Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Thiol-Functionalized Covalent Organic Frameworks as Thermal History Indictor for Temperature and Time History Monitoring

Various products, including foods and pharmaceuticals, are sensitive to temperature fluctuations. Thus, temperature monitoring during production, transportation, and storage is critical. Facile indicators are required to monitor temperature conditions via color changes in real time. This study aimed to prepare and apply thiol-functionalized covalent organic frameworks (COFs) as a novel indicator for monitoring thermal history and temperature abuse. The COFs underwent obvious color changes from bright yellow to purple after exposure to different temperatures for varying durations. The reaction kinetics are analyzed under isothermal conditions, which reveal that the order of reaction rates is k_−20°C < k_4°C < k_20°C < k_35°C < k_55°C. The activation energy (E_a) of the COFs is calculated using the Arrhenius equation as 50.71 kJ moL⁻¹. The COFs are capable of sensitive color changes and offer a broad temperature tracking range, thereby demonstrating their application potential for the monitoring of temperature and time exposure history during production, transportation, and storage. This excellent performance thermal history indicator also shows promise for expanding the application field of COFs.     

Removal of imidacloprid and acetamiprid from tea infusions by microfiltration membrane

Removal of imidacloprid and acetamiprid in tea infusions by microfiltration membrane using dead‐end model was investigated in the present study. The results showed that microfiltration significantly promoted the removal of both pesticides (P < 0.05) in tea infusions. Furthermore, the extent of removal was strongly influenced by the pore size of membrane, operational pressure and the concentrations of tea infusions. The initial concentration of imidacloprid and acetamiprid showed no significant effect on their removal rates. The maximum removal rates were 79.7% for imidacloprid and 81.9% acetamiprid. The changes in major chemical components of tea infusions after microfiltration were evaluated. The results indicated that microfiltration caused no considerable changes in total polyphenols and total free amino acids, and small but statistically significant losses (6.3–18.0%) of eight catechins and three methylxanthines when filtration volume reached to 200 mL. The present study validated the application of microfiltration as a potentially feasible and promising method for the removal of imidacloprid and acetamiprid residues from tea infusions.     

Highly active sites of low spin FeⅡN4species:The identification and the ORR performance

Over recent years,catalytic materials of Fe-N-C species have been recognized being active for oxygen reduction reaction(ORR).However,the identification of active site remains challenging as it generally involves a pyrolysis process and mixed components being obtained.Herein Fe₃C/C and Fe₂N/C samples were synthesized by temperature programmed reduction of Fe precursors in 15%CH₄/H₂and pure NH₃,respectively.By acid leaching of Fe₂N/C sample,only single sites of FeN₄species were presented,providing an ideal model for identification of catalytic functions of the single sites of FeN₄in ORR.A correlation was conducted between the concentration of Fe^ⅡN₄in low spin state by Mossbauer spectra and the kinetic current density at 0.8 V in alkaline media,and such a structure-performance correlation assures the catalytic roles of low spin Fe^ⅡN₄ species as highly active sites for the ORR.     

Preparation and characterization of mullite whisker reinforced ceramics made from coal fly ash

Ceramics with mullite whiskers were prepared from coal fly ash and Al₂O₃ raw materials, with AlF₃ used as an additive. The phase structures and microstructures of the ceramics were identified via X-ray diffraction and scanning electron microscopy, respectively. The results show that pickling of coal fly ash is an effective method for enhancing the flexural strength of ceramics. Sintering temperature and AlF₃ addition were also key factors influencing the creation of ideal ceramics. The ceramic made from pickled coal fly ash, 6?wt% AlF₃, and sintered at 1200?°C, exhibited the highest flexural strength of 59.1?MPa, and had a bulk density of 1.32?g/cm³ and porosity of 26.8%. The results show that ceramic materials made under these conditions are ideal candidates for manufacturing ceramic proppants for the exploitation of unconventional oil and gas resources.