Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

Thermodynamic properties of sodium hexatitanate (Na2Ti6O13) at high temperature (298.15–1573 K)

Sodium hexatitanate (Na₂Ti₆O₁₃) was reported as an anode side material for Sodium ion batteries owing to low material cost, high energy efficiency, good thermal stability and long cycle life. Therefore, studies pertaining to the thermodynamic properties of Na₂Ti₆O₁₃ are indispensable for improving its service performance. However, a significant number of literature reviews concerning thermodynamic properties indicated that heat capacity of Na₂Ti₆O₁₃ at high temperatures should be confirmed. In this study, the 99.5% purity of Na₂Ti₆O₁₃ sample was successfully prepared via solid-state reaction using TiO₂ and Na₂CO₃ as initial materials. Heat capacity of the as-synthesized samples in the temperature range of 573–1523 K was measured using a multi-high temperature calorimeter 96 line. Heat capacity, Cp, from 298.15 to 1573 K was modeled as a polynomial formula with a prediction error of 3%: Cp = 474.08143 + 0.06286T-8.04068 × 10⁶ T⁻² (J⋅mol⁻¹⋅K⁻¹). In combination with the low-temperature data, heat capacity of Na₂Ti₆O₁₃ from 0 to 1573 K was given in present study. Values of changes in enthalpy, Gibbs free energy and entropy in the temperature range of 298.15–1573 K were calculated based on the temperature dependence of heat capacity.     

Compositional design,structure stability,and microwave dielectric properties in Ca3MgBGe3O12 (B = Zr,Sn) garnet ceramics with tetravalent cations on B-site

Two garnet-structured Ca₃MgBGe₃O₁₂ (B = Zr, Sn) ceramics with tetravalent cations at B-site were prepared by conventional solid state reaction. The crystal structure, microstructure evolution, and microwave dielectric performance were investigated using X-ray powder diffraction, Rietveld refinement, scanning electron microscopy, Raman spectroscopy, and infrared spectroscopy techniques. Dense Ca₃MgZrGe₃O₁₂ and Ca₃MgSnGe₃O₁₂ ceramics were obtained at sintering temperatures of 1420 and 1400 °C, respectively. The dielectric constant, unloaded quality factor, and temperature coefficient of resonance frequency of Ca₃MgZrGe₃O₁₂ were 10.80 ± 0.2; 79,600 ± 1000 GHz (f = 12.61 GHz); and ?66.8 ± 1 ppm/°C, respectively, and the corresponding values for Ca₃MgSnGe₃O₁₂ were 9.68 ± 0.2; 83,400 ± 1000 GHz (f = 14.19 GHz); and ?57.9 ± 1 ppm/°C, respectively. The dielectric performances of the two ceramics were compared by analyzing the ionic polarizability, packing fraction, and bond valence. The intrinsic dielectric properties were predicted by fitting the infrared reflectivity spectra.     

Ultrasonically dispersed multi-composite strategy of NiCo2S4/Halloysite nanotubes/carbon: An efficient solid-state hybrid supercapacitor and hydrogen evolution reaction material

Herein, we have developed a novel hybrid material based on NiCo₂S₄ (NCS), halloysite nanotubes (HNTs), and carbon as promising electrodes for supercapacitors (SCs). Firstly, mesoporous NCS nanoflakes were prepared by co-precipitation method followed by physically mixing with HNTs and carbon, and screen printed on nickel foam. After ultrasonication, a uniform distribution of the Carbon/HNTs complex was observed, which was confirmed by surface morphological analysis. When used as electrode material, the NCS/HNTs/C hybrid displayed a maximum specific capacity of 544 mAh g^?1 at a scan rate of 5 mV s^?1. Later, a solid-state hybrid SCs was fabricated using activated carbon (AC) as the negative and NCS/HNTs/C as the positive electrode (NCS/HNTs/C//AC). The device delivers a high energy density of 42.66 Wh kg^?1 at a power density of 8.36 kW kg^?1. In addition, the device demonstrates long-term cycling stability. Furthermore, the optimized NCS, NCS/HNTs, and NCS/HNTs/C nanocomposites also presented superior hydrogen evolution reaction (HER) performance of 201, 169, and 116 mV in the acidic bath at a current density of 10 mA cm^?2, respectively. Thus, the synthesis of NCS/HNTs/C nanocomposite as positive electrodes for hybrid SCs opens new opportunities for the development of next-generation high energy density SCs.     

碳酸性侵蚀与AAR作用下纳米混凝土的耐久性

地铁混凝土处于地下空间,容易受到地下水的碳酸性侵蚀；碱集料反应 (AAR)是一种严重的混凝土耐久性问题,既难以发现又难以修补,由两者共同作用引起的混凝土耐久性降低严重影响地铁隧道的正常使用.为研究纳米材料对地铁混凝土在碳酸性侵蚀和AAR共同作用下耐久性的影响,在普通混凝土中掺入适量纳米SiO₂和纳米Fe₂O₃,利用自行研制的碳酸性侵蚀试验箱进行试验,采用碳酸性侵蚀深度、膨胀率和声速作为测试指标来评价纳米混凝土在碳酸性侵蚀和AAR共同作用下的耐久性.试验结果表明:掺入纳米颗粒后,混凝土的膨胀率和侵蚀深度有了明显降低,而声速有了明显提升,说明纳米混凝土的耐久性优于普通混凝土；在182 d龄期时,掺量为2%的纳米SiO₂混凝土耐久性改善最明显,侵蚀深度和膨胀率最小,声速最大且声速下降幅度最小；其次是掺量为1%的纳米Fe₂O₃混凝土.由于纳米颗粒特殊的物理化学性质,改善了混凝土内部的微观结构和孔溶液的化学组成,使碳酸性侵蚀和碱集料反应共同作用下混凝土的耐久性得到了提高.     

Astragali Radix-derived nitrogen-doped porous carbon: An efficient electrocatalyst for the oxygen reduction reaction

The development of biomass-derived nitrogen-doped porous carbons (NPCs) for the oxygen reduction reaction (ORR) is important for sustainable energy systems. Herein, NPCs derived from Astragali Radix (AR) via a cost-effective strategy are reported for the first time. The as-prepared AR-950-5 catalyst shows a stacked layer-like structure and porosity. Notably, the optimized AR-950-5 delivers catalytic activity comparable to that of commercial Pt/C (C-Pt/C), with high onset potential, positive half-wave potential and large limiting current density. It also displays superior long-term stability and methanol tolerance for ORR. This work will pave the way for a new approach in the development of highly active and low-cost NPCs for fuel cells.     

A Generalized Surface Chalcogenation Strategy for Boosting the Electrochemical N2 Fixation of Metal Nanocrystals

Electrocatalytic nitrogen reduction reaction (NRR) is a promising process relative to energy-intensive Haber–Bosch process. While conventional electrocatalysts underperform with sluggish paths, achieving dissociation of N₂ brings the key challenge for enhancing NRR. This study proposes an effective surface chalcogenation strategy to improve the NRR performance of pristine metal nanocrystals (NCs). Surprisingly, the NH₃ yield and Faraday efficiency (FE) (175.6 ± 23.6 mg h^–1 g^–1_Rh and 13.3 ± 0.4%) of Rh-Se NCs is significantly enhanced by 16 and 15 times, respectively. Detailed investigations show that the superior activity and high FE are attributed to the effect of surface chalcogenation, which not only can decrease the apparent activation energy, but also inhibit the occurrence of the hydrogen evolution reaction (HER) process. Theoretical calculations reveal that the strong interface strain effect within core@shell system induces a critical redox inversion, resulting in a rather low valence state of Rh and Se surface sites. Such strong correlation indicates an efficient electron-transfer minimizing NRR barrier. Significantly, the surface chalcogenation strategy is general, which can extend to create other NRR metal electrocatalysts with enhanced performance. This strategy open a new avenue for future NH₃ production for breakthrough in the bottleneck of NRR.     

Activity-Directed Synthesis: A Flexible Approach for Lead Generation

Activity-directed synthesis (ADS) is a structure-blind, functional-driven molecular discovery approach. In this Concept, four case studies highlight the general applicability of ADS and showcase its flexibility to support different medicinal chemistry strategies. ADS deliberately harnesses reactions with multiple possible outcomes, and allows many chemotypes to be evaluated in parallel. Resources are focused on bioactive molecules, which emerge in tandem with associated synthetic routes. Some of the future challenges for ADS are highlighted, including the realisation of an autonomous molecular discovery platform. The prospects for ADS to become a mainstream lead generation approach are discussed.