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.     

Electrodeposition of the manganese-doped nickel-phosphorus catalyst with enhanced hydrogen evolution reaction activity and durability

Hydrogen technology is widely considered a novel clean energy source, and electrolysis is an effective method for hydrogen evolution. Therefore, efficient hydrogen evolution reaction (HER) catalysts are urgently needed to replace precious metal catalysts and meet ecological and environmental protection standards. Herein, Ni–Mn–P electrocatalysts are synthesized using facile electrodeposition technology. The influence of the Mn addition on the catalytic behavior is studied by the comprehensive analysis of catalytic performance and morphology of the catalysts. Among them, the Ni–Mn–P0.01 catalyst exhibits small coral-like structures, greatly improving the adsorption and desorption of hydrogen ions and reducing the overpotential hydrogen evolution. Consequently, overpotential at 10 mA cm^?2 electric current density is 113 mV, and the value of the Tafel slope achieves 74 mV/dec. Furthermore, the Ni–Mn–P catalyst shows long-time (20 h) stability at current densities of 10 and 60 mA/cm². The results confirm that the synergistic effect of Ni, Mn, and P accelerates the electrochemical reaction. Meanwhile, the addition of manganese element can change the micromorphology of the catalyst, thereby exposing more active sites to participate in the reaction, enhancing water ionization, improving the catalytic performance. This study opens a new way toward improving the activity of the catalyst by adjusting Mn concentration during the electrodeposition process.     

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.     

Use of the Retarded Solution-Reprecipitation Process to Attain a Higher Initial Permeability in MnZn Ferrites

We investigated the effect of various amounts of liquid phase on microstructure development during sintering and the resulting magnetic permeability of MnZn ferrite (MZF) samples. Our results revealed that the microstructure and the final magnetic permeability depend on the thickness of the liquid-phase film during sintering. The solution-reprecipitation (S-R) process, which is associated with an intensive microstructure development in MZF, starts when a continuous liquid-phase film of critical thickness δ_o, which wets the MZF grains, is formed. The solid-state sintering that takes place before the formation of the continuous liquid-phase film is essential for the final microstructure of MZF.