Thioureas from 3-aminoquinazolin-4(3H)-one. 2. Unusual alkaline recyclization of 3-(N",N",S-trialkylisothioureido)quinazolin-4(3H)-ones into new 1,3,4-oxadiazoles

3-(N",N",S-trialkylisothioureido)quinazolin-4(3H)-ones obtained by the reactions of 3-(N",N"-dialkylthioureido)quinazolin-4(3H)-ones with alkyl halides undergo unusual recyclization into 5-(2-aminophenyl)-2-dialkylamino-1,3,4-oxadiazoles under the action of aqueous solutions of alkali, hydrazine, and primary aliphatic amines. A plausible mechanism of the recyclization was proposed.     

Study of the Influence of Alkaline Ions (Li, Na and K) on the Structure of the Silicate Entities in Silico Alkaline Sol and on the Formation of the Silico-Calco-Alkaline Gel

The study of silico-calco-alkaline gel is essential to warn against the degradation of concrete due to the alkali-silica reaction. In the laboratory, those gels are simulated by the destabilization of a silico-alkaline sol by calcium ions. Their speed of formation depends on the alkali species. The influence of alkaline ions (Li, Na and K) on the structure of silicate entities in sol and on the gel formation has been studied. The state of polymerization of the silico-alkaline sol was determined by NMR and depends on the alkali species and the molar ratio (Rm = [SiO2]/[A2O] with A = Li, Na or K). It appears that lithium enhances the polymerization. By scattering techniques (SAXS and ELS), the evolution of size and number of scattering particles during gelation can be determined from scattering curves with Guinier approximation. The mechanism of gelation appears as a hierarchic structure composed of several discrete sizes.     

Double bond isomerization of 5-vinylbicyclo[2.2.1]hept-2-ene to 5-ethylidenebicyclo[2.2.1]hept-2-ene over alkaline earth oxides

All the alkaline earth oxides exhibit activities for double, bond isomerization of 5-vinylbicyclo[2.2.1]hept-2-ene (VBH) to 5-ethylidenebicyclo[2.2.1]hept-2-ene (EBH) at a reaction temperature of 273 K. The order of the activity on the basis of unit weight of catalyst was CaO>MgO>SrO>BaO when compared under optimum pretreatment conditions. The E/Z ratio in the products is determined by the reaction temperature regardless of the type of catalyst; the ratios were 82/18 and 88/12 for the reaction temperatures of 323 and 273 K, respectively.     

Electrostatic Interactions Leading to Hierarchical Interpenetrating Electroconductive Networks in Silicon Anodes for Fast Lithium Storage

Recently, the frequency of combining MXene, which has unique properties such as metal-level conductivity and large specific surface area, with silicon to achieve excellent electrochemical performance has increased considerably. There is no doubt that the introduction of MXene can improve the conductivity of silicon and the cycling stability of electrodes after elaborate structure design. However, most exhaustive contacts can only improve the electrode conductivity on the plane. Herein, a MXene@Si/CNTs (HIEN-MSC) composite with hierarchical interpenetrating electroconductive networks has been synthesized by electrostatic self-assembly. In this process, the CNTs are first combined with silicon nanoparticles and then assembled with MXene nanosheets. Inserting CNTs into silicon nanoparticles can not only reduce the latter‘s agglomeration, but also immobilizes them on the three-dimensional conductive framework composed of CNTs and MXene nanosheets. Therefore, the HIEN-MSC electrode shows superior rate performance (high reversible capacity of 280 mA h⁻¹ even tested at 10 A g⁻¹), cycling stability (stable reversible capacity of 547 mA h g⁻¹ after 200 cycles at 1 A g⁻¹) and applicability (a high reversible capacity of 101 mA h g⁻¹ after 50 cycles when assembled with NCM622 into a full cell). These results may provide new insights for other electrodes with excellent rate performance and long-cycle stability.     

Effect of Dy3+‐doping on Electrochemical Properties of LiFePO4/C Cathode for Lithium‐Ion Batteries

Dy doping and carbon coating are adopted to synthesize a LiFePO₄ cathode material in a simple solution environment. The samples were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Their electrochemical properties were investigated by cyclic voltammetry (CV) and galvanostatic charge‐discharge tests. An initial discharge capacity of 153 mAh/g was achieved for the LiDy_0.02Fe_0.98PO₄/C composite cathode with a rate of 0.1 C. In addition the electronic conductivity of Dy doped LiFePO₄/C was enhanced to 1.9 × 10^?2 Scm^?1. The results suggest that the improvement of the electrochemical properties are attributed to the dysprosium doping and carbon coating which facilitates the phase transformation between triphylite and heterosite during cycling. XRD data indicate that doping did not destroy the lattice structure of LiFePO₄. To evaluate the effect of Dy substitution, cyclic voltammetry was used at room temperature. prepared. From Cv measurement a more symmetric curve with smaller interval between the cathodic and anodic peak current was obtained by Dy substitution. This denoted a decreasing of polarization with Dy substitution, which illustrated an enhancement of electrochemical performances.     

Presodiation Strategies for the Promotion of Sodium-Based Energy Storage Systems

Nowadays sodium-based energy storage systems (Na-based ESSs) have been widely researched as it possesses the possibility to replace traditional energy storage media to become next generation energy storage system. However, due to the irreversible loss of sodium ions in the first cycle, development of Na-based ESSs is limited. Presodiation, as a strategy of adding excess sodium ions to the system in advance, accomplishes the enhancement of electrochemical performance. In this minireview, different presodiation strategies applied in sodium-based energy storage systems will be summarized in detail, their functions and corresponding mechanisms will be discussed as well. Furthermore, the current novel application of presodiation method in other aspects of Na-based ESSs will be mentioned additionally. At last, in the view of present research status of presodiation, issues that can be mitigated are put forward and guidelines are given on how to deliberate in-depth presodiation technology in the future, dedicating to promote the further development of Na-based ESSs.     

Tunable and Specific Formation of C@NiCoP Peapods with Enhanced HER Activity and Lithium Storage Performance

The superior properties of nanomaterials with a special structure can provide prospects for highly efficient water splitting and lithium storage. Herein, we fabricated a series of peapodlike C@Ni_2?xCo_xP (x≤1) nanocomposites by an anion‐exchange pathway. The experimental results indicated that the HER activity of C@Ni_2?xCo_xP catalyst is strongly related to the Co/Ni ratio, and the C@NiCoP got the highest HER activity with low onset potential of ～45 mV, small Tafel slope of ～43 mV dec^?1, large exchange current density of 0.21 mA cm^?2, and high long‐term durability (60 h) in 0.5 m H₂SO₄ solutions. Equally importantly, as an anode electrode for lithium batteries, this peapodlike C@NiCoP nanocomposite gives excellent charge–discharge properties (e.g., specific capacity of 670 mAh g^?1 at 0.2 A g^?1 after 350 cycles, and a reversible capacity of 405 mAh g^?1 at a high current rate of 10 A g^?1). The outstanding performance of C@NiCoP in HER and LIBs could be attributed to the synergistic effect of the rational design of peapodlike nanostructures and the introduction of Co element.     

Filling the Charge–Discharge Voltage Gap in Flexible Hybrid Zinc-Based Batteries by Utilizing a Pseudocapacitive Material

The high charge–discharge voltage gap is one of the main bottlenecks of zinc–air batteries (ZABs) because of the kinetically sluggish oxygen reduction/evolution reactions (ORR/OER) on the oxygen electrode side. Thus, an efficient bifunctional catalyst for ORR and OER is highly desired. Herein, honeycomb-like MnCo₂O_4.5 spheres were used as an efficient bifunctional electrocatalyst. It was demonstrated that both ORR and OER catalytic activity are promoted by Mn^IV-induced oxygen vacancy defects and multiple active sites. Importantly, the multivalent ions present in the material and its defect structure endow stable pseudocapacitance within the inactive region of ORR and OER; as a result, a low charge–discharge voltage gap (0.43 V at 10 mA cm⁻²) was achieved when it was employed in a flexible hybrid Zn-based battery. This mechanism provides unprecedented and valuable insights for the development of next-generation metal–air batteries.