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.     

某铁矿强磁尾矿反浮选回收试验研究

针对我国西部某铁矿强磁选尾矿进行了反浮选回收铁资源的试验研究, 探讨了pH值、抑制剂可溶性淀粉用量、阳离子捕收剂十二胺用量对浮选指标的影响。结果表明, 在矿浆pH=10、可溶性淀粉用量2 400 g/t、十二胺用量400 g/t条件下进行一粗一精(精选药剂用量减半)闭路反浮选, 可获得铁品位43.88%、回收率50.93%的铁精矿产品。     

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.     

大豆蛋白纳米纤维对铁纳米颗粒的稳态化作用

为明确大豆蛋白纳米纤维的结构形成和扩宽铁强化剂的食品工业应用，以大豆分离蛋白（soy protein isolate，SPI）为原料，通过5 h的酸热处理制备纳米纤维（soy protein isolate fibrils，Fib SPI），系统研究纤维形成前后蛋白结构的变化，并进一步制备铁纳米颗粒（iron nanoparticles，Fe NPs），探究Fib SPI对铁的稳态化作用。研究结果表明：在酸热处理过程中，SPI产生大量的β-折叠结构，其与硫磺素T结合，显示出增强的荧光强度；此外，7S组分先发生降解，利于纤维成核形成，随后11S逐渐被水解，促进纤维生长；同时水解产生大量的小肽组分，提高了产物的还原力。研究进一步利用Fib SPI递送铁纳米颗粒（Fe NPs），发现与原始SPI相比，铁纳米颗粒可在Fib SPI原位形成胶体稳定的铁-大豆蛋白纳米纤维复合物（Fe FibSPI），并以Fe（II）形式存在，其对乳液体系色泽及稳定性的影响较硫酸亚铁或氯化铁小。该研究可为构建新型植物基铁强化剂递送体系提供理论和方法指导。     

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.     

Co2FeO4@rGO composite: Towards trifunctional water splitting in alkaline media

Development of efficient, low cost and multifunctional electrocatalysts for water splitting to harvest hydrogen fuels is a challenging task, but the combination of carbon materials with transition metal-based compounds is providing a unique and attractive strategy. Herein, composite systems based on cobalt ferrite oxide-reduced graphene oxide (Co₂FeO₄) @(rGO) using simultaneous hydrothermal and chemical reduction methods have been prepared. The proposed study eliminates one step associated with the conversion of GO into rGO as it uses direct GO during the synthesis of cobalt ferrite oxide, consequently rGO based hybrid system is achieved in-situ significantly, the optimized Co₂FeO₄@rGO composite has revealed an outstanding multifunctional applications related to both oxygen evolution reaction (OER) and hydrogen counterpart (HER). Various metal oxidation states and oxygen vacancies at the surface of Co₂FeO₄@rGO composites guided the multifunctional surface properties. The optimized Co₂FeO₄@rGO composite presents excellent multifunctional properties with onset potential of 0.60 V for ORR, an overpotential of 240 mV at a 20 mAcm^?2 for OER and 320 mV at a 10 mAcm^?2 for HER respectively. Results revealed that these multifunctional properties of the optimized Co₂FeO₄@ rGO composite are associated with high electrical conductivity, high density of active sites, crystal defects, oxygen vacancies, and favorable electronic structure arisinng from the substitution of Fe for Co atoms in binary spinel oxide phase. These surface features synergistically uplifted the electrocatalytic properties of Co₂FeO₄@rGO composites. The multifunctional properties of the Co₂FeO₄@ rGO composite could be of high interest for its use in a wide range of applications in sustainable and renewable energy fields.     

Essential (Mg,Fe, Zn and Cu) and Non-Essential (Cd and Pb) Elements in Predatory Insects (Vespa crabro and Vespa velutina): A Molecular Perspective

The recent introduction of the Asian yellow-legged hornet, Vespa velutina, into Europe has raised concern regarding the threat to honeybees and the competition with the European hornet, Vespa crabro. The aim of this study was to investigated essential (Mg, Fe, Zn, Cu) and non-essential (Cd and Pb) elements in these two species. Element concentrations were determined in the whole body and separately in the head, thorax and abdomen using atomic absorption spectrometry (AAS). The changes in essential element concentration and speciation during metamorphosis were also studied using size exclusion chromatography followed by AAS and proteomic analysis. In both species, the essential elements were more concentrated in the abdomen due to the presence of fat bodies. Magnesium, Fe and Zn concentrations were significantly higher in V. crabro than in V. velutina and could have been related to the higher aerobic energy demand of the former species required to sustain foraging flight. Low concentrations of Cd and Pb were indicative of low environmental exposure. The concentration and speciation of essential elements, particularly Fe, varied among the developmental stages, indicating a modification of ligand preferences during metamorphosis. Overall, the results in the present study provide a better understanding of the hornet metal metabolism and a foundation for additional studies.     

Tailored-Made Polydopamine Nanoparticles to Induce Ferroptosis in Breast Cancer Cells in Combination with Chemotherapy

Ferroptosis is gaining followers as mechanism of selective killing cancer cells in a non-apoptotic manner, and novel nanosystems capable of inducing this iron-dependent death are being increasingly developed. Among them, polydopamine nanoparticles (PDA NPs) are arousing interest, since they have great capability of chelating iron. In this work, PDA NPs were loaded with Fe³⁺ at different pH values to assess the importance that the pH may have in determining their therapeutic activity and selectivity. In addition, doxorubicin was also loaded to the nanoparticles to achieve a synergist effect. The in vitro assays that were performed with the BT474 and HS5 cell lines showed that, when Fe³⁺ was adsorbed in PDA NPs at pH values close to which Fe(OH)₃ begins to be formed, these nanoparticles had greater antitumor activity and selectivity despite having chelated a smaller amount of Fe³⁺. Otherwise, it was demonstrated that Fe³⁺ could be released in the late endo/lysosomes thanks to their acidic pH and their Ca²⁺ content, and that when Fe³⁺ was co-transported with doxorubicin, the therapeutic activity of PDA NPs was enhanced. Thus, reported PDA NPs loaded with both Fe³⁺ and doxorubicin may constitute a good approach to target breast tumors.