Nonlinearity in regulating the metal to insulator transition of ReNiO3 towards low temperature range

Among the existing material family of the correlated oxides, the rare earth nickelates (ReNiO₃) exhibit broadly adjustable metal to insulator transition (MIT) properties that enables correlated electronic applications, such as thermistors, thermochromics, and logical devices. Nevertheless, how to accurately control the critical temperature (T_MIT) of ReNiO₃ via the co-occupation of the rare-earth elements is yet worthy to be further explored. Herein, we demonstrate the non-linearity in adjusting the T_MIT of ReNiO₃ towards lower temperatures via introducing Pr co-occupation within ReNiO₃ (e.g., Pr_xNd_1-xNiO₃ and Pr_xSm_1-xNiO₃) as synthesized by KCl molten-salt assisted high oxygen pressure reaction approach. Although the T_MIT is effectively reduced via Pr substitution, it does not strictly follow a linear relationship, in particular, when there is large difference in the ionic radius of the co-occupation rare-earth elements. Furthermore, the most significant deviation in T_MIT from the expected linear relationship appears at an equal co-occupation ratio of the two different rare-earth elements, while the abruption in the variation of resistivity across T_MIT is also reduced. The present work highlights the importance to use adjacent rare-earth elements with co-occupation ratio away from 1:1 for achieving more linear adjustment in designing the metal to insulator transition properties for ReNiO₃.     

Magnetic field-enhanced photocatalytic nitrogen fixation over defect-rich ferroelectric Bi2WO6

Photocatalytic N₂ fixation is a promising and sustainable manufacturing process of ammonia (NH₃); however, the NH₃ production rate by this method is very low, thus severely restricting further application of this sustainable technology. Therefore, developing an efficient photocatalyst for N₂ fixation under mild conditions is urgently required. Herein, ferroelectric Bi₂WO₆ materials with different surface oxygen defects were prepared, and the concentration of corresponding defects was controlled by adjusting the thermal reduction time. The abundant oxygen defects in Bi₂WO₆ can provide more reactive sites to promote the effective adsorption of N₂, and the photogenerated charge carrier can be efficiently separated benefiting from the internal electric field. These would weaken the N₂ triple bond and reduce the activation energy barrier for the conversion of N₂ to NH₃ under mild conditions. In the absence of sacrificial agents and cocatalysts, the optimized Bi₂WO₆ with oxygen defects shows an indigenous NH₃ yield of 132.175 μmol·g^-1·L^-1·h^-1, which is more than two times higher than that of the original Bi₂WO₆. Surprisingly, the Bi₂WO₆ with oxygen defects produced more than eight times NH₃ (471.13 μmol·g^-1·L^-1·h^-1) than that of the original Bi₂WO₆ when assisted by an external magnetic field, thus providing a new perspective for further enhancing the N₂ fixation performance.     

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.     

Psychrophilic hydrogen production from petrochemical wastewater via anaerobic sequencing batch reactor: techno-economic assessment and kinetic modelling

Independent hydrogen production from petrochemical wastewater containing mono-ethylene glycol (MEG) via anaerobic sequencing batch reactor (ASBR) was extensively assessed under psychrophilic conditions (15–25 °C). A lab-scale ASBR was operated at pH of 5.50, and different organic loading rates (OLR) of 1.00, 1.67, 2.67, and 4.00 gCOD/L/d. The hydrogen yield (HY) progressed from 134.32 ± 10.79 to 189.09 ± 22.35 mL/gMEG_initial at increasing OLR from 1.00 to 4.00 gCOD/L/d. The maximum hydrogen content of 47.44 ± 3.60% was achieved at OLR of 4.0 gCOD/L/d, while methane content remained low (17.76 ± 1.27% at OLR of 1.0 gCOD/L/d). Kinetic studies using four different mathematical models were conducted to describe the ASBR performance. Furthermore, two batch-mode experiments were performed to optimize the nitrogen supplementation as a nutrient (C/N ratio), and assess the impact of salinity (as gNaCl/L) on hydrogen production. HY substantially dropped from 62.77 ± 4.09 to 6.02 ± 0.39 mL/gMEG_initial when C/N ratio was increased from 28.5 to 114.0. Besides, the results revealed that salinity up to 10.0 gNaCl/L has a relatively low inhibitory impact on hydrogen production. Eventually, the cost/benefit analysis showed that environmental and energy recovery revenues from ASBR were optimized at OLR of 4.0 gCOD/L/d (payback period of 7.13 yrs).     

Synthesis of manganese titanate and its precursors from xerogel

An overview of research on the synthesis of manganese titanates is presented. The xerogel of Mn–Ti–O–C–H composition was synthesized from manganese acetate and titanium tetrabutylate via liquid-phase method using organic solvents. The calcination of xerogel in air at 450 °C and 700 °C yielded manganese titanate precursors in the form of a nanostructured mixture of Mn₂O₃ and TiO₂. Annealing at 1000 °C, manganese metatitanate MnTiO₃ was obtained. Reference experiments with initial reagents included, separately, thermal decomposition of Mn(CH₃COO)₂×4H₂O and the product of Ti(OC₄H₉)₄ hydrolysis. The composition, structure, and properties of the products were studied using X-ray diffraction, scanning electron microscopy, elemental analysis, diffuse reflectance IR Fourier spectroscopy, thermogravimetry, and by measuring specific surface area. The data presented by these different techniques are basically consistent with each other (with an increase in the annealing temperature, an increase in globule size and decrease in specific surface area are observed; structuring occurs within the long- and short-range order; the size of the crystallites does not exceed that of the globules; elemental composition correlates with phase composition; the endothermic character of the reaction of MnTiO₃ formation at 900 °C is confirmed by a thermodynamic calculation). Nevertheless, some unexpected effects were revealed (based on the FTIR diffuse reflection spectra, mixed oxide Mn–Ti–O is formed in the surface layer of particles already at 450 °C and 700 °C; etc.). Application of the proposed technique for modifying Al₂O₃ powders, with the aim of implementing low-temperature sintering of corundum ceramics, is discussed.     

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.     

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.     

Analysis of nitrogen oxide emissions from modern vehicles using hydrogen or other natural and synthetic fuels in combustion chamber

The paper presents a calculated analysis of the equilibrium emission of nitrogen oxides on the exhaust of carburetor and diesel internal combustion engines. The temperature of fuel oxidation is assumed to be 1,400 °C while the pressure for carburetor and diesel engines is assumed to be 60 atm and 80 atm respectively. The studies have been carried out for natural and synthetic fuels such as hydrogen, ethanol, methanol, petroleum, diesel fuel and methane at the excess air coefficient corresponding to the fuel oxidation temperature of 1,400 °C. In the paper, the method for calculating the equilibrium composition based on the equilibrium constant and mass conservation equations has been applied. It is shown that with an increase in pressure from 1 atm to 60 atm for carburetor engines and up to 80 atm for diesel engines, the reaction of nitrogen dioxide formation may shift towards an increase in NO₂. The formation of NO may be not affected by the increase in pressure by virtue of the fact that the reaction proceeds without changes in the amount. It has been determined that NO is the major atmospheric pollutant. However, it would be advisable to use more extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol), since nitrogen dioxide (NO₂) related to the 2nd hazard class is appeared to be the most dangerous to humans. It has been revealed that the reduction in oxidation temperature using hydrogen as a fuel for electrochemical current generators may allow reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE.     

Enhanced thermoelectric properties of atomic-layer-deposited Hf:Zn16O/18O superlattice films by interface-engineering

This study examines three novel approaches for enhancing the thermoelectric (TE) properties of atomic-layer-deposited (ALD) ZnO thin films: 1) Hf-doping, which preserved the crystallinity of ZnO and provided effective phonon scattering owing to Hf's similar atomic radius to and large mass difference with Zn, leading to high power factor (PF) and low thermal conductivity (κ); 2) controlling the distribution of Hf into an alternating scattered phase/clustered phase superlattice, which balanced the high PF of the scattered phases with the low κ of the clustered phases, while providing significant energy-filtering effect to raise the Seebeck coefficient; 3) introducing ¹⁸O/¹⁶O periodicity into the Hf:ZnO films—by alternately using H₂¹⁶O and H₂¹⁸O as oxidants in the ALD processes, which further suppressed κ without compromising PF. The combination of the three approaches resulted in a maximum improvement in ZT of ~1600% over that of the undoped ZnO.     

Preparation of nanocrystalline nickel oxide from nickel hydroxide using spark plasma sintering and inverse Hall-Petch related densification

Nanocrystalline nickel oxide (NiO) was prepared from nickel hydroxide by Spark plasma sintering (SPS) and the mechanisms involved in the densification of NiO were studied. Reverse precipitated nickel hydroxide powders were SPS processed at 400, 600 and 700?°C with 70?MPa pressure. Pure NiO with 12?nm crystallite size formed after 400?°C sintering process. However NiO grains had grown to 18 and 38?nm after 600 and 700?°C sintering respectively. NiO pellets prepared using 600 and 700?°C SPS sintering schedules had relative densities of 83% and 94% respectively. Two displacement rate regimes were observed during densification of NiO in both 600 and 700?°C sintering processes. Decomposition of nickel hydroxide and particle sliding of NiO led to first displacement rate maximum while inverse Hall-Petch based plastic deformation facilitated densification during the constant second displacement rate regime. No densification occurred during sintering holding times indicating the limited role that diffusion played during densification.