Amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets as Janus electrocatalyst for efficient water splitting

Efficient and sustainable Janus catalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are highly desirable for future hydrogen production via water electrolysis. Herein we report an active Janus electrocatalyst of amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets on nickel foam (CoMoP/CoP/NF) for efficient electrolysis of alkaline water. As-reported CoMoP/CoP/NF consists of amorphous bimetal phosphide nanosheets doped with crystalline CoMoP/CoP heterostructured nanoparticles on NF. It can efficiently catalyze both HER (η = 127 mV@100 mA cm^?2) and OER (η = 308 mV@100 mA cm^?2) in alkaline electrolyte with long-term durability. Serving as anode and cathode of water electrolyzer, CoMoP/CoP/NF generates electrolytic current of 10, 50 and 100 mA cm^?2 at low voltage of 1.50, 1.59, and 1.67 V, respectively.     

Effect of mass transfer on the deactivation model and GPLE parameters of Co/γ-Al2O3 catalysts in the Fischer Tropsch synthesis

The activity of catalysts with various sizes was compared in a fixed-bed Fischer–Tropsch reactor under similar operating conditions by determining the deactivation model. Catalyst size had no impact on the type of deactivation model. The smaller catalyst showed a smaller deactivation constant of catalyst (k_d) and a lower deactivation rate in the initial stage. The decline in the activities of the catalyst with a mesh size of 40 was lower than the other catalysts, suggesting its higher long-term stability (a_ss). Larger catalyst sizes led to the fouling of carbon and heavy hydrocarbons, decreasing the specific surface of the catalyst, thus increasing the pore diffusion resistance and further decrementing the catalyst activities.     

Flowsheet Options for Cobalt Recovery in African Copper–cobalt Hydrometallurgy Circuits

The price of cobalt has increased by some 450% in the past two years, mainly due to increasing demand for lithium–ion batteries. With an official 2017 production of 64 kt, the Democratic Republic of Congo produces more than half of the world’s cobalt. African Copperbelt operations have traditionally focused on copper production; however, it has now become imperative to also consider cobalt recovery from these ores. A plethora of processing routes is possible. Most hydrometallurgical flowsheets recover cobalt from the raffinate of the low-grade copper solvent-extraction circuit. Downstream purification processes include sequential precipitation with a variety of reagents, solvent extraction, and ion exchange. Product choices include hydroxide, carbonate, sulfate, and metal cathode. This study assesses technical and economic advantages and limitations of various approaches to the hydrometallurgical processing of cobalt in an African context.     

Mineralization of Para-Chlorobenzoic Acid in Water by Cobalt-Incorporated MCM-41 Catalyzed Ozonation

Cobalt-incorporated MCM-41(Co-MCM-41) was used as a heterogeneous catalyst for the ozonation of para-chlorobenzoic acid (p-CBA) in aqueous solution. Cobalt oxide supported on MCM-41(Co/MCM-41) was synthesized for comparison. Their textural properties were elucidated by various characterization techniques to understand the relationship between surface texture and catalytic activity. TOC removal at 60 min reached 91% with Co-MCM-41, 83% with Co/MCM-41 and only 52% with ozone alone, respectively. Observations from diffuse reflection spectroscopy demonstrated that different metal phases were formed in these cobalt-modified molecular sieves samples. Radical scavenger experiments indicated the formation of hydroxyl radicals that were responsible for the effective degradation of p-CBA. An integrated approach to the catalytic mechanism was proposed by considering the variation of pH in the course of ozonation as well as its subsequent influence on the dissociation of targeted compounds and surface charge of the catalyst. In the reusability experiments, the reused Co-MCM-41 was able to regain the same catalytic capability as the fresh one within 5 cycles. X-ray photoelectron spectroscopy results indicated that a part of Co²⁺ was oxidized to Co³⁺ after oxidation reaction.     

Structural,magnetic and magnetostrictive properties of Co1-xLixFe2O4 synthesized by cathode materials of spent Li-ion batteries

In this study, we investigated the effects of substituting Li⁺ for Co²⁺ at the B sites of the spinel lattice on the structural, magnetic and magnetostrictive properties of cobalt ferrites. The Li⁺ substituted cobalt ferrites, Co_1-xLi_xFe₂O₄, with x varying from 0 to 0.7 in 0.1 increments, were synthesized with a sol-gel auto-combustion method using the cathode materials of spent Li-ion batteries. X-ray diffraction analysis revealed that all the Co_1-xLi_xFe₂O₄ nanopowders had a single-phase spinel structure and the lattice parameters decreased with increasing Li⁺ content, which can be proved by slight shifts towards higher diffraction angle values of the (311) peak. Field emission scanning electron microscopy was used to observe the fractured inner surface of the sintered cylindrical rods and the increased porosity resulted in a decreased magnetostriction. The oxidation states of Co and Fe in the cobalt ferrite samples were examined by X-ray photoelectron spectroscopy. High resolution transmission electron microscopy micrographs showed that most particles were roughly spherical and with sizes of 25–35?nm. Li⁺ substitution had a strong effect on the saturation magnetization and coercivity, which were characterized with a vibrating sample magnetometer. The Curie temperature was reduced due to the decrease in magnetic cations and the weakening of the exchange interactions. The magnetostrictive properties were influenced by the incorporation of Li⁺ at the B sites of the spinel structure and correlated with the changes in porosity, magnetocrystalline anisotropy and the cation distribution.     

Highly dispersed cobalt nanoparticles onto nitrogen-doped carbon nanosheets for efficient hydrogen generation via catalytic hydrolysis of sodium borohydride

Porous carbon nanostructures are promising supports for stabilizing the highly dispersed metal nanoparticles and facilitating the mass transfer during the reaction, which are critical to achieve the high efficiency of hydrogen generation from sodium borohydride dehydrogenation. Herein, the catalytically active porous architectures are simply prepared by using 2-methylimidazole and melamine as reactive sources. The structural and compositional characterizations reveal the coexistence of metallic cobalt and N-doped carbon in porous architectures. Electron microscopy observations indicate that the synthesized products are smartly constructed from the carbon nanosheets with densely dispersed Co nanoparticles. Due to the notable structural features, the prepared Co@NC-600 sample presents the highly efficient activity for catalytic hydrolysis of NaBH₄ with a hydrogen generation rate of 2574 mL min⁻¹ g_cat⁻¹ and an activation energy of 47.6 kJ mol⁻¹. The catalytically active metallic Co and suitable support-effect of N-doped carbon are responsible for catalytic dehydrogenation.     

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.     

Water‐Stable,Magnetic Silica–Cobalt/Cobalt Oxide–Silica Multishell Submicrometer Spheres

A method to produce monodisperse magnetic composite spheres with diameters from less than 100 nm to more than 1 μm in water solution is reported. The spheres consist of a dielectric silica core and a cobalt/cobalt oxide shell which can be protected from further oxidation with an outer shell of silica or, alternatively, they can be covered with the polymer polyvinylpyrrolidone as a stabilizer. The formation of a uniform magnetic shell proceeds with the adsorption of metallic cobalt seeds, produced by the reduction of cobalt chloride with sodium borohydride, on a self‐assembled layer of polyelectrolytes on the silica core. In the second step, an outer silica shell can be formed by the hydrolysis and condensation of (3‐aminopropyl)trimethoxysilane and tetraethoxysilane. The double‐shell composite spheres show excellent sphericity, monodispersity, and a magnetic hysteresis loop at room temperature.     

流动注射分光光度法测定钴

研究了将ＰＡＮ用于流动注射（ＦＩＡ）分光光度法测定微量钴，在５６０ｎｍ处绘制标准曲线，线性范围为０～４５μｇ／ｍｌ，相关系数０．９９６，方法的相对标准偏差（ＲＳＤ）小于３％，加标回收率为９５％～１０５％，进样频率８０次／ｈ。本法简单快速，用于面粉、分子筛，铝合金测定结果令人满意。     

从含钴催化剂废料中回收氧化钴的研究

选用酸溶——沉淀化学法，对含钴催化剂废料提取氧化钴的实验研究。实验结果表明，回收氧化钴产品中含钴量71％，氧化钴的实收率85％。同时将铁回收为铁红产品（含Fe2O3≤65％），铁的实收率高达88％。其它的技术经济指标较高。这是一种工艺技术及设备可行的新途径。