Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Bi-templated grain growth maximizing the effects of texture on piezoelectricity

Templated grain growth is beneficial for piezoelectric materials, the properties of which become the best in their single crystalline form. Nevertheless, a textured ceramic prepared by a templated grain growth technique often fails in exhibiting as good properties as expected in single crystals even with a high degree of orientation factor. Here, we propose a new strategy for maximizing texturing effect by suppressing the growth of untextured matrix grains. The textured ceramics made by our method, so-called bi-templated grain growth, are featured by ultrahigh piezoelectric properties (d₃₃ = ～1,031 pC/N, d?g = ～59,000, k_p = ～0.76). A special emphasis is on the achieved electric-field-induced strain of 0.13 % at 1 kV/mm, which is as high as that of single crystals. This work demonstrates that not only the degree of texture but also the coarsening of untextured matrix grains should be well-controlled to best exploit the templated grain growth technique.     

Optimization of sensitizer concentration for upconversion photoluminescence of Yb3+/Er3+: La10W22O81 nanophosphor rods

Yb³⁺/Er³⁺codoped La₁₀W₂₂O₈₁ (LWO) nanophosphor rods have been successfully synthesized by a facile hydrothermal assisted solid state reaction method, and their upconversion photoluminescence properties were systematically studied. X-ray diffraction patterns revealed that the nanophosphors have an orthorhombic structure with space group Pbcn (60). A microflowers-like morphology with irregular hexagonal nanorods was observed using field emission scanning electron microscopy for the Yb³⁺(2 mol%)/Er³⁺(2 mol%):LWO nanophosphor. The shape and size of the nanophosphor and the elements along with their ionic states in the material were confirmed by TEM and XPS studies, respectively. A green upconversion emission was observed in the Er³⁺: LWO nanophosphors under 980 nm laser excitation. A significant improvement in upconversion emission has been observed in the Er³⁺: LWO nanophosphors by increasing the Er³⁺ ion concentration. A decrease in the upconversion emission occurred due to concentration quenching when the doping concentration of Er³⁺ ions was greater than 2 mol%. An optimized Er³⁺(2 mol%): LWO nanophosphor exhibited a strong near infrared emission at 1.53 μm by 980 nm excitation. The green upconversion emission of Er³⁺(2 mol%): LWO was remarkably enhanced by co-doping with Yb³⁺ ions under 980 nm excitation because of energy transfer from Yb³⁺ to Er³⁺. The naked eye observed this upconversion emission when co-doping with 2 mol% Yb³⁺. In order to obtain the high upconversion green emission, the optimized sensitizer concentration of Yb³⁺ ions was found to be 2 mol%. The upconversion emission trends were studied as a function of stimulating laser power for an optimized sample. Moreover, the NIR emission intensity has also been enhanced by co-doping with Yb³⁺ ions due to energy transfer from Yb³⁺ to Er³⁺. The energy transfer dynamics were systematically elucidated by energy level scheme. Colorimetric coordinates were determined for Er³⁺ and Yb³⁺/Er³⁺: LWO nanophosphors. The energy transfer mechanism was well explained and substantiated by several fluorescence dynamics of upconversion emission spectra and CIE coordinates. The results demonstrated that the co-doped Yb³⁺(2 mol%)/Er³⁺(2 mol%): LWO nanophosphor material is found to be a suitable candidate for the novel upconversion photonic devices.     

ZIF-12在检测抗坏血酸和L-色氨酸中的应用

采用室温搅拌法合成分子筛咪唑框架-12(ZIF-12),对其进行了X-射线衍射、电镜扫描和红外表征.将其制备成ZIF-12/gelatin/GCE电化学传感器,并采用循环伏安法对检测抗坏血酸、L-色氨酸及抗坏血酸和L-色氨酸进行同步检测.结果表明,ZIF-12作为电化学传感器材料应用于对抗坏血酸、L-色氨酸及抗坏血酸和L-色氨酸的同步检测,有良好的电化学响应.     

Enhanced the photocatalytic activity of B–C–N–TiO2 under visible light:Synergistic effect of element doping and Z-scheme interface heterojunction constructed with Ag nanoparticles

In order to enhance the photocatalytic activity of TiO₂ under visible light, Ag nanoparticles were introduced into tridoped B–C–N–TiO₂ (TT) catalyst by photoreduction deposition. Ag/B–C–N–TiO₂ (ATT) catalysts with the functions of reducing band gap and carrier recombination were prepared. At the same time, the effect of the amount of Ag on the photocatalytic performance of ATT catalyst was investigated. Through XRD, XPS, PL and other characterization methods, the (211)/(101)/Ag interface heterojunction mechanism similar to the traditional Z-scheme heterojunction was proposed. The intervention of Ag nanoparticles changed the P–N interface heterojunction between (211)/(101) to the (211)/(101)/Ag Z-scheme interface heterojunction. The results show that ATT catalyst exhibits the highest photocatalytic activity when the molar amount of Ag is 0.005% with the MB degradation rate of the ATT catalyst (0.01707 min^?1), which is 14.59 times of TiO₂ (0.00117 min^?1) and 2.02 times of TT (0.00847 min^?1). In addition, the four cycles efficiencies of ATT for MB degradation were all above 94.00%.This study reveals the possibility of construction of Z-scheme heterojunctions between precious metal nanoparticles and different interfaces of TiO₂, and provides a reference for the construction of Z-scheme interface heterojunctions.     

城市街道峡谷单侧自然通风研究进展

自然通风广泛存在于城市之中，了解城市自然通风建筑室内环境质量现状及存在的问题，是改善城市建筑室内环境质量的基础. 通过文献整理，首先研究城市街道峡谷中单侧自然通风的驱动因素，其次从建筑几何特征、通风能力、污染率、颗粒物浓度以及街谷设施等方面综述单侧自然通风的相关研究，最后提出建议. 研究表明，合理的展弦比、更好的城市布局以及精心的街谷设施设计能够最大限度地利用单侧自然通风，提升城市街道峡谷的室内环境品质.     

气藏平均地层压力跟踪计算新方法

平均地层压力是产能评价和动态分析的基础，准确、快速获取平均地层压力对高效开发气藏意义重大。基于地层压力随时间变化的规律，分析了平均地层压力的变化规律。研究结果表明：平均地层压力等效点仅随时间发生改变，平均地层压力的下降速率等于或者近似等于井底流压的下降速率。从封闭弹性驱动气藏的物质平衡方程出发，考虑偏差系数和井底流压随平均地层压力的变化，推导建立了平均地层压力跟踪计算新方法，根据生产数据可迭代计算平均地层压力。方法验证结果显示，采气速度和采出程度共同影响模型的计算结果。应用实例表明，跟踪计算法与压力恢复试井和物质平衡法之间的相对误差均较小，满足工程计算精度要求，且跟踪计算法不需依托生产测试数据，节约了测试费用，避免了测试占产。     

Nitrate Additives Coordinated with Crown Ether Stabilize Lithium Metal Anodes in Carbonate Electrolyte

Lithium metal anodes (LMAs) are promising for next-generation batteries but have poor compatibility with the widely used carbonate-based electrolytes, which is a major reason for their severe dendrite growth and low Coulombic efficiency (CE). A nitrate additive to the electrolyte is an effective solution, but its low solubility in carbonates is a problem that can be solved using a crown ether, as reported. A rubidium nitrate additive coordinated with 18-crown-6 crown ether stabilizes the LMA in a carbonate electrolyte. The coordination promotes the dissolution of NO₃⁻ ions and helps form a dense solid electrolyte interface that is Li₃N-rich which guides uniform Li deposition. In addition, the Rb (18-crown-6)⁺ complexes are adsorbed on the dendrite tips, shielding them from Li deposition on the dendrite tips. A high CE of 97.1% is achieved with a capacity of 1 mAh cm⁻² in a half cell, much higher than when using the additive-free electrolyte (92.2%). Such an additive is very compatible with a nickel-rich ternary cathode at a high voltage, and the assembled full battery with a cathode material loading up to 10 mg cm⁻² shows an average CE of 99.8% over 200 cycles, indicating a potential for practical use.     

Nanocrystallization and optical properties of CsPbBr3−xIx perovskites in chalcogenide glasses

The confinement of CsPbX₃ (X = Cl, Br, and I) perovskite nanocrystals (NCs) in a stabilized inorganic glass matrix is a new strategy for improving their long-term stability and promoting their applications in the optoelectronic field. Here, in situ nanocrystallization strategy is developed to precipitate CsPbBr_3?xI_x NCs with arbitrary I/Br ratio among an elaborately designed GeS₂–Sb₂S₃-based chalcogenide glass matrix. Spherical CsPbBr_3?xI_x NCs are homogeneously distributed in the glass matrix after thermal treatment. The photoluminescence (PL) spectra show that the emission peaks of CsPbBr_3?xI_x NCs can be tuned from 570 nm to 722 nm with the replacement of Br by I. The fs transient absorption (TA) spectra reveal that there exists some structural defects in the NCs, leading to short PL decay life. This work would shed light on confining CsPbX₃ NCs into glassy matrices, facilitating their future applications in photoelectronic fields.     

Spontaneous Directional Self-Cleaning on the Feathers of the Aquatic Bird Anser cygnoides domesticus Induced by a Transient Superhydrophilicity

In nature, the feathers of the goose Anser cygnoides domesticus stay superhydrophobic over a long term, thought as the main reason for keeping the surface clean. However, contaminants, especially those that are oleophilic or trapped within textures, cannot be removed off the superhydrophobic feathers spontaneously. Here, a different self-cleaning strategy based on superhydrophilic feathers is revealed that is imparted by self-coating of the amphiphilic saliva, which enables removing away low-surface-tension and/or small-size contaminants by forming directional water sheeting depending on their unique anisotropic microstructures. Particularly, the surface superhydrophilicity is switchable to superhydrophobicity upon exposure to air for maintaining a clean surface for a long time, which is further enhanced by coating with self-secreted preening oil. By alternate switching between a transient superhydrophilicity and a long-term stable superhydrophobicity, the goose feathers exhibit an integrated smart self-cleaning strategy, which is also shared by other aquatic birds. An attractive point is the re-entrant structure of the feathers, which facilitates not only liquid spreading on superhydrophilic feathers, but also long-term stability of the cleaned surface by shedding water droplets off the superhydrophobicity feathers. Thus, artificial self-cleaning microtextures are developed. The result renews the common knowledge on the self-cleaning of aquatic bird feathers, offering inspiration for developing bioinspired self-cleaning microtextures and coatings.