Oxidation State Modulation of Bismuth for Efficient Electrocatalytic Nitrogen Reduction to Ammonia

Electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia (NH₃) production under ambient conditions. However, it is severely impeded by the challenging activation of the NN bond and the competing hydrogen evolution reaction (HER), which makes it crucial to design electrocatalysts rationally for efficient NRR. Herein, the rational design of bismuth (Bi) nanoparticles with different oxidation states embedded in carbon nanosheets (Bi@C) as efficient NRR electrocatalysts is reported. The NRR performance of Bi@C improves with the increase of Bi⁰/Bi³⁺ atomic ratios, indicating that the oxidation state of Bi plays a significant role in electrochemical ammonia synthesis. As a result, the Bi@C nanosheets annealed at 900  ° C with the optimal oxidation state of Bi demonstrate the best NRR performance with a high NH₃ yield rate and remarkable Faradaic efficiency of 15.10  ± 0.43% at − 0.4 V versus RHE. Density functional theory calculations reveal that the effective modulation of the oxidation state of Bi can tune the p-filling of active Bi sites and strengthen adsorption of *NNH, which boost the potential-determining step and facilitate the electrocatalytic NRR under ambient conditions. This work may offer valuable insights into the rational material design by modulating oxidation states for efficient electrocatalysis.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Manganese oxides treated with organic compounds as catalysts for water oxidation reaction

Manganese oxides of different crystalline structures: α-MnO₂, δ-MnO₂, α,γ-MnO₂ and Mn₂O₃; were treated with the organic compounds picolinic acid, ethylenediamine and pyridine; and were applied as catalysts in the chemical water oxidation reaction using Ce(IV) ammonium nitrate as sacrificial oxidant. The treatment led to modifications in the oxides properties, such as reduction of the particle size, increase of surface area and partial reduction of Mn⁴⁺ to Mn³⁺ for the Mn(IV) oxides, or of Mn³⁺ to Mn²⁺ for Mn₂O₃, because of favored interactions of the organic molecules with the lattice planes with higher d spacing. Oxygen evolution reaction (OER) tests showed the superior catalytic activity of the treated Mn(IV) oxides, for instance α,γ-MnO₂-en presented TOF five times higher than pure α,γ-MnO₂. The increase in surface area as well as the higher Mn³⁺ content caused by the treatment of the Mn(IV) oxides were correlated with the improvement in the OER catalytic activity.     

Zinc doped Fe2O3 for boosting Electrocatalytic Nitrogen Fixation to ammonia under mild conditions

Artificial nitrogen fixation is emerging as a promising approach for synthesis of ammonia at mild conditions. Inspired by biological nitrogen fixation based on bacteria containing iron, zinc doped Fe₂O₃ nanoparticles are proposed as an efficient and earth abundant electrocatalyst for converting N₂ to NH₃. In neutral media, it achieves a maximum Faradaic efficiency (FE) of 10.4% and a large NH₃ yield rate of 15.1 μg h^?1 mg^?1_cat. at ?0.5 V vs. reversible hydrogen electrode. This catalyst also exhibits excellent selectivity and stability. Theoretical calculations suggest the reaction follows the associative enzymatic mechanism and it has a barrier of as low as 0.68 eV.     

Vacancy-engineered V2O5-x films for ultrastable electrochromic applications

In the present study, we prepared vacancy-engineered V₂O_5-x films for electrochromic (EC) applications. To investigate the vacancy effect of V₂O_5-x films with high EC performance capabilities, precursor concentrations of V-based sol solutions were varied at 1 wt%, 5 wt%, and 10 wt%. Among them, V₂O_5-x films with a precursor concentration of 5 wt% (V₂O₅-5wt%) showed superior EC performance outcomes due to the (001)-plane-oriented crystal structure, which provides high electrical conductivity with the oxygen vacancy (V_o). In addition, the gravel-like uniform surface morphology with the optimized film thickness provides a stable electrochemical reaction during the EC measurement. As a result, V₂O₅-5wt% exhibited fast switching speeds (2.1 s for coloration and 3.6 s for bleaching), high transmittance modulation (ΔT) (51.32%), high coloration efficiency (CE) (52.3 cm²/C), and excellent cycle stability (85.85% ΔT retention after 500 cycles). In addition, V₂O₅-5wt% showed energy storage capability of 443.7 F/g at a current density of 2 A/g, thus proving its potential for use in multi-functional applications. Therefore, these results provide valuable insight related to the engineering of vacancies in EC films to achieve high-performance EC devices and additional multi-functional applications.     

Effect of sintering conditions on structural and morphological properties of Y- and Co-doped BaZrO3 proton conductors

BaZrO₃-based materials doped with a trivalent cation have excellent chemical stability and relatively high proton conductivity which makes them potential proton conducting oxide materials for various electrochemical device applications such as hydrogen processing, high-temperature electrolysis, and solid electrolyte in fuel cells. However, BaZrO₃ showed poor sinterability, requiring high sintering temperatures (1700–2100 °C) with longtime sintering (20–100 h) to achieve the desired microstructure and grain growth. This sintering problem can be solved by slightly doping BaZrO₃ with a sintering aid element. Therefore, in this study, two different zirconate proton conductors: BaZr_0·9Y_0·1O_3-α (BZY) and BaZr_0·955Y_0·03Co_0·015O_3-α (BZYC) were sintered in an air atmosphere and an oxygen atmosphere for 20 h in the temperature range of 1500–1640 °C. The sinterability was evaluated by analyzing the XRD diffraction patterns, lattice constant, lattice strain, crystallite size, relative density, open porosity, closed porosity, surface morphology, grain size, and grain boundary distribution, using the XRD, SEM, EDX, and Archimedes density measurement methods. It is concluded that in an oxygen atmosphere, sintering aid Co not only improves the relative density but also produces highly dense fine particles with clear grain boundaries which are promising for electrochemical hydrogen device applications.     

Highly sensitive and wide-range flexible sensor based on hybrid BaWO4@CS nanocomposite

Flexible photoelectronic devices are in demand right now. In this work, a new family of biopolymer-based photodetectors is described. Chitosan (CS) was utilized as a safe, biodegradable host biopolymer, and nanostructured barium tungstate (BaWO₄) particles were used as the nanofiller of the biopolymer matrix to prepare flexible optical sensors. The co-precipitation process was used to produce the filler powders, which were then dried at room temperature without using any surfactants or hazardous solvents. The fabricated sensor showed high flexibility and sensitivity to UV/proton/alpha and laser irradiation. X-ray diffraction (XRD), XPS, FTIR, EDX-map analysis also confirmed the successful synthesis, related chemical binding, and elements in the nanocomposite structure. According to the TEM images, the average particle size of synthesized BaWO₄ NPs was obtained at about 110 nm. A considerable luminescence emission was observed in the constructed sensor's blue/green and ultraviolet spectral regions under various excitation sources. The developed sensor was nontoxic to the cells and provided soft, thin, antibacterial activity, flexible, and comfortable contact with skin, and promising ionizing ray detection applications in flexible optical sensors.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Effect of preparation method on physicochemical properties and catalytic performances of LaCoO_3 perovskite for CO oxidation

Perovskite oxides LaCoO_3 prepared by templating, co-precipitation and sol-gel method with different complexants were systematically characterized and its catalytic performances for CO oxidation were investigated. The samples were characterized by X-ray diffraction, thermogravimetry analysis and differential scanning calorimetry, N_2 physisorption, transmission electron microscopy, temperature program reduction of hydrogen, temperature program desorption of oxygen and X-ray photoelectron spectroscopy measurement, results of which show that the properties of LaCoO_3, such as surface morphology, surface area, surface compositions, redox capability, oxygen vacancy, as well as the calcination temperature and formation mechanism, depend intimately on the preparation method. Catalytic tests indicate that the sample prepared by carbon templating method shows the best activity for CO oxidation, with full CO conversion obtained at 135 ℃. In particular, the catalyst can be activated and significant increase of activity can be obtained with the increase of reaction time. The cyclic and longterm stability of catalysts were discussed and compared.