RESUMEN
High-entropy alloy nanoparticles (HEANs) possessing regulated defect structure and electron interaction exhibit a guideline for constructing multifunctional catalysts. However, the microstructure-activity relationship between active sites of HEANs for multifunctional electrocatalysts is rarely reported. In this work, HEANs distributed on multi-walled carbon nanotubes (HEAN/CNT) are prepared by Joule heating as an example to explain the mechanism of trifunctional electrocatalysis for oxygen reduction, oxygen evolution, and hydrogen evolution reaction. HEAN/CNT excels with unmatched stability, maintaining a 0.8V voltage window for 220 h in zinc-air batteries. Even after 20 h of water electrolysis, its performance remains undiminished, highlighting exceptional endurance and reliability. Moreover, the intrinsic characteristics of the defect structure and electron interaction for HEAN/CNT are investigated in detail. The electrocatalytic mechanism of trifunctional electrocatalysis of HEAN/CNT under different conditions is identified by in situ monitoring and theoretical calculation. Meanwhile, the electron interaction and adaptive regulation of active sites in the trifunctional electrocatalysis of HEANs were further verified by density functional theory. These findings could provide unique ideas for designing inexpensive multifunctional high-entropy electrocatalysts.
RESUMEN
In this study, aiming at the problem of low strength and high creep caused by medium-low modulus flexible resin based on the formulation design idea of high-molecular-weight epoxy resin (E12)-reinforced flexible epoxy-terminated urethane resin (EUR), a flexible epoxy prepreg resin with high strength and low bending creep was prepared to be suitable for hot melt processing technology. Flexible EUR was synthesized by grafting flexible polyurethane segments onto the epoxy side chain by urethane bonding. By adjusting the ratio of E12 and EUR, the effects of different ratios of the two components on the mechanical properties and viscoelasticity of the resin were systematically studied with dicyandiamide as the latent curing system. Research has found that when the E12 content is between 20%wt and 40%wt, the resin system has the best coating viscosity at 65 °C to 85 °C. The molecular weight and the content of aromatic heterocyclic groups of the resin determine the strength and creep behavior of the resin. When the content of E12 in the system is less than 50%wt, modulus and strength increase linearly, but after more than 50%wt E12 content, the modulus is almost unchanged and the strength begins to decrease. By increasing the content of E12 in the resin, the creep behavior of the resin is greatly reduced. When the content of E12 increases to 50%wt, the bending creep is the lowest.
RESUMEN
Lithium-sulfur (Li-S) batteries stand out for their high theoretical specific capacity and cost-effectiveness. However, the practical implementation of Li-S batteries is hindered by issues such as the shuttle effect, tardy redox kinetics, and dendrite growth. Herein, an appealingly designed covalent organic framework (COF) with bi-functional active sites of cyanide groups and polysulfide chains (COF-CN-S) is developed as cooperative functional promoters to simultaneously address dendrites and shuttle effect issues. Combining in situ techniques and theoretical calculations, it can be demonstrated that the unique chemical architecture of COF-CN-S is capable of performing the following functions: 1) The COF-CN-S delivers significantly enhanced Li+ transport capability due to abundant ion-hopping sites (cyano-groups); 2) it functions as a selective ion sieve by regulating the dynamic behavior of polysulfide anions and Li+ , thus inhibiting shuttle effect and dendrite growth; 3) by acting as a redox mediator, the COF-CN-S can effectively control the electrochemical behavior of polysulfides and enhance their conversion kinetics. Based on the above advantages, the COF-CN-S endows Li-S batteries with excellent performance. This study highlights the significance of interface modification and offers novel insights into the rational design of organic materials in the Li-S realm.
RESUMEN
A FeCo/DA@NC catalyst with the well-defined FeCoN6 moiety is customized through a novel and ultrafast Joule heating technique. This catalyst demonstrates superior oxygen reduction reaction activity and stability in an alkaline environment. The power density and charge-discharge cycling of znic-air batteries driven by FeCo/DA@NC also surpass those of Pt/C catalyst. The source of the excellent oxygen reduction reaction activity of FeCo/DA@NC originates from the significantly changed charge environment and 3d orbital spin state. These not only improve the bonding strength between active sites and oxygen-containing intermediates, but also provide spare reaction sites for oxygen-containing intermediates. Moreover, various in situ detection techniques reveal that the rate-determining step in the four-electron oxygen reduction reaction is *O2 protonation. This work provides strong support for the precise design and rapid preparation of bimetallic catalysts and opens up new ideas for understanding orbital interactions during oxygen reduction reactions.
RESUMEN
The detrimental growth of lithium dendrites and unstable solid electrolyte interphase (SEI) inhibit the practical application of lithium-metal batteries. Herein, atomically dispersed cobalt coordinate conjugated bipyridine-rich covalent organic framework (sp2 c-COF) is explored as an artificial SEI on the surface of the Li-metal anode to resolve these issues. The single Co atoms confined in the structure of COF enhance the number of active sites and promote electron transfer to the COF. The synergistic effects of the CoâN coordination and strong electron-withdrawing cyano-group can adsorb the electron from the donor (Co) at a maximum and create an electron-rich environment, hence further regulating the Li+ local coordination environment and achieving uniform Li-nucleation behavior. Furthermore, in situ technology and density functional theory calculations reveal the mechanism of the sp2 c-COF-Co inducing Li uniform deposition and promoting Li+ rapid migration. Based on these advantages, the sp2 c-COF-Co modified Li anode exhibits a low Li-nucleation barrier of 8 mV, and excellent cycling stability of 6000 h.
RESUMEN
A novel type of covalent organic frameworks has been developed by assembling definite cobalt-nitrogen-carbon configurations onto carbon nanotubes using linkers that have varying electronic effects. This innovative approach has resulted in an efficient electrocatalyst for oxygen reduction, which is understood by a combination of in situ spectroelectrochemistry and the bond order theorem. The strong interaction between the electron-donating carbon nanotubes and the electron-accepting linker mitigates the trend of charge loss at cobalt sites, while inducing the generation of high spin state. This enhances the adsorption strength and electron transfer between the cobalt center and reactants/intermediates, leading to an improved oxygen reduction capability. This work not only presents an effective strategy for developing efficient non-noble metal electrocatalysts through reticular chemistry, but also provides valuable insights into regulating the electronic configuration and charge behavior of active sites in designing high-performance electrocatalysts.
RESUMEN
The stiffness of composite laminates is easily affected by wrinkle defects. In this paper, a new effective analytical model was proposed to predict the three-dimensional equivalent elastic properties of multidirectional composite laminates with wrinkle defects. Firstly, a geometric model was established according to the microscopic characteristics of wrinkle defects. Then, based on the classical laminate theory and homogenization method, the constitutive equation and flexibility matrix of the wrinkle region were established. Finally, the equivalent stiffness parameters of unidirectional and multidirectional laminates were derived, and the effects of different wrinkle parameters and ply-stacking sequences on the stiffness of unidirectional and multidirectional laminates were studied by using the analytical model. The results show that the mechanical properties of the lamina and laminates are affected by the out-of-plane angle and in-plane angle of the wrinkle defects. The accuracy of the analytical model has been verified by the numerical model and other theoretical models, and it has the characteristics of few parameters and a high efficiency. The analytical model can be used to predict the stiffness of composite structures with wrinkle defects simply, effectively, and quantitatively. It can also be used as a tool to provide the mechanical response information of laminates with wrinkle defects.
RESUMEN
NASICON-type Na3Zr2Si2PO12 (NZSP) is supposed to be one of the best potential solid electrolytes with the characteristics of high ionic conductivity and safety for use in solid-state sodium batteries. Many methods have been used to enhance the ionic conductivity of NZSP, among which liquid phase sintering is a simple and rapid method. However, the transport mechanism of sodium ions in a NZSP electrolyte obtained by liquid phase sintering is not clear, and its application in solid-state batteries has not been confirmed. In this study, we synthesized NZSP with Na2SiO3 additives by liquid phase sintering to reduce the sintering temperature and improve the ionic conductivity. NZSP with 5 wt% Na2SiO3 (NZSP-NSO-5) achieves the highest ionic conductivity of 1.28 mS cm-1 and the lowest activation energy of 0.21 eV. Furthermore, the DFT study proves the Na+ diffusion mechanism and the decline in activation energy after addition. Lastly, the Na/Na3V2(PO4)3 battery with a Na2SiO3-added NZSP solid electrolyte exhibits a remarkably extended cycling capacity of 96.6% capacity retention after being cycled at 0.1 C 100 times. The liquid phase sintering with addition of low melting point salt compounds to electrolyte powder represents a rapid and straightforward technique for improving other ceramic electrolytes.
RESUMEN
Solar-driven CO2 reduction into gas fuels is desirable for a sustainable carbon cycle. To improve the photocatalytic activity of CO2RR, the unique rich oxygen (Vo) vacant hollow CeO2@MoSe2 is designed. The introduction of Vo is conducive to the capture of electrons by CO2 and promotes the process of photocatalytic CO2RR. The heterojunction formed by introducing the narrow band gap semiconductor MoSe2 increases the absorption range of visible light and improves the separation efficiency of photogenerated carriers. The hollow structure improves the CO2 adsorption capacity and improves the use of light effect. Therefore, the prepared H-Vo-CeO2@49.7 wt% MoSe2 exhibits enhanced photocatalytic activity for CO2RR. The yield of CH4 and CO is 10.2 µmol and 33.2 µmol in 4 h. Moreover, the photocatalytic mechanism is discussed through DFT and in-situ DRIFTS. This work provides new insights to the role of Vo in active CO2 photoconversion and exploits an important application of CO2 reduction.
RESUMEN
It is well-known that the acoustic stealth of an underwater vehicle composed of a non-watertight structure has been facing severe challenges. The origins of this effect are associated with the fact that the coupling between the water and the mechanical structure is not negligible because both sides are in the water. Along these lines, the idea of forward absorption and backward reflection was proposed in this work to address this issue. More specifically, a composite underwater acoustic metamaterial (AM) was designed based on different layers, namely a sound absorption layer and a sound insulation layer from the outside to the inside. The sound absorption layer was made of a soft rubber matrix with embedded steel scatterers (ESs) to enrich the coupled resonance effects, while the sound insulation layer was composed of hard rubber with a built-in cavity to improve the impedance mismatching between the AM and the water. The impact of the number and thickness of the embedded ESs on the acoustic performance of the AM was also thoroughly investigated via a finite element method (FEM). A fast non-dominated genetic algorithm (NAGA-II) with elite strategy was used to optimize the position and the size of the ESs. The optimization results revealed the high absorption at the forward incidence and the high reflection at the backward incidence. Thus, our work provides a novel and effective approach for improving the acoustic stealth of underwater vehicles composed of non-watertight structures.
