Synergistic Effect of P and Co Dual Doping Endows CuNi with High-Performance Hydrogen Evolution Reaction.

The rational design of highly active and durable non-noble electrocatalysts for hydrogen evolution reaction (HER) is significantly important but technically challenging. Herein, a phosphor and cobalt dual doped copper-nickel alloy (P, Co-CuNi) electrocatalyst with high-efficient HER performance is prepared by one-step electrodeposition method and reported for the first time. As a result, P, Co-CuNi only requires an ultralow overpotential of 56 mV to drive the current density of 10 mA cm-2, with remarkable stability for over 360 h, surpassing most previously reported transition metal-based materials. It is discovered that the P doping can simultaneously increase the electrical conductivity and enhance the corrosion resistance, while the introduction of Co can precisely modulate the sub-nanosheets morphology to expose more accessible active sites. Moreover, XPS, UPS, and DFT calculations reveal that the synergistic effect of different dopants can achieve the most optimal electronic structure around Cu and Ni, causing a down-shifted d-band center, which reduces the hydrogen desorption free energy of the rate-determining step (H2O + e- + H* → H2 + OH-) and consequently enhances the intrinsic activity. This work provides a new cognition toward the development of excellent activity and stability HER electrocatalysts and spurs future study for other NiCu-based alloy materials.

Two-step facile synthesis of Co3O4@C reinforced PbO2 coated electrode to promote efficient oxygen evolution reaction for zinc electrowinning.

The conventional Pb-Ag alloy possesses a high oxygen evolution reaction overpotential, poor stability, and short service life in acidic solutions, making it an unsuitable sort of anode material for the zinc electrowinning process. Therefore, a layered carbon-covered cobalt tetroxide (Co3O4@C)-reinforced PbO2-coated electrode is fabricated via a facile two-step pyrolysis-oxidation and subsequent electrodeposition process. As a result, the reinforced PbO2-coated electrode exhibits a low OER overpotential of 517 mV at 500 A m-2 and a Tafel slope of 0.152 V per decade in a zinc electrowinning simulation solution (0.3 M ZnSO4 and 1.53 M H2SO4). The reduced overpotential of 431 mV at 500 A m-2 compared to traditional Pb-0.76%Ag alloy leads to improved energy savings, which is attributable to the presence of Co3O4@C to refine the grain size and thus increase the effective contact area. Moreover, the reinforced PbO2-coated electrode has a prolonged service life of 93 h at 20 000 A m-2 in 1.53 M H2SO4. Therefore, an accessible and efficient strategy for preparing a coated electrode to improve OER performance for zinc electrowinning is presented in this research.

Facile synthesis MnCo2O4.5@C nanospheres modifying PbO2 energy-saving electrode for zinc electrowinning.

The oxygen evolution reaction kinetics in industrial zinc electrowinning is sluggish, resulting in low electrocatalytic activity and substantial energy expenditure (about one-third of energy was wasted due to the strong polarization effect). Herein, the paper described a core-shell structured MnCo2O4.5@C modified PbO2 electrode through the pyrolysis and co-electrodeposition as a promising candidate for zinc electrowinning. As a result, the obtained Pb-0.2%Ag/α-PbO2/ß-PbO2-MnCo2O4.5@C composite electrode showed a sandwich-like structure, where Pb-0.2%Ag as a core, α-PbO2 as a mid-layer, and ß-PbO2-MnCo2O4.5@C served as an electrocatalytic layer. It also possessed improved OER catalytic activity, only required 680 mV to achieve a current density of 50 mA cm-2 and a Tafel slope of 216.04 mV dec-1 in an acidic solution containing 50 g L-1 Zn2+ and 150 g L-1 H2SO4. The current efficiency increased by 0.7% and the cell voltage reduced by 360 mV as compared to a conventional Pb-0.76%Ag alloy electrode, leading to a remarkable energy-consumption reduction of 283.5 kW h for producing per ton metallic zinc. Furthermore, Pb-0.2%Ag/α-PbO2/ß-PbO2-MnCo2O4.5@C exhibited a prolonged service life, which worked about 44 h under an ultra-high current density of 2 A cm-2. Hence, this paper provides the strategy to design and construct non-precious, high-performance catalyst for electrolysis and other applications.

PbO2 modified with TiO2-NTs composite materials with enhanced OER electrocatalytic activity for Zn electrowinning.

The high oxygen evolution overpotential of the Pb-Ag anode is one of the main reasons for the high energy consumption in Zn electrowinning. PbO2, owing to its high conductivity, good corrosion resistance and low cost, is widely used as an excellent coating material. In present research, a novel composite Ti/TiO2-NTs/PbO2 material was synthesized through a facile anodization, annealing, electrochemical reduction and galvanostatic deposition. The surface morphology, internal structure and the mechanisms of TiO2-NTs enhancing electrochemical performance were discussed. The results show that the self-organized high aspect ratio TiO2-NTs with diameter of ∼120 nm and length of ∼8 µm were obtained on Ti substrate. The Ti/TiO2-NTs/PbO2 composite material exhibits excellent oxygen evolution performance and good stability in Zn electrowinning simulation solution (50 g L-1 Zn2+, 150 g L-1 H2SO4) at 35 °C. Its oxygen evolution overpotential is only 630 mV under current density 50 mA cm-2, which is 332 m lower than that of Pb-0.76 wt% Ag (η = 962 mV) and only increases 22 mV after 5000 cycles of CV scanning. Its outstanding electrochemical performance is mainly ascribed to the introduction of TiO2-NTs in Pb(CH3COO)2 media since it refines the crystal grains, increases the electrochemical surface area, greatly reduces the charge transfer resistance (25.4 Ω cm2 to 2.337 Ω cm2) and enhances corrosion resistance. Therefore, the Ti/TiO2-NTs/PbO2 material prepared in Pb(CH3COO)2 medium may be an ideal anode for Zn electrowinning.

α(ß)-PbO2 doped with Co3O4 and CNT porous composite materials with enhanced electrocatalytic activity for zinc electrowinning.

The high energy consumption during zinc electrowinning is mainly caused by the high overpotential of the oxygen evolution for Pb-Ag alloys with strong polarization. The preparation of new active energy-saving materials has become a very active research field, depending on the synergistic effects of active particles and active oxides. In this research, a composite material, α(ß)-PbO2, doped with Co3O4 and CNTs on the porous Ti substrate was prepared via one-step electrochemical deposition and the corresponding electrochemical performance was investigated in simulated zinc electrowinning solution. The composite material showed a porous structure, finer grain size and larger electrochemical surface area (ECSA), which indicated excellent electrocatalytic activity. Compared with the Pb-0.76 wt% Ag alloy, the overpotential of oxygen evolution for the 3D-Ti/PbO2/Co3O4-CNTs composite material was decreased by about 452 mV under the current density of 500 A m-2 in the simulated zinc electrowinning solution. The decrease in the overpotential of oxygen evolution was mainly ascribed to the higher ECSA and lower charger transfer resistance. Moreover, it showed the lowest self-corrosion current density of 1.156 × 10-4 A cm-2 and may be an ideal material for use in zinc electrowinning.

Histone lysine demethylase KDM5B maintains chronic myeloid leukemia via multiple epigenetic actions.

The histone lysine demethylase KDM5 family is implicated in normal development and stem cell maintenance by epigenetic modulation of histone methylation status. Deregulation of the KDM5 family has been reported in various types of cancers, including hematological malignancies. However, their transcriptional regulatory roles in the context of leukemia remain unclear. Here, we find that KDM5B is strongly expressed in normal CD34+ hematopoietic stem/progenitor cells and chronic myeloid leukemia (CML) cells. Knockdown of KDM5B in K562 CML cells reduced leukemia colony-forming potential. Transcriptome profiling of KDM5B knockdown K562 cells revealed the deregulation of genes involved in myeloid differentiation and Toll-like receptor signaling. Through the integration of transcriptome and ChIP-seq profiling data, we show that KDM5B is enriched at the binding sites of the GATA and AP-1 transcription factor families, suggesting their collaborations in the regulation of transcription. Even though the binding of KDM5B substantially overlapped with H3K4me1 or H3K4me3 mark at gene promoters, only a small subset of the KDM5B targets showed differential expression in association with the histone demethylation activity. By characterizing the interacting proteins in K562 cells, we discovered that KDM5B recruits protein complexes involved in the mRNA processing machinery, implying an alternative epigenetic action mediated by KDM5B in gene regulation. Our study highlights the oncogenic functions of KDM5B in CML cells and suggests that KDM5B is vital to the transcriptional regulation via multiple epigenetic mechanisms.

Preparation of ZnSO4·7H2O using filter cake enriched in calcium and magnesium from the process of zinc hydrometallurgy.

ZnSO4∙7H2O was prepared using a filter cake enriched in calcium and magnesium that was generated during the process of zinc hydrometallurgy. The study was optimized to obtain process parameters. The results show that the optimal acid leaching parameters are a solid-to-liquid ratio of 1:3.5, a sulfuric acid concentration of 16%, an acid leaching time of 20 min, a final pH of 4.1-4.4, a cooling and settling time of 120 min, an oxidation time of 20 min, a stirring speed of 300 r/min, a H2O2 dosage of 25 mL/L, a crystallization temperature of 20 °C, and a crystallization time of 60 min. The ZnSO4∙7H2O content in the product is 98.6%, and the zinc recovery efficiency is 97.5%. This process is characterized by simple flow and low cost, while the circulation and accumulation problems with calcium and magnesium ions in the zinc hydrometallurgy process are also solved.