Optimizing the stability and electrical transport properties of CeNbO4+δ-based oxide ceramics by regulating oxygen ion content

CeNbO_4+δ ceramics have attracted extensive research interest because of their unique mixed ion-electron transport characteristics and interesting structure-functional characteristics caused by the difference in oxygen ion content. Although the change of oxygen ion content brings rich redox properties, it also causes serious crystal transformation and abnormal electrical transport properties. In order to obtain stable structure and excellent electrical transport properties, the directional regulation of the oxygen ion content has been realized through introducing Al₂O₃ and high temperature aging. After 600 h of aging at 1073 K, the prepared composite ceramics not only obtain a stable structure without crystal transformation, but also show good negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K–1273 K, in which the linear fitting maximum Pearson's r of the relationship between lnρ and 1000/T can reach 99.97%. The proposed method provides a new thought for the design and application of high-temperature electronic ceramics.     

表面离子印迹聚合物金属离子吸附材料研究进展

离子印迹聚合物吸附材料对模板离子具有强识别能力，对其可实现高选择吸附，因而离子印迹技术常用于制备高选择性吸附材料。但传统方法制备的离子印迹吸附材料，因识别位点容易被包埋导致其吸附容量小、吸附-脱附速率低，而表面离子印迹技术则是采用模板离子和聚合单体直接在载体表面或附近区域构筑选择性识别位点，所有活性位点均暴露，从而有效地解决了上述问题。本文从技术原理与合成原料、制备工艺方法以及载体材料类型等方面对表面印迹聚合物吸附材料近期研究进展情况进行了概述。针对相关研究现状，从载体材料、功能单体、目标离子等角度分析和讨论了表面离子印迹聚合物吸附材料当前发展中的不足及其所面临的挑战，并对表面离子印迹技术发展趋势和前景进行了展望。     

Replacing Mg2+ by Fe2+ for RNA-Cleaving DNAzymes

It has been proposed that Mg²⁺ and Fe²⁺ are very similar in interacting with ribozymes and some protein-based enzymes, but their activities with DNAzymes have yet to be studied. Here, the activity of Fe²⁺ as cofactor for a few RNA-cleaving DNAzymes is investigated. 17E is a well-studied DNAzyme that is active in the presence of many different divalent metal ions; it is highly active with Fe²⁺ with an apparent K_d of 29.7±2.3 μm and a k_obs of 1.12±0.11 min⁻¹ in the presence of 1 mm Fe²⁺ at pH 7.5. Fe²⁺ has 21-fold higher activity than Mg²⁺. Six different DNAzymes are then tested, and only the DNAzymes active with Mg²⁺ (17E, 8–17, and E5) are active with Fe²⁺. Fe²⁺ has 25 and one- to twofold higher activity than Mg²⁺ for the 8–17 and E5 DNAzymes, respectively. In pH>7 buffer and in presence of air, 1 mm Fe²⁺ results in a nonspecific degradation of the DNA strand due to reactive oxygen species (ROS). Cleavage reactions in anoxic environment and antioxidant ascorbate can be used to overcome the effect of oxidation. The findings provide insights for potential DNAzyme catalysis in the early Earth, and they further support the similarity between Mg²⁺ and Fe²⁺ in enzyme catalysis.     

Layered Birnessite Cathode with a Displacement/Intercalation Mechanism for High-Performance Aqueous Zinc-Ion Batteries

Mn-based rechargeable aqueous zinc-ion batteries(ZIBs)are highly promising because of their high operating voltages,attractive energy densities,and eco-friendliness.However,the electrochemical performances of Mn-based cathodes usually suffer from their serious structure transformation upon charge/discharge cycling.Herein,we report a layered sodium-ion/crystal water co-intercalated Birnessite cathode with the formula of Na0.55Mn2O4·0.57H2O(NMOH)for high-performance aqueous ZIBs.A displacement/intercalation electrochemical mechanism was confirmed in the Mn-based cathode for the first time.Na+and crystal water enlarge the interlayer distance to enhance the insertion of Zn^2+,and some sodium ions are replaced with Zn^2+ in the first cycle to further stabilize the layered structure for subsequent reversible Zn^2+/H^+ insertion/extraction,resulting in exceptional specific capacities and satisfactory structural stabilities.Additionally,a pseudo-capacitance derived from the surface-adsorbed Na^+ also contributes to the electrochemical performances.The NMOH cathode not only delivers high reversible capacities of 389.8 and 87.1 mA h g^−1 at current densities of 200 and 1500 mA g^−1,respectively,but also maintains a good long-cycling performance of 201.6 mA h g^−1 at a high current density of 500 mA g^−1 after 400 cycles,which makes the NMOH cathode competitive for practical applications.     

Synthesis of SnO2@MnO2@graphite nanosheet with high reversibility and stable structure as a high-performance anode material for lithium-ion batteries

In this study, SnO₂@MnO₂@graphite (SMG) anode material is prepared via a facile ball-milling approach combined with hydrothermal treatment. SnO₂ and MnO₂ nanoparticles are evenly dispersed on numerous sheet-like graphite. MnO₂ can not only play a catalytic role for facilitating the conversion reaction of Sn/Li₂O to SnO₂, but also as a barrier to impede the coarsening of Sn in the composite. Meanwhile, graphite nanosheets could serve as an ideal volume expansion buffer and good electron conductor. Consequently, the SMG anode delivers superior reversible capacity of 1048.5 mAhg⁻¹, ideal rate capability of 522.2 mAhg⁻¹ at 5.0 A g^-1 and stable long-life cyclic performance of 814.8 mAhg⁻¹ at 1.0 A g^-1 after 1000 cycles. This result indicates that the incorporation of MnO₂, graphite nanosheet and SnO₂ have a great potential in enhancing the performance of SnO₂-based anode for battery applications.     

Synthesis of strontium (Sr) doped hydroxyapatite (HAp) nanorods for enhanced adsorption of Cr (VI) ions from wastewater

The development of high-efficiency adsorbents for heavy metal ion removal from wastewater is highly desirable and challenging due to their synthesis complexity and low adsorption capacities. Herein, we reported the synthesis of strontium (Sr) doped hydroxyapatite (HAp) for the increased Cr (VI) adsorption. The effects of pH, temperature, and time on adsorption performances were studied. As a result, the Sr-HAp nanorods can achieve a Cr (VI) adsorption capacity of 443 mg/g, which is significantly higher than that of HAp nanorods (318 mg/g). To better understand the adsorption mechanism, the Langmuir isotherm model was established. The modeling results indicated that Langmuir monolayer chemical adsorption contributed to the efficient Cr (VI) ion removal for Sr-HAp nanorods adsorbents. The surface area and surface functional groups (O–H) contributed to the different Cr (VI) adsorption capacities between HAp and Sr-HAp.     

Microstructural and electrical changes in Ca0.9R0.1CeNbMoO8 (R = Y,Sm, Nd,La) ceramics induced by rare-earth ion doping

Rare-earth ions doped Ca_0.9R_0.1CeNbMoO₈ (R = Y, Sm, Nd, La) ceramics have been successfully prepared by solid-state method, and their modifications to the microstructure and electrical properties are also investigated. The rare-earth ions doped ceramics exhibit the scheelite structure. With the increase in the radius of rare-earth ions, the lattice distortion and bond interaction will be enhanced, and the consistency of grain size will be reduced. The ceramics exhibit negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K-1273 K, and the activation energy decreases with the increase of the radius of rare-earth ions. Rare-earth ions doping can increase the content of Ce³⁺ ions and promote the conductivity of ceramics. Except for Sm³⁺-doped ceramics, the high-temperature aging rate of other ceramics is less than 2%. The existence of some metastable Sm²⁺ ions in Sm³⁺-doped ceramics not only increases the activation energy, but also reduces the high-temperature stability of the ceramics.     

Ultralow-threshold wideband-tunable single-mode ultraviolet lasing from lanthanide-doped upconversion nanomaterials

Ultraviolet (UV) lasers with dynamic wavelength-tunability and high monochromaticity are crucial in a multitude of practical applications yet still remarkable challenges. Here, we show wide wavelength-tuning of single-mode UV lasing based on lanthanide-doped upconversion nanoparticles (UCNPs). The rationally designed Yb³⁺/Er³⁺/Tm³⁺/Gd³⁺/Ce³⁺ co-doped multilayer UCNPs, which exhibits a broad gain spectrum with the full width of half maximum of around 57 nm in the UV regime, are developed. More importantly, by taking advantages of a diffraction grating as the tuning component, stable single-mode emission can be achieved in the UCNPs-based external-cavity-extended Fabry–Pérot laser at room temperature. Specifically, the lasing threshold is around 137 µJ cm^–2, which is two orders of magnitude lower than that in the previously reported articles. Precise wavelength-tuning from 310 to 363 nm can be realized by adjusting the Littrow angle. This achievement highlights a portable alternative to continuously wideband-tunable UV lasers and opens up new opportunities for constructing compact solid-state UV photon sources.     

Potassium ions stabilized hollow Mn-based prussian blue analogue nanocubes as cathode for high performance sodium ions battery

Mn-based Prussian blue analogue is regarded as one of the promising cathodes for sodium ions battery owing to its high theoretical capacity and low cost. However, the unstable structure during charging/discharging process and the poor cycle life hinder its commercial application. In this work, potassium ions stabilized hollow Mn-based Prussian blue analogue is synthesized through a simple sodium citrate assisted method using for cathode of sodium-ions batteries. Although unique hollow structure could suffer volume variation during charging/discharging process, the K⁺ is introduced to further stabilize its structure. The PBAs cathode exhibits a high reversible specific capacity of 128 mA h g^?1 at 50 mA and superior rate performance of 72 mA h g^?1 at a high current density of 3200 mA g^?1, which is attributed to its stable structure and enhanced sodium ions transport kinetics. Ex-situ XRD/Raman tests and electrochemical measurements further prove the synergistic effect of various alkali ions (K⁺/Na⁺) and unique hollow structure. They work together to improve the structural stability and promote sodium ions diffusion rate of Mn-based PBAs.     

基于三维纳米阵列结构的表面增强拉曼技术研究及其在痕量铀酰离子探测中的应用

表面增强拉曼散射(SERS)是一种新型痕量表征技术，其灵敏度高、样品用量少、特征谱易辨识，尤其适用于铀酰离子等危化品的探测。在过去十几年里, 纳米材料和纳米技术在新兴技术和SERS的应用方面获得了长足发展，将先进的纳米制造技术引入了SERS领域。本文总结了利用光刻、原子层沉积等技术，开发了一系列高质量的三维阵列纳米材料作为SERS基底，并应用于痕量铀酰离子的检测。其中，以Al₂O₃、HfO₂等惰性氧化物包裹修饰的银纳米棒三维阵列作为基底，灵敏度高，稳定性好，根据不同特征的拉曼振动频谱，可识别多个不同种态的铀酰离子，检出限低至nmol/L，具有潜在的实际应用价值。