Hydrangea like composite catalysts of ultrathin Mo2S3 nanosheets assembled on N,S-dual-doped graphitic biocarbon spheres with highly electrocatalytic activity for HER

Water electrolysis is the most clean and high-efficiency technology for production of hydrogen, an ultimate clean energy in future. Highly efficient non-noble electrocatalysts for hydrogen evolution reaction (HER) are desirable for large scale production of hydrogen by water electrolysis. Especially, exposing as many active sites as possible is a vital way to improve activities of the catalysts. Herein, a series of new hydrangea like composite catalysts of ultrathin Mo₂S₃ nanosheets assembled uprightly and interlacedly on N, S-dual-doped graphitic biocarbon spheres were facilely prepared. The unique structure endowed the catalysts highly exposed edge active sites and prominently high activities for HER. Especially, the optimized catalyst Mo₂S₃/NSCS-50 exhibited as low as 106 mV of overpotential at 10 mA/cm² (denoted as ?₁₀). The catalyst also showed low Tafel slope of 53 mV/dec, low electron transfer resistance of 34 Ω and high stability evidenced by the result that the current density only attenuated 11.7% after 10 h i-t test. The catalyst has shown broad prospect for commercial application in water electrolysis.     

Wavelength-dependent photoactivity of ZnxCd1−xS and ZnCo2O4/ZnxCd1−xS for H2 and H2O2 production

Zinc cadmium sulfide (Zn_xCd_1?xS) is a good photocatalyst for hydrogen evolution reaction (HER), but an optimum x (x_m) at which a maximum HER rate is reached varies from one report to another. In this work, we examine the effect of light wavelength, not only for the HER to H₂ in the presence of Na₂S and Na₂SO₃, but also for oxygen reduction reaction (ORR) without addition of any sacrifices. For the HER under a 365 and 420 nm LED lamp, the x_m were 0.9 and 0.7, respectively. For the HER under a 330 and 395–515 nm cut-off xenon lamp, the x_m were 0.7 and 0.5, respectively. For the ORR under a 420 nm cut-off halogen lamp, a maximum production of H₂O₂ was observed at x = 0.3. Furthermore, after 4% ZnCo₂O₄ loading, Zn_xCd_1?xS had an increased activity and stability, either for the HER or for the ORR. Through a (photo)electrochemical measurement, it is proposed that the photocatalytic activity of Zn_xCd_1?xS is determined by its light absorptivity and electron reactivity. The improved performance of n-type Zn_xCd_1?xS by p-type ZnCo₂O₄ is due to formation of a p-n junction, promoting the HER (ORR) on Zn_xCd_1?xS, and the sulfide (water) oxidation on ZnCo₂O₄. This work highlights that Zn_xCd_1-xS is a promising photocatalyst for H₂ and H₂O₂ production, respectively.     

Zeolitic-imidazolate frameworks-derived Co3S4/NiS@Ni foam heterostructure as highly efficient electrocatalyst for oxygen evolution reaction

Transition metals sulfide-based nanomaterials have recently received significant attention as a promising cathode electrode for the oxygen evolution reaction (OER) due to their easily tunable electronic, chemical, and physical properties. However, the poor electrical conductivity of metal-sulfide materials impedes their practical application in energy devices. Herein, firstly nano-sized crystals of cobalt-based zeolitic-imidazolate framework (Co-ZIF) arrays were fabricated on nickel-form (NF) as the sacrificial template by a facile solution method to enhance the electrical conductivity of the electrocatalyst. Then, the Co₃S₄/NiS@NF heterostructured arrays were synthesized by a simple hydrothermal route. The Co-ZIFs derived Co₃S₄ nanosheets are grown successfully on NiS nanorods during the hydrothermal sulfurization process. The bimetallic sulfide-based Co₃S₄/NiS@NF-12 electrocatalyst demonstrated a very low overpotential of 119 mV at 10 mA cm^?2 for OER, which is much lower than that of mono-metal sulfide NiS@NF (201 mV) and ruthenium-oxide (RuO₂) on NF (440 mV) electrocatalysts. Furthermore, the Co₃S₄/NiS@NF-12 electrocatalyst showed high stability during cyclic voltammetry and chronoamperometry measurements. This research work offers an effective strategy for fabricating high-performance non-precious OER electrocatalysts.     

S/Se dual-doping promotes the formation of active Ni/Fe oxyhydroxide for oxygen evolution reaction of (sea)water splitting

Surface reconstruction produces metal oxyhydroxide (1OOH) active sites, and promoting surface reconstruction is essential for the design of OER electrocatalysts. In this paper, we reported that a large amount of active NiFeOOH was generated in-situ on the surface of nickel-iron sulfide selenide, thus exposing more active sites and efficiently catalyzing OER. In 1 M KOH solution, NiFeOOH(S,Se) achieves an ultra-low overpotential of 195 mV at the current density of 10 mA cm^?2, and the Tafel slope is only 31.99 mV dec^?1, showing excellent catalytic performance. When the current density is 100  mA cm^?2, the over-potential of NiFeOOH(S,Se) in KOH + seawater solution is 239 mV, which is almost equivalent to 231 mV in KOH solution. The excellent OER stability of the NiFeOOH(S,Se) catalyst in alkaline electrolytes was confirmed, and the overpotential did not change significantly after 4 days of testing in KOH + seawater solution.     

Fabrication of NixCo3-xS4 hollow nanosphere as wideband electromagnetic absorber at thin matched thickness

Nowadays, transition metal sulfide (TMS), especially for spinel crystal structure (A_xB_3-xS₄), have been proved to be a promising electromagnetic (EM) absorber if been used to deal with the severe electromagnetic pollution. However, EM performance degradation and absorption layer thickness-decreasing at present remains a big challenge, owning to the poor EM attenuation ability. To overcome this barrier, herein we reported a Ni_xCo_3-xS₄ (x = 0, 0.3, 0.6, 1.0) absorber with hollow sphere structure to realize a good EM performance with a thinner matched thickness (<1.5 mm). The average sizes of these Ni_xCo_3-xS₄ distributed in 450–550 nm. The dielectric loss ability (ε'') can be boosted by tuning the molar ratio of Ni/Co, which attributes to EM performance. Additionally, hollow structure would lead to the electromagnetic multi-reflection, also benefited to EM performance. The results demonstrated that the maximum qualified absorption bandwidth (f_E) of 3.8 GHz can be achieved for the Ni_0·3Co_2·7S₄ sample when specimen thickness only equals to 1.3 mm.     

镁对非调质钢中组织及硫化物的影响

摘要：为了探究不同镁含量对非调质钢中组织和硫化物形态、尺寸、分布及成分的影响，采用蔡司金相显微镜、扫描电子显微镜、小样电解等方法，分析了经高温电阻炉冶炼不同镁添加量的49MnVS3非调质钢。结果表明，由于镁蒸气压较高，在实验室冶炼中大量挥发，导致钢中镁的实际平均收得率仅为310%；镁的质量分数为0～22×10-6时，随着镁的质量分数的增加，钢中硫化物形态由Ⅱ类逐渐向Ⅰ类、Ⅲ类转变；钢中硫化物尺寸增大，硫化物的分布均匀性得到显著改善；钢中复合夹杂物比例明显增加，但MnS的比例出现下降；形成了细小弥散的氧化物，增加了奥氏体形核质点，具有细化组织的趋势。     

Ternary metal sulfides MoCoNiS derived from metal organic frameworks for efficient oxygen evolution

Developing a highly active and low-cost non-precious metal electrocatalyst for oxygen evolution has been urgent for the clean energy system. Herein, the ternary metal sulfides MoCoNiS supported on nickel foam (MoCoNiS/NF) are successfully prepared using Mo doping Co-based metal-organic framework (Co-MOF) as precursor, which may be helpful for the good dispersion of different metal element. The uniform elements distribution of Mo, Co and Ni on MoCoNiS/NF is determined by all kinds of physical characterization. Mo doping may regulate the electronic environment around Co and Ni, suggesting the potential synergistic effects between different heteroatoms. Electrochemical test shows that MoCoNiS/NF exhibits the excellent OER activity than other single metal or binary metal sulfides as comparison samples, needing only 151 and 226 mV overpotential to achieve current density of 10 (η₁₀ = 151 mV) and 100 mA cm⁻² (η₁₀₀ = 226 mV), respectively. The excellent stability of MoCoNiS/NF has been achieved. The remarkable OER performance of MoCoNiS/NF may due to the synergistic effects and good electrical conductivity as well as the three-dimensional structure of NF as substrate. Therefore, the rational design of MOF derived multi transition metal-based electrocatalysts will be an effective way for increasing OER performance.     

基于双转子连续混炼挤出机的PPS/CF复合材料制备及性能研究

采用双转子连续混炼挤出机并通过熔融共混法制备了碳纤维(CF)增强聚苯硫醚(PPS)复合材料，并对其微观形貌、动态力学性能、力学性能和导电性能进行了研究，且对相关的影响因素进行了分析。结果表明，适当降低挤出机转子转速、提高CF含量可以改善PPS/CF复合材料的力学性能和导电性能；当转子转速为200r/min时，采用含量为20 % (质量分数，下同)的CF制得的PPS/CF复合材料的冲击强度达到49.94 J/m，体积电阻率达到60.65 Ω·cm，均优于纯PPS。     

Deactivation of hydrodesulfurization catalysts during reactor startup

Metal sulfide catalysts for ultra-deep hydrodesulfurization of diesel generally lose a fraction of their catalytically active sites during reactor startup. The underlying mechanisms are discussed. A laboratory diagnostic tool consisting of three probe molecules is developed for testing metal sulfide catalysts' start-of-run (SOR) activity maintenance. It is found that a significant fraction of the active sites on a commercial supported catalyst are deactivated permanently, but this is not the case with a bulk metal sulfide catalyst. The SOR deactivation of the bulk catalyst is completely reversible, while that of the supported catalyst is partially reversible. The diagnostic tool may provide a basis for developing a high-throughput approach for evaluating and enhancing catalyst SOR stability, thereby increasing plant productivity.     

某高硫矽卡岩型金铜矿选矿试验研究

针对高硫矽卡岩金铜矿中黄铁矿含量高、难抑制特点,采用对黄铁矿捕收能力非常弱的Z-200和丁基铵黑药作为浮选捕收剂,在低碱度条件下(pH值9.5)实现了铜与金的综合回收。研究结果表明:闭路试验混合精矿铜品位为21.15%、金品位为24.11g/t,铜和金的回收率分别可达93.92%和83.73%,选矿指标较为理想。