⁺-containing brine owing to its cost-effectiveness, excellent adsorption performance, and environmental friendliness. Nevertheless, the defects of complex regulation and control of technological parameters in the preparation process of Li ion sieve and poor recycling efficiency limit its application. In this study, spinel-type H₄Ti₅O₁₂ ion sieves (HTO) were successfully prepared through a high-temperature solid-state method for recovering Li⁺ from aqueous resources. Through the experiment of optimizing the key preparation process parameters of HTO, it was found that the optimum preparation conditions were as follows: lithium ion source of CH₃COOLi‧H₂O, calcination temperature of 800 °C, and acid (HCl) washing concentration of 0.3 mol/L. The uptake of Li⁺ by HTO aligned with the pseudo-second-order kinetic model, which was a chemical adsorption process controlled by reversible Li–H ion exchange reaction. HTO exhibited extremely high regeneration cycle characteristics, and after five cycles, it retained 96.06% of its initial adsorption capacity. The present work highlighted that spinel-type HTO has high industrial application potential in the field of Li⁺ recovery from oilfield brine. Full article

Levoglucosenone (LGO) smoothly undergoes microwave-assisted hetero-Diels–Alder reactions with thiochalcones in THF solution at 60 °C. The studied reactions are completed after 10 min, and the expected tricyclic 2,3-dihydro-4H-thiopyran derivatives are formed in a highly regio- and moderately stereoselective manner via competitive exo- and endo-attacks of the 1-thiadiene moiety onto the activated C=C bond of dienophile LGO. Although eight isomers are possible, only the formation of exo,exo- (major) and exo,endo- (minor) cycloadducts was observed. In most cases, isomeric products were separated by preparative layer chromatography and identified by means of spectroscopic methods. Some of the cycloadducts were obtained as single crystalline solids, and X-ray analyses enabled unambiguous confirmation of their structures. In order to explain the observed selectivity of the studied hetero-Diels–Alder reactions, DFT studies were carried out to determine the thermodynamic and kinetic properties of all regio- and stereoisomers. The results of these calculations predict the preferred formation of the two experimentally observed isomers. In addition, remarkable details on the electronic structure of E-1,3-diphenylprop-2-en-1-thione and on involved and hypothetical transition states could be elucidated. Full article

Co-electrolysis of CO₂ and H₂O offers a promising route for efficient and controllable syngas production from greenhouse gases and water. However, the atomic-scale reaction mechanism remains elusive, especially on complex oxide surfaces. In this study, we employ density functional theory (DFT) to investigate the adsorption and activation of CO₂ and H₂O on the FeMoO-terminated (001) surface of Sr₂Fe_1.5Mo_0.5O₆ (SFM), a double perovskite of growing interest for solid oxide electrolysis. Our results show that CO₂ strongly interacts with surface lattice oxygen, adopting a bent configuration with substantial charge transfer. In contrast, H₂O binds more weakly at Mo sites through predominantly electrostatic interactions. Co-adsorption analyses reveal a bidirectional interplay: pre-adsorbed H₂O enhances CO₂ binding by altering its adsorption geometry, whereas pre-adsorbed CO₂ weakens H₂O adsorption due to competitive site occupation. This balance suggests that moderate co-adsorption may facilitate proton–electron coupling, while excessive coverage of either species suppresses activation of the other. Bader charge analysis, charge density differences, and projected density of states highlight the key role of Fe/Mo–O hybridized states near the Fermi level in mediating surface reactivity. These results, obtained for a perfect defect-free surface, provide a theoretical benchmark for disentangling intrinsic molecule–surface and molecule–molecule interactions, and offer guidance for designing high-performance perovskite electrocatalysts for CO₂ + H₂O co-electrolysis. Full article

Mechanochemistry has become a fundamental method in various sciences including biology and chemistry. Despite its popularity, the mechanisms behind mechanochemically induced reactions are not very well understood. In previous work, we investigated molecular-recognition processes of molecules capable of forming racemic phases in ball mill devices. Solid-state nuclear magnetic resonance (solid-state NMR) was used as the key technique to analyze such events. We now extended this study and focused on mechanochemically induced racemic-phase formations of two representative amino acids, alanine and serine, in a resonant acoustic mixer. The data reveal the importance of adding small amounts of solvents (here water) to facilitate the underlying solid-state molecular-recognition processes. The role of water therein is further studied by deuterium magic-angle spinning (MAS) NMR experiments, also revealing that resonant acoustic mixing (RAM) enables efficient hydrogen to deuterium exchange in enantiopure serine, paving the way to deuterate organic compounds in the RAM device. Full article

Mg₂TiO₄:Mn⁴⁺ (MTO:Mn⁴⁺) red phosphor has important applications in areas such as red LEDs and forensic science, but the preparation of MTO:Mn⁴⁺ through the solid-state reaction method requires a high sintering temperature. Herein, MTO:Mn⁴⁺ red phosphor was synthesized using the solid-state reaction method with LiCl flux, and its crystallographic structure and photoluminescence properties were studied to determine the influence of experimental parameters like the amount of fluxing agent added and sintering temperature in producing a bright red phosphor suitable for LEDs. The experimental results showed that samples with added LiCl could form pure MTO after sintering at 950 °C, whereas those without LiCl still contained a mixture of MTO and MgTiO₃, even when sintered at 1400 °C. The optimal performance was achieved with a sample doped with 0.2 mol% Mn⁴⁺, synthesized using 50 wt% LiCl flux and sintered at 950 °C for 12 h. This sample exhibited a broad excitation band and a narrow red emission band peaking at 662 nm, confirming its excellent luminescence properties. Furthermore, a prototype red LED fabricated with a 377 nm chip and MTO:0.2% Mn⁴⁺ phosphor achieved photoelectric conversion efficiency of 78.5% at a 100 mA drive current, confirming its viability for high-performance red LED manufacturing. Full article

Two new long-chain N-alkyl imidazole derivatives, 2-(1-octadecyl-imidazol-2-yl)pyridine and 2-(furan-2-yl)-1-(octadecane-1-yl)-1H-imidazole, were synthesized via the Radziszewski reaction followed by N-alkylation. This is the first report of furan-imidazole obtained by this route using furfuraldehyde as a renewable biomass-derived precursor. FTIR, 1D/2D solution NMR, and HRMS confirmed the structural elucidation, while XRD and solid-state ¹³C CPMAS NMR corroborated the crystal structures of the precursors. Notably, previously misassigned ¹H and ¹³C chemical shifts reported in the literature for pyridine and furan-imidazole precursors were corrected. Furthermore, ¹³C CPMAS NMR spectra of those precursors are reported here for the first time. These findings expand the scope of the Radziszewski reaction and provide new insights into the structural characterization of imidazole-based systems. Full article

Vanadium–titanium magnetite (VTM) is an iron ore abundantly available in China. The dominant utilization route is blast furnace smelting; however, Ti in the ore deteriorates sinter strength, making it urgent to clarify Fe-Ti-Ca interactions during sintering. In this work, single-phase FeTiO₃ and Fe₂TiO₄ were synthesized and each paired with CaO to fabricate diffusion couples. The couples were heated at 1200 °C for 30, 60, 90, and 120 min to investigate their interdiffusion behaviors and microstructure recombination mechanisms. The results show that, at 1200 °C, solid-state diffusion—not interfacial reaction—controls mass transfer in both FeTiO₃-CaO and Fe₂TiO₄-CaO systems. Distinct Fe-rich and Ti-rich sublayers appear within the reaction zone, and banded CaTiO₃ forms adjacent to the FeTiO₃/Fe₂TiO₄ matrices. The interdiffusion coefficients were determined to be 4.08 × 10⁻¹⁰ cm²·s⁻¹ and 7.81 × 10⁻¹⁰ cm²·s⁻¹, and the growth of the reaction layer follows a parabolic law, which can be expressed as x² = 2 × 1.562 × 10⁻⁹ t and x² = 2 × 0.8159 × 10⁻⁹ t, respectively. The coefficients of determination exceed 0.90, indicating reliable regression fits. Full article

W-type hexaferrites with compositions Ba_0.5Sr_0.5Zn_2-xMe_xFe₁₆O₂₇ (Me = Fe, Ni, Co, Cu, Mn; x = 1) and Ba_0.5Sr_0.5Zn_2−xMn_xFe₁₆O₂₇ (x = 0–2.0) were synthesized via solid-state reaction and optimized using a two-step calcination process to obtain single-phase or nearly single-phase structures. Their electromagnetic (EM) wave absorption properties were investigated by fabricating composites with 10 wt% epoxy and measuring the complex permittivity and permeability across two frequency bands: 0.1–18 GHz and 26.5–40 GHz. Reflection loss (RL) was calculated and visualized as two-dimensional (2D) maps with respect to frequency and sample thickness. In the 0.1–18 GHz range, only the Co-substituted sample exhibited strong ferromagnetic resonance (FMR) and broadband absorption, achieving a minimum RL of −41.5 dB at 4.84 GHz and a −10 dB bandwidth of 11.8 GHz. In contrast, the other Ba_0.5Sr_0.5Zn_2-xMe_xFe₁₆O₂₇ samples (Me = Fe, Mn, Ni, Cu) showed no significant absorption in this range due to the absence of FMR. However, all these samples clearly exhibited FMR characteristics and distinct absorption peaks in the 26.5–40 GHz range, particularly the Mn-substituted series, which demonstrated RL values below −10 dB over the 32.0–40 GHz range with absorber thicknesses below 1 mm. The FMR frequency varied depending on the substitution type and amount. In the Mn-substituted series, the FMR frequency was lowest at x = 1.0 and increased as x deviated from this composition. This study confirms the potential of Co-free W-type hexaferrites as efficient, cost-effective, and broadband EM wave absorbers in the 26.5–40 GHz range. Full article