Microstructural and electrical changes in Ca0.9R0.1CeNbMoO8 (R = Y,Sm, Nd,La) ceramics induced by rare-earth ion doping

Rare-earth ions doped Ca_0.9R_0.1CeNbMoO₈ (R = Y, Sm, Nd, La) ceramics have been successfully prepared by solid-state method, and their modifications to the microstructure and electrical properties are also investigated. The rare-earth ions doped ceramics exhibit the scheelite structure. With the increase in the radius of rare-earth ions, the lattice distortion and bond interaction will be enhanced, and the consistency of grain size will be reduced. The ceramics exhibit negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K-1273 K, and the activation energy decreases with the increase of the radius of rare-earth ions. Rare-earth ions doping can increase the content of Ce³⁺ ions and promote the conductivity of ceramics. Except for Sm³⁺-doped ceramics, the high-temperature aging rate of other ceramics is less than 2%. The existence of some metastable Sm²⁺ ions in Sm³⁺-doped ceramics not only increases the activation energy, but also reduces the high-temperature stability of the ceramics.     

Core-shell cobalt particles Co@CoO loaded on nitrogen-doped graphene for photocatalytic water-splitting

It is of great significance to explore a bifunctional catalyst that can produce both hydrogen and oxygen to accelerate the development of water-splitting technology. In this work, Co@CoO/NG was obtained via calcinating ZIF-67 and in-situ preparation process, which exhibited excellent performance (water oxidation AQE 10.22% at λ = 450 nm and oxygen production rate 543198 μmol g⁻¹ h⁻¹ and hydrogen production rate 330 μmol⁻¹ g⁻¹ h⁻¹). A comprehensive analysis of SEM, XRD, TEM, UV–vis, EIS, and PL showed that Co@CoO/NG-7 prepared has a perfect skeleton and more crystal defects, which can provide more reactive sites. The core-shell structure Co@CoO has a synergistic effect with graphene, which is beneficial to the light absorption, separation of photo-generated charges. Meanwhile, cyclic experiments of water oxidation and water reduction showed that the catalyst exhibited high stability during the reaction process. This study has provided a universal strategy to design efficient bifunctional catalyst for water-splitting.     

Novel thermal-sensitive properties of NBT-BZT composite ceramics for high-temperature NTC thermistors

We found for the first time that (1 − x) Na_0.5Bi_0.5TiO₃-xBiZn_0.5Ti_0.5O₃ (NBT–BZT) composite ceramics showed negative temperature coefficient (NTC) at a high temperature. The NBT–BZT nanopowders were successfully prepared by Pechini method. Their ceramics were sintered at 1100°C. The NBT–BZT ceramic exhibited a good linear relationship between logarithm of electrical resistivity (Inρ) and reciprocal of absolute temperature (1000/T) at 250°C–1050°C. The obtained ρ₆₀₀, ρ₉₀₀, and B_600/900 constants of the NBT–ZBT NTC thermistors are approximately 5.92 × 10⁶ to 3.01 × 10⁴ Ω cm, 7.03 × 10³ to 7.60 × 10² Ω cm and 2.3 × 10⁴-1.3 × 10⁴ K, respectively. The electrical characteristics can be tuned to the desired value by changing the Na_0.5Bi_0.5TiO₃ content in the compound. The electrical conductivity in these compounds is due to the electron jumps between Ti³⁺ and Ti⁴⁺ and oxygen-ion conductivity. Results demonstrate a tremendous potential of the studied system for perovskite materials with NTC performance.     

Correlation between B value deviation and sintering temperature of perovskite solid solution materials

The effects of different sintering temperatures on the system of Ba_0.5Sr_0.5TiO₃–La_0.8Ca_0.2MnO₃ (BST-LCM) material were investigated by means of scanning electron microscopy, X-ray, resistance-temperature measurements, and X-ray photoelectron spectroscopy. X-ray diffraction and X-ray photoelectron spectroscopy confirm that BST-LCM is completely miscible and BST is the main phase, which under the premise of following the theory of small polaron conduction, titanium ions interact with manganese ions, which affects the electrical properties of the system of BST-LCM material. For the electrical properties of related, the LCM content is inversely proportional to the activation energy. Through the linear fitting of the experimental data, the empirical formula between the sintering temperature B value and the content of solid solution is obtained, and the approximate B value within a certain range can be preliminarily calculated.     

A Colorimetric Artificial Olfactory System for Airborne Improvised Explosive Identification

The detection of ultralow or nonvolatile target analytes remains a significant challenge for artificial olfactory systems even after decades of development, which severely limits their widespread application. To overcome this challenge, an artificial olfactory system based on a colorimetric hydrogel array is constructed for the first time as a universal representative. As an effective extension of conventional artificial olfactory systems that integrates the merits of its predecessors, the proposed system accurately mimics olfactory mucosa and specific odorant binding proteins using hydrogels endowed with specific colorimetric reagents for the detection of hypochlorite, chlorate, perchlorate, urea, and nitrate. Therefore, the proposed system is capable of detecting and discriminating between these five airborne improvised explosive microparticulates with a detection limit as low as 39.4 pg. Additionally, the system demonstrates good reusability over ten cycles, rapid response time of ≈0.2 s, and excellent discrimination properties, despite significant variation. This proof-of-concept study on colorimetric artificial olfactory systems yields a novel strategy for the direct and discriminative detection of nonvolatile airborne microparticulates.     

Core–shell NTC materials with low thermal constant and high resistivity for wide-temperature thermistor ceramics

Core–shell structures have been proposed to improve the electrical properties of negative-temperature coefficient (NTC) thermistor ceramics. In this work, Al₂O₃-modified Co_1.5Mn_1.2Ni_0.3O₄ NTC thermistor ceramics with adjustable electrical properties were prepared through citrate-chelation followed by conventional sintering. Co_1.5Mn_1.2Ni_0.3O₄ powder was coated with a thin Al₂O₃ shell layer to form a core–shell structure. Resistivity (ρ) increased rapidly with increasing thickness of the Al₂O₃ layer, and the thermal constant (B) varied moderately between 3706 and 3846 K. In particular, Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ ceramic with 0.08 wt% Al₂O₃ showed the increase of ρ double, and the change in its B was less than 140 K. The Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ NTC ceramics showed high stability, and their grain size was relatively uniform due to the protection offered by the shell. The aging coefficient of the ceramic was less than 0.2% after aging for 500 hours at 125°C. Taken together, the results indicate that as-prepared Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ NTC ceramics with a core–shell structure may be promising candidates for application as wide-temperature NTC thermistor ceramics.     

Performance optimization of microbial electrolysis cell (MEC) for palm oil mill effluent (POME) wastewater treatment and sustainable Bio-H2 production using response surface methodology (RSM)

Microbial electrolysis cells (MECs) are a new bio-electrochemical method for converting organic matter to hydrogen gas (H₂). Palm oil mill effluent (POME) is hazardous wastewater that is mostly formed during the crude oil extraction process in the palm oil industry. In the present study, POME was used in the MEC system for hydrogen generation as a feasible treatment technology. To enhance biohydrogen generation from POME in the MEC, an empirical model was generated using response surface methodology (RSM). A central composite design (CCD) was utilized to perform twenty experimental runs of MEC given three important variables, namely incubation temperature, initial pH, and influent dilution rate. Experimental results from CCD showed that an average value of 1.16 m³ H₂/m³ d for maximum hydrogen production rate (HPR) was produced. A second-order polynomial model was adjusted to the experimental results from CCD. The regression model showed that the quadratic term of all variables tested had a highly significant effect (P < 0.01) on maximum HPR as a defined response. The analysis of the empirical model revealed that the optimal conditions for maximum HPR were incubation temperature, initial pH, and influent dilution rate of 30.23 ^°C, 6.63, and 50.71%, respectively. Generated regression model predicted a maximum HPR of 1.1659 m³ H₂/m³ d could be generated under optimum conditions. Confirmation experimentation was conducted in the optimal conditions determined. Experimental results of the validation test showed that a maximum HPR of 1.1747 m³ H₂/m³ d was produced.     

Optimizing the stability and electrical transport properties of CeNbO4+δ-based oxide ceramics by regulating oxygen ion content

CeNbO_4+δ ceramics have attracted extensive research interest because of their unique mixed ion-electron transport characteristics and interesting structure-functional characteristics caused by the difference in oxygen ion content. Although the change of oxygen ion content brings rich redox properties, it also causes serious crystal transformation and abnormal electrical transport properties. In order to obtain stable structure and excellent electrical transport properties, the directional regulation of the oxygen ion content has been realized through introducing Al₂O₃ and high temperature aging. After 600 h of aging at 1073 K, the prepared composite ceramics not only obtain a stable structure without crystal transformation, but also show good negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K–1273 K, in which the linear fitting maximum Pearson's r of the relationship between lnρ and 1000/T can reach 99.97%. The proposed method provides a new thought for the design and application of high-temperature electronic ceramics.     

基于溶剂极性的双环戊二烯氢甲酰化反应探索研究

以三苯基膦改性的铁磁性氧化物担载的钴铑双金属为催化剂,考察了不同极性溶剂对双环戊二烯（DCPD）氢甲酰化反应合成三环癸烷不饱和单醛和三环癸烷二甲醛的影响。结果表明,溶剂的极性对反应速率和目标产物的选择性有较大的影响,三环癸烷不饱和单醛的生成速率随着溶剂极性的增加呈现增加的趋势;三环癸烷二甲醛的反应速率和选择性随着溶剂极性的增加先增加后降低。以极性值为5.4的丙酮作为溶剂时,合成三环癸烷二甲醛最佳,选择性达到了72%。     

Synthesis of Gemini‐Like Methyl Acrylate‐Acrylic Acid‐Methyl Acrylate Triblock Copolymers Surfactants by RAFT Polymerization in Solution and Investigation of their Behavior at the Air–Water Interface

A series of methyl acrylate‐acrylic acid amphiphilic triblock copolymers (PMA‐PAA‐PMA) were prepared by solution polymerization using S,S′‐bis (α,α‐dimethy1acetic acid) trithiocarbonate (BDAT) as a reversible addition fragmentation chain transfer (RAFT) agent and methyl acrylate (MA) as the first monomer. The triblock copolymers and their common MA homopolymer precursors were characterized in terms of their compositions, molecular weights and behavior at the air–water interface using ¹H‐NMR spectroscopy, thermogravimetric analysis, gel permeation chromatography, surface tension, transmission electron microscopy (TEM) and dynamic light scattering respectively. The results indicated that PMA‐PAA‐PMA was successfully synthesized through RAFT polymerization. The polydispersity index (PDI) decreased when the molar ratio [n(MA)/n(AA)] increased, the lowest PDI was obtained at 5.23 wt% RAFT and the molecular weights were consistent with the theoretical value as the RAFT agent percentage varied. The polymer neutralized by sodium hydroxide solution shows a low critical micelle concentration (CMC), which was <10^?2 mol L^?1 in water. The A_min values increased and showed a maximum with decreased AA chain length. TEM showed that the neutralized polymer formed a special vesicle structure with large pore structure which led to a low CMC and surface tension of water.