Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H₂O in the HER.

Since sluggish Li⁺ desolvation leads to severe capacity degradation of carbon anodes at subzero temperatures, it is urgently desired to modulate electron configurations of surface carbon atoms toward high capacity for Li-ion batteries. Herein, a carbon-based anode material (O-DF) was strategically synthesized to construct the Riemannian surface with a positive curvature, which exhibits a high reversible capacity of 624 mAh g^-1 with an 85.9% capacity retention at 0.1 A g^-1 as the temperature drops to -20 °C. Even if the temperature drops to -35 °C, the reversible capacity is still effectively retained at 160 mAh g^-1 after 200 cycles. Various characterizations and theoretical calculations reveal that the Riemannian surface effectively tunes the low-temperature sluggish Li⁺ desolvation of the interfacial chemistry via locally accumulated charges of non-coplanar sp ^x (2 < x < 3) hybridized orbitals to reduce the rate-determining step of the energy barrier for the charge-transfer process. Ex-situ measurements further confirm that the sp ^x -hybridized orbitals of the pentagonal defect sites should denote more negative charges to solvated Li⁺ adsorbed on the Riemannian surface to form stronger Li-C coordinate bonds for Li⁺ desolvation, which not only enhances Li-adsorption on the curved surface but also results in more Li⁺ insertion in an extremely cold environment.