“Dark hole” cure in Ba4.2Nd9.2Ti18O54 microwave dielectric ceramics

Large size Ba_4.2Nd_9.2Ti₁₈O₅₄ (BNT) ceramics doped with MnCO₃, CuO and CoO were prepared by the conventional solid-state method. Only a single BaNd₂Ti₄O₁₂ phase was formed in all samples. No second phase was found in the XRD patterns. The bulk density increases slightly because of the dopants. The SEM results showed that the grain size of Mn²⁺and Cu²⁺-doped BNT ceramics became larger with the increasing amount of dopants. The permittivity of all samples stays the same. However, the Q×f value of BNT ceramics increases by doping, especially with Mn²⁺ ions. The conductivity of BNT ceramic doped with Mn²⁺(0.5 mol‰) under high temperature is lower than that without doping. There are fewer defects in Mn²⁺-doped BNT ceramics. The XPS results indicated that Ti reduction was suppressed in BNT ceramics doped with 0.5 mol‰ Mn²⁺. BNT ceramics doped with 0.5 mol‰ Mn²⁺ ions sintered at 1320 °C for 2 h exhibited good microwave dielectric properties, with ε_r=88.67, Q×f=7408 GHz and τf = 82.98 ppm/°C.     

Insight into the selective oxidation mechanism of glycerol to 1,3-dihydroxyacetone over AuCu–ZnO interface

Directional regulation of polyol oxidation selectivity by constructing active sites with specific structure is a critical yet challenging problem. Herein, the specific Au-based catalyst with efficient Au–Cu–ZnO interfacial active sites was successfully designed to promote selective oxidation of glycerol to 1,3-dihydroxyacetone under mild conditions. X-ray absorption spectroscopy revealed that the increased electron transfer between Au and Cu increases the content of Au⁺, resulting in the higher catalytic activity (turnover frequency: 402.5 h⁻¹). Meanwhile, small AuCu alloy nanoparticles (ca., 2.7 nm) could be inserted into the ZnO lattice with the formation of Au(Cu)–O–Zn linkages, resulting in the enrichment of interfacial oxygen vacancies. These interfacial oxygen vacancies induce the activation and adsorption of the secondary hydroxyl group of glycerol on the interfacial active sites, improving the selectivity of 1,3-dihydroxyacetone (83.4%). Furthermore, in situ Fourier transform infrared, structure-dependent kinetics and density functional theory calculation demonstrated that Au–Cu–ZnO interfacial active sites could enhance the participation of OH* and oxygen vacancies in activating the O H and C H bonds, respectively, promoting the improvement of the catalytic performance. The outcome of this work offers new insights for the rational design of high effective catalyst for the selective oxidation of polyol.     

Porous TiO2/rGO nanocomposites prepared by cold sintering as efficient electrocatalyst for nitrogen reduction reaction under ambient conditions

Haber–Bosch process as the current dominant artificial NH₃ production process in industry, requires relatively high temperature (350–550 °C) and pressure (150–350 atm). Electrocatalytic nitrogen reduction reaction (NRR) as a green and sustainable strategy for ammonia production has raised intensive research interest in recent years but still remains a significant challenge because of the lack of high performance electrocatalysts. In this work, porous TiO₂-reduced graphene oxide (TiO₂/rGO) nanocomposite as self-supporting efficient electrocatalyst for NRR under ambient conditions were prepared by cold sintering associated with sacrificial template method. The porous TiO₂/rGO nanocomposite with grain size of ～40 nm were prepared by cold sintering process at 220 °C and 147 MPa. Given the 220 °C as cold sintering temperature, anatase TiO₂ were preserved as the final phase which exhibit much better NRR electrocatalytic performance than the rutile phase. The oxygen vacancy densities in the nanocomposites were also tuned by heat treatment at 450 °C under different atmosphere, while samples heat treated under H₂/Ar atmosphere gave the best electrocatalytic NRR performance with a FE of 8.88 % and an NH₃ yield of 7.75 μg h^?1 cm^?2 at ambient conditions. Experiments also shows that the addition of rGO significantly improved the electrocatalytic NRR performance especially the conductivity. This work not only designed a framework of ceramic nanocomposites based self-supporting and durable electrocatalysts system but also paves a feasible way towards preparing electrocatalysts that are sensitive to high temperature fabrication process.     

Simultaneously improving the electrical properties and long-term stability of ZnO varistor ceramics by reversely manipulating intrinsic point defects

Excellent electrical properties and the improved long-term stability of ZnO varistor ceramics were simultaneously achieved by doping NiO. The microstructural features were investigated using X-ray diffractometer, scanning electron microscopy, and energy dispersive spectroscopy, while the intrinsic point defects were characterized using frequency domain dielectric spectroscopy and verified by photoluminescence and Raman spectra. The results indicated that in the ZnO varistor ceramics, a reverse manipulation of donor point defects, i.e., suppressing mobile zinc interstitial but increasing stable oxygen vacancy, was achieved. The long-term stability of NiO-doped ZnO ceramics was improved via a decrease in zinc interstitial density, with a degradation rate of 0.064 μA cm^?2 h^?0.5. Meanwhile, due to an increase in oxygen vacancy density, the excellent nonlinear current–voltage performance, i.e., a high nonlinear coefficient (72.9), low leakage current density (0.08 μA cm^?2), and low grain resistivity (13.43 × 10^?3 Ω m), was maintained. The findings of this study provide a possible method for developing high-performance ZnO varistor ceramics by manipulating point defects.     

Ultrafast high-temperature sintering of barium titanate ceramics with colossal dielectric constants

Application of Ultrafast High-temperature Sintering (UHS) technique to rapidly densify barium titanate ceramics has been explored for the first time. Bulk ceramic with ~94% density was obtained by UHS at ~1340 °C for 60 seconds. The densification process was accompanied with progressive sample discolouration from light to dark grey. Further analysis indicates that oxygen vacancy and its associated Ti-rich phase Ba₄Ti₁₂O₂₇ are present in the ceramics. Their roles in ultrafast densification and sample discoloration are discussed. Due to the presence of oxygen vacancies, the UHSed ceramics generally exhibit a colossal dielectric constant of ~ 15–30k at 1 kHz, with dielectric loss of ~0.07–0.10, while the ceramics without oxygen vacancy retain a dielectric constant of ~3000–6000 and dielectric loss of ~ 0.06 at 1 kHz which are comparable to that of the conventionally sintered ceramics. Furthermore, the challenges in applying UHS to sinter thick BT ceramics are discussed, aided by thermal simulations.     

Sintering of high-entropy nanoparticles obtained by polyol process: A case study of (La0.2Y0.2Nd0.2Sm0.2Gd0.2)2Ce2O7-δ

High-entropy (HE) ceramics nanoparticles have received much attention due to their interesting properties. However, very limited studies have been conducted on their sintering. Here, we report the sintering behavior of HE A₂B₂O₇ type rare earth oxide nanoparticles obtained by polyol process. HE cerate (HECe) (La_0.2Y_0.2Nd_0.2Sm_0.2Gd_0.2)₂Ce₂O_7-δ is chosen as an exemplary case, which is considered as a good candidate for thermal insulation. HECe nanoparticles with size of 2.6–7.1 nm can be synthesized through polyol process followed by annealing in air at 300–700 °C. HECe nanoparticle compact can be densified by directly sintering at 1500 °C. The sintering temperature could be further decreased using a two-step sintering process, i.e., 1500 °C 5 min-1300 °C 5 h. Our results show that fine particle and abundant oxygen vacancies probably dominate the densification process. By controlling the sintering regime, we can tune the microstructure of HECe ceramics and thermal conductive properties accordingly.     

Tuning of dielectric and ferroelectric properties in single phase BiFeO3 ceramics with controlled Fe/Fe ratio

Single phase multiferroic BiFeO₃ (BFO) ceramics were synthesized with controllable amount of Fe²⁺ and oxygen vacancies in a very wide concentration range. Double ferroelectric hysteresis loops are observed in fresh BFO ceramics at room temperature without any aging processes. Detailed study shows that this is due to the defect dipoles which have preferential orientations antiparallel to the direction of spontaneous polarization, providing a driving force for domain back-switching. The dielectric constant of BFO could be enormously enhanced by 100 times by increasing the Fe²⁺ content, employing a polaronic relaxation process.     

Effect of lanthanum content on the conduction behaviors and relaxation processes of lead lanthanum zirconate titanate antiferroelectric ceramics

(Pb_1-xLa_x) (Zr_0.92Ti_0.08)_1-x/4O₃ (PLZT x/92/8, x = 3, 5 and 7 at%) ceramics with compositions near the antiferroelectric (AFE)-ferroelectric (FE) phase boundary were fabricated by a solid-state reaction method. The effect of lanthanum content on the conduction behaviors and relaxation processes has been investigated. It was verified that the main phase with orthorhombic structure was formed in all compositions. The increase of lanthanum substitution resulted in an enhancement of diffuse phase transition. Impedance analysis suggested that the ac conductivity decreased with increasing lanthanum content. Moreover, thermally stimulated depolarization current study was utilized to establish the correlation between defect structures and relaxation processes. It showed three peaks with distinct characteristics, which originated from dipole orientation, oxygen vacancy migration and phase transition respectively. The oxygen vacancy-related defects induced by lanthanum doping were mainly responsible for the variation of conduction behaviors and relaxation processes.     

Electric field dependence of ferroelectric stability in BiFeO3 thin films co-doped with Er and Mn

Bi_0.9Er_0.1Fe_1−xMn_xO₃ (BEFM_xO, x = 0.00–0.03) films are synthesized by a sol–gel technique. The BEFO film exhibits a conduction mechanism based on electron tunneling. The high applied electric field causes dissociation of the defect complex, and the resulting oxygen vacancies contribute to fake polarization. Consequently, the BEFO film has poor polarization stability at high applied electric fields. Coexistence of two phases (with space groups R3c:H and R3m:R) and reduced concentrations of oxygen vacancies and Fe²⁺ in BEFM_xO are achieved by co-doping with Er and Mn. The presence of bulk-based conduction in the BEFM_xO films then leads to ferroelectric domain switching contributing to the real polarization and to excellent ferroelectric stability. In addition, the BEFM_0.02O film shows a typical symmetrical butterfly curve, the highest remnant polarization of ~109 μC/cm², and the highest switching current of ~1.66 mA. It also has the smallest oxygen vacancy concentration and thus the smallest amount of defect complex, which means that there are fewer pinning effects on ferroelectric domains and therefore excellent ferroelectric stability. This excellent ferroelectric stability makes the BEFM_xO films obtain good stability and reliability in the application of ferroelectric memory devices.     

Catalytic combustion of methane over a highly active and stable NiO/CeO2 catalyst

In the last decades, many reports dealing with technology for the catalytic combustion of methane (CH₄) have been published. Recently, attention has increasingly focused on the synthesis and catalytic activity of nickel oxides. In this paper, a NiO/CeO₂ catalyst with high catalytic performance in methane combustion was synthesized via a facile impregnation method, and its catalytic activity, stability, and water-resistance during CH₄ combustion were investigated. X-ray diffraction, low-temperature N₂ adsorption, thermogravimetric analysis, Fourier transform infrared spectroscopy, hydrogen temperature programmed reduction, methane temperature programmed surface reaction, Raman spectroscopy, electron paramagnetic resonance, and transmission electron microscope characterization of the catalyst were conducted to determine the origin of its high catalytic activity and stability in detail. The incorporation of NiO was found to enhance the concentration of oxygen vacancies, as well as the activity and amount of surface oxygen. As a result, the mobility of bulk oxygen in CeO₂ was increased. The presence of CeO₂ prevented the aggregation of NiO, enhanced reduction by NiO, and provided more oxygen species for the combustion of CH₄. The results of a kinetics study indicated that the reaction order was about 1.07 for CH₄ and about 0.10 for O₂ over the NiO/CeO₂ catalyst.