Oxygen vacancy-induced short-range ordering as a sole mechanism for enhanced magnetism of spinel ZnFe2O4 prepared via a one-step treatment

Despite being difficult to identify, extremely dilute oxygen vacancies have been widely reported to play an important role in enhancing magnetism in ZnFe₂O₄. The mechanisms underlying this enhanced magnetism have not been well understood for a long time and remain controversial because the formation of oxygen vacancy-rich ZnFe₂O₄ can be accompanied by changes in the chemical/physical characteristics, especially the composition, particle size, surface morphology and cation distribution, which can significantly affect the magnetization. An open and important question is whether and to what extent the enhanced magnetization can be attributed only to oxygen vacancies. In this study, the relationship between the magnetization and oxygen vacancies in ZnFe₂O₄ was definitively determined by using a carefully designed “shake-and-heat” treatment to prepare vacancy-rich samples while keeping the other crystal/surface parameters constant. Compared to the nearly vacancy-free paramagnetism samples, the vacancy-rich samples exhibited a higher magnetization of approximately 5 emu/g at both 300 K and 2 K. The Fe³⁺-O^2--Fe³⁺ superexchange paths broken by oxygen vacancies then resulting in the Fe³⁺-Fe³⁺ ferromagnetism configuration. Meanwhile, the oxygen vacancy is highly diluted then the ferromagnetism configuration is confined in a single super-cell, favoring a short-range magnetic ordering at room temperature. The concentration of oxygen vacancies was calculated to be 0.68% by magnetization measurement. Our results may shed a light on how oxygen vacancies affect magnetism.     

Perovskite ceramic oxide as an efficient electrocatalyst for nitrogen fixation

The electrochemical conversion of N₂ to NH₃ is an interesting research topic as it provided an alternative and energy-saving method compared with the traditional way of NH₃ production. Although different materials have been proposed for N₂ reduction, the use of defects in oxides was only reported recently and the relevant working mechanism was not fully revealed. In this study, Sr was used as the dopant for LaFeO₃ to create oxygen vacancies, forming the Sr-doped LFO (La_0.5Sr_0.5FeO_3-δ) perovskite oxide. The La_0.5Sr_0.5FeO_3-δ ceramic oxide used as a catalyst achieves an NH₃ yield of 11.51 μgh^?1 mg^?1 and the desirable faradic efficiency (F.E.) of 0.54% at ?0.6 V vs reversible hydrogen electrode (RHE), which surpassed that of LaFeO₃ nanoparticles. The ¹⁵N isotope labeling method was employed to prove the La_0.5Sr_0.5FeO_3-δ catalyst had the function of converting N₂ into NH₃ under the electrolysis condition. The first principle calculations were used to investigate the mechanism at the atomistic level, revealing that the free energy barriers changed significantly with the introduction of oxygen vacancies that accelerated the overall nitrogen reduction reaction (NRR) procedure.     

高新能源占比系统的低频减载优化方法

电网系统中大规模新能源的并网对电网的安全稳定提出新的挑战,在高新能源占比电网中,系统的第三道防线的适应能力对于系统的安全稳定尤为重要,低频减载是第三道防线中频率紧急控制的主要手段.该文介绍适用于低频减载整定计算的频率响应模型,在此模型的基础上分析得出传统低频减载方案对高新能源占比系统的适应性较差的结论,提出基于df/d...     

Enhanced performance of Ni catalysts supported on ZrO2 nanosheets for CO2 methanation: Effects of support morphology and chelating ligands

A series of Ni/ZrO₂ catalysts was prepared by the impregnation method with modification of the morphology of ZrO₂ support as well as the impregnation procedure and tested for CO₂ methanation. The catalysts supported on the ZrO₂ nanosheets displayed superior catalytic performance as compared with that on ZrO₂ nanoparticles, which could be mainly attributed to the abundant oxygen vacancies promoting the adsorption and dissociation of CO₂ molecules as well as the high dispersion of Ni species. With the introduction of ethylenediamine (En) in the impregnation procedure, the resulting Ni-15En/ZrO₂-1.5 catalyst showed the optimal activity with CO₂ conversion of 86% significantly higher than Ni/ZrO₂-0 of 44% and Ni/ZrO₂-1.5 of 79% at 0.5 MPa and 300 °C. The excellent performance was attributed to increased moderately basic sites for CO₂ adsorption in ZrO₂ nanosheets, as well as the enhanced dispersion of nickel caused by the complexation of Ni ions with En, which inhibited the aggregation of nickel particles in the subsequent thermal treatments. In conclusion, the synergistic effects of the morphology of ZrO₂ nanosheets as well as the chelating behavior of En contributed to the enhanced performance of Ni-15En/ZrO₂-1.5 in the CO₂ methanation reaction. The strategy shows good prospects for controlling the size of active metals, especially those that were dispersed on the surface of the two-dimensional (2D) metal oxide materials.     

High cycling stability enabled by Li vacancy regulation in Ta-doped garnet-type solid-state electrolyte

Ta-doped solid-state electrolyte (SSE) is employed to reveal Li vacancy regulation process and densification mechanism through thermodynamic analysis. The vacancy concentration has an optimal value corresponding to the lowest free energy of the Ta-doped SSE system. Low system free energy accelerates grain growth and promotes grain fusion for SSE densification, which is consistent with microstructure evolution. The relative density and Li-ion conductivity reach 96.1 % and 6.47 × 10^?4 S cm^?1 at 0.5 of Ta doping. Symmetric Li battery exhibits stable cycling at a high current density of 1.41 mA cm^?2 and cycles 250 h without polarization at 0.2 mA cm^?2. Full battery with LiFePO₄ cathode keeps stability with high Coulombic efficiency of ～99 % after 150 cycles at 0.5 C. This work provides theoretical insights into the Li vacancy regulation of Ta-doped SSE, constituting a significant step toward practical applications.     

Defect redistribution along grain boundaries in SrTiO3 by externally applied electric fields

During thermal annealing at 1425 °C nominal electric field strengths of 50 V/mm and 150 V/mm were applied along the grain boundary planes of a near 45° (100) twist grain boundary in SrTiO₃. Electron microscopy characterization revealed interface expansions near the positive electrode around 0.8 nm for either field strength. While the interface width decreased to roughly 0.4 nm after annealing at 50 V/mm, the higher field strength caused decomposition of the boundary structure close to the negative electrode. Electron energy-loss and X-ray photoelectron spectroscopies demonstrated an increased degree of oxygen sublattice distortion at the negative electrode side, and enhanced concentrations of Ti³⁺ and Ti²⁺ compared to bulk for both single crystals and bicrystals annealed with an external electric field, respectively. Oxygen migration due to the applied electric field causes the observed alteration of grain boundary structures. At sufficiently high field strength the agglomeration of anion vacancies may lead to the decomposition of the grain boundary.     

Oxygen vacancy-rich ZnO nanorods-based MEMS sensors for swift trace ethanol recognition

Ethanol vapor plays a significant role in the aspects of human health and industrial production, thus necessitating a swift, sensitive, and low-power ethanol detection in the field of future gas sensors. In this work, we prepared micro–electro–mechanical system ethanol sensors based on ZnO nanorods (NRs) and nanoparticles (NPs) for trace ethanol detection. Both ZnO samples were synthesized by a facile hydrothermal method. The comparison results exhibited that ZnO NRs based sensors prevailed over NPs-based counterparts in terms of sensitivity, optimal operation temperature, and reaction speeds. Briefly, that ZnO NRs-based sensors presented a large response (11.5 toward 5 ppm), fast response/recovery times (5 s/5 s), ultralow detection limit (400 ppb), and tiny power consumption (30 mW) at 245°C, surpassing most of recently reported ethanol sensors and commercial products based metal oxides. The abundant oxygen vacancies, large specific surface area, and porous structure were primarily responsible for the excellent sensor performance. This work also offers a facile and competitive approach to realize a sensitive and swift trace ethanol recognition with minimal power consumption, catering for the demanding requirements of future gas sensors in the fields of wearable devices and Internet of Things.     

Phase formation and magnetic properties of M-type lanthanum substituted strontium ferrites

Rare earth ion substitution is one of the most important methods for adjusting the magnetic properties of M-type hexagonal ferrites; however, the regularity of these phase formations has rarely been studied. In this work, La substituted Sr hexaferrite La_xSr_1-xO·nFe₂O₃ (La-SrM, 4.9 ≤ n ≤ 6.0, 0 ≤ x ≤ 0.6) was prepared using the traditional ceramic method. The effects of the Fe/Sr molar ratio (n), calcining temperature, and La³⁺ substitution (x) on SrM phase formation, the crystalline structure, and magnetic properties were investigated. With an increase of x up to a maximum value of 0.5–0.6, a higher calcining temperature is required to form the single M-phase of La-SrM samples. However, the optimal n values of single-phase La-SrM samples differ as the La substitution varies: when x = 0.1, n = 5.5–6.0; x = 0.2, n = 5.5–5.9; x = 0.3, 0.4 and 0.5, n = 5.7–5.8. The magnetic measurements show that La_0.2Sr_0.8O·5.8Fe₂O₃ has the highest specific saturation magnetization (σ_s), which is 2.2% higher than that of unsubstituted SrM (SrO·6Fe₂O₃), while the anisotropic field (H_A), the anisotropic constant (K₁), and Neel point (T_N) of La³⁺ substituted SrM decreased. Detailed structure analyses were conducted to explain the changes in magnetic properties. Fe³⁺ in the spin-up 2a sublattice of La_xSr_1-xO·5.8Fe₂O₃ decreased by approximately 5% from 98.5% (x = 0) to 93.85% (x = 0.4) with an increase in x. Additionally, a small amount of Fe³⁺ was reduced to Fe²⁺ in the spin-down 4f₂ sublattice with the maximum reduction amount of 4.13% reached at x = 0.2, thereby improving σ_s. The decrease in the bond angle of (4f₁) Fe3–O2–Fe5 (12k), (2a) Fe1–O4–Fe3 (4f₁), and (4f₁) Fe3–O4–Fe5 (12k) lead to the weakening of Fe–O–Fe superexchange of La-SrM so that H_A, K_1, and T_n decreased with increasing values of x. This work lays a solid foundation for the study of process regulation and ion substitution of permanent magnet ferrite.     

Oxygen vacancy enabled mesoporous Mn–Co oxide material for high-performance formaldehyde sensor worked at room temperature

In recent years, the exploration of hazardous gases at room temperature (RT) has remained one of the key focuses in the research field of the semiconductor gas sensors. Herein, mesoporous manganese-cobalt (Mn–Co) oxides with abundant oxygen vacancies were synthesized by the combustion method assisted with the green reducing agent l-Ascorbic acid (LA). The synthesized Mn–Co oxides were performed by X-ray spectroscopy (XPS) and Raman spectrometer to research their chemical state of surface elements. The results manifested that the Mn–Co oxides with LA adding during preparation possessed abundant oxygen vacancies. Additionally, the gas sensitivity tests indicated that the Mn–Co oxides with a mole ratio of LA to metal elements (MCO-0.3L) exhibited best formaldehyde sensing properties compared to other prepared Mn–Co oxides in the concentration of 0.25–30 ppm at RT. Notably, its response to 5 ppm formaldehyde at RT was more than 7 times of that of the Mn–Co oxides prepared without LA adding (8.1 vs 1.1). The MCO-0.3L sensor has a limit of detection (LOD) as low as 5.2 ppb. It also showed good selectivity and reliability. The improved formaldehyde sensitivity of the Mn–Co oxides sensors is supposed as the synergistic action of the abundant oxygen vacancies and the mesoporous structure.     

Boosting ammonia synthesis over molybdenum nitride through nickel-mediated nitrogen activation and hydrogen transfer

Synergistic optimization of nitrogen dissociation and hydrogen transfer might be an efficient strategy to develop a highly efficient ammonia synthesis catalyst. Herein, the Ni-modified molybdenum nitride is used as the catalyst of ammonia synthesis. The presence of the highly dispersed Ni metal results in enhancement of nitrogen vacancy, causing the acceleration of the exchange and reaction of the lattice N species with the nitrogen species from the gaseous phase. In addition, the presence of Ni species facilitates the hydrogen transfer and spillover, as well as easy hydrogen release. As a result, the optimized molybdenum nitride catalyst with 0.1 wt% Ni shows a 2.5-times higher catalytic activity than that of the catalyst without Ni species at 400°C owing to the coupling of nitrogen activation and hydrogen transfer effects. This general approach could inspire the rational design of other metal catalysts for ammonia synthesis.