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Novel porous ZnO/ZnFe2O4/C octahedra with hollow interiors are fabricated by a facile self-sacrificing template method involving the refluxing synthesis of hollow, metal-organic framework octahedra in solution and subsequent thermal annealing in N2 . When evaluated as an anode material for lithium-ion batteries, these porous hollow ZnO/ZnFe2O4/C octahedra exhibit significantly enhanced electrochemical performances with high rate capability, high capacity, and excellent cycling stability.

For lithium-sulfur batteries, commercial application is hindered by the insulating nature of sulfur and the dissolution of the reaction intermediates of polysulfides. Here, we present an ordered meso-microporous core-shell carbon (MMCS) as a sulfur container, which combines the advantages of both mesoporous and microporous carbon. With large pore volume and highly ordered porous structure, the "core" promises a sufficient sulfur loading and a high utilization of the active material, while the "shell" containing microporous carbon and smaller sulfur acts as a physical barrier and stabilizes the cycle capability of the entire S/C composite. Such a S/MMCS composite exhibits a capacity as high as 837 mAh g(-1) at 0.5 C after 200 cycles with a capacity retention of 80% vs the second cycle (a decay of only 0.1% per cycle), demonstrating that the diffusion of the polysulfides into the bulk electrolyte can be greatly reduced. We believe that the tailored highly ordered meso-microporous core-shell structured carbon can also be applicable for designing some other electrode materials for energy storage.

In lithium‐sulfur batteries, small S2–4 molecules show very different electrochemical responses from the traditional S8 material. Their exact lithiation/delitiation mechanism is not clear and how to select proper electrolytes for the S2–4 cathodes is also ambiguous. Here, S2–4 and S8/S2–4 composites with highly ordered microporous carbon as a confining matrix are fabricated and the electrode mechanism of the S2–4 cathode is investigated by comparing the electrochemical performances of the S2–4 and S2–4/S8 electrodes in various electrolytes combined with theoretical calculation. Experimental results show that the electrolyte and microstructure of carbon matrix play important roles in the electrochemical performance. If the micropores of carbon are small enough to prevent the penetration of the solvent molecules, the lithiation/delithiation for S2–4 occurs as a solid‐solid process. The irreversible chemically reactions between the polysulfudes and carbonates, and the dissolution of the polysulfides into the ethers can be effectively avoided due to the steric hindrance. The confined S2–4 show high adaptability to the electrolytes. The sulfur cathode based on this strategy exhibits excellent rate capability and cycling stability.

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The key descriptor that dominates the kinetics of the alkaline hydrogen evolution reaction (HER) has not yet been unequivocally identified. Herein, we focus on the adsorbed hydroxyl (OHad) transfer process (OHad + e− ⇄ OH−) and reveal its crucial role in promoting the overall kinetics of alkaline HER based on Ni/Co‐modified MoSe2 model catalysts (Ni‐MoSe2 and Co‐MoSe2) that feature almost identical water dissociation and hydrogen adsorption energies, but evidently different activity trends in alkaline (Ni‐MoSe2 ≫ Co‐MoSe2) and acidic (Co‐MoSe2 ≥ Ni‐MoSe2) media. Experimental and theoretical calculation results demonstrate that tailoring MoSe2 with Ni not only optimizes the hydroxyl adsorption, but also promotes the desorption of OH− and the electron‐involved conversion of OHad to OH−, all of which synergistically accelerate the kinetics of OHad + e− ⇄ OH− and thereby the overall kinetics of the alkaline HER.