Cobalt nanoparticles supported on magnetic core-shell structured carbon as a highly efficient catalyst for hydrogen generation from NaBH4 hydrolysis

A novel recyclable cobalt nanocatalyst, supported on magnetic carbon with core-shell structure, was successfully synthesized by using wetness impregnation-chemical reduction method for hydrogen generation from hydrolysis of NaBH₄. The resultant nanocomposite was characterized to determine the structural and physical-chemical properties by a series of analytical techniques such as FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscope), EDX (energy-dispersive X-ray spectroscopy), TEM (transmission electron microscopy), etc. The results demonstrated that amorphous cobalt nanoparticles were homogeneously surrounded on the surface of the support due to having abundant hydrophilic groups (such as aldehyde and hydroxyl groups) on the surface of carbon layer for the effective immobilization of metal ions. The supported catalyst showed superior catalytic performance towards the hydrolysis reaction of NaBH₄ at room temperature. The total rate of hydrogen generation and activation energy were calculated to be 1403 ml H₂ g_cat^?1 min^?1 and 49.2 kJ mol^?1, respectively, which were comparable to the values of most cobalt-based catalyst reported for hydrogen production from hydrolysis of NaBH₄. Additionally, reusability test revealed that the hydrogen in NaBH₄ substrate could be completely released within 25 min with a minimum hydrogen generation rate of 832 ml H₂ g_cat^?1 min^?1 even after five runs of hydrolytic reaction, implying the as-prepared Co/Fe₃O₄@C composite could be considered as a promising candidate catalyst for portable hydrogen fuel system such as PEMFC (proton exchange membrane fuel cells).     

Ultra-High Capacity and Cyclability of β-phase Ca0.14V2O5 as a Promising Cathode in Calcium-Ion Batteries

Crystalline water-free β-phase Ca_0.14V₂O₅ is reported for the first time as a viable cathode material for calcium-ion batteries (CIBs). In contrast to layered α-V₂O₅ and δ-Ca_xV₂O₅·nH₂O, which have limited capacity, the β-phase delivers a reversible capacity of ≈247 mAh g⁻¹, which corresponds to the insertion/extraction of Ca²⁺ between Ca_0.14V₂O₅ and Ca_1.0V₂O₅. The process of Ca²⁺ insertion process and the accompanying structural relaxation are theoretically and experimentally verified. The initial insertion of Ca²⁺ into Ca_0.14V₂O₅ causes a slight shift of oxygen atoms surrounding hepta-coordination sites, creating penta-coordinated sites that are then partially filled up to Ca_0.33V₂O₅. Further insertion occurs through the stepwise occupation of up to 50% of neighboring hexa- and tetra-coordination sites to form Ca_0.67V₂O₅ and Ca_1.0V₂O₅, respectively. The rearrangement of oxygen atoms in Ca_0.14V₂O₅ also minimizes dimensional changes, leading to high cyclic stability during repeated charge/discharge cycles. The remarkable electrochemical performance of full cells containing a Ca_0.14V₂O₅ cathode and a K metal anode in Ca²⁺/K⁺ hybrid electrolytes, is also demonstrated, thanks to the inertness of K⁺ insertion into Ca_0.14V₂O₅ and the absence of calcium plating/stripping. The cyclic stability and high capacity of Ca_0.14V₂O₅ is not compromised in hybrid electrolytes, making it a viable CIB cathode.     

Road Map for In Situ Grown Binder-Free MOFs and Their Derivatives as Freestanding Electrodes for Supercapacitors

Among several electrocatalysts for energy storage purposes including supercapacitors, metal–organic frameworks (MOFs), and their derivatives have spurred wide spread interest owing to their structural merits, multifariousness with tailor-made functionalities and tunable pore sizes. The electrochemical performance of supercapacitors can be further enhanced using in situ grown MOFs and their derivatives, eliminating the role of insulating binders whose “dead mass” contribution hampers the device capability otherwise. The expulsion of binders not only ensures better adhesion of catalyst material with the current collector but also facilitates the transport of electron and electrolyte ions and remedy cycle performance deterioration with better chemical stability. This review systematically summarizes different kinds of metal–ligand combinations for in situ grown MOFs and derivatives, preparation techniques, modification strategies, properties, and charge transport mechanisms as freestanding electrode materials in determining the performance of supercapacitors. In the end, the review also highlights potential promises, challenges, and state-of-the-art advancement in the rational design of electrodes to overcome the bottlenecks and to improve the capability of MOFs in energy storage applications.