Theoretical calculations reveal that intrinsic pentagons in the basal plane can contribute to the local electronic redistribution and the contraction of band gap, making the carbon matrix possess superior binding affinity and electrochemical reactivity. To experimentally verify this, a pentagon‐defect‐rich carbon nanomaterial was constructed by means of in situ etching of fullerene molecules (C60). The electrochemical tests show that, relative to hexagons, such a carbon‐based material with abundant intrinsic pentagon defects makes much greater contribution to the electrocatalytic oxygen reduction activity and electric double layer capacitance. It shows a four‐electron‐reaction mechanism similar to commercial Pt/C and other transition‐metal‐based catalysts, and a higher specific capacitance than many reported metal‐free carbon materials. These results show the influence of intrinsic pentagon defects for developing carbon‐based nanomaterials toward energy conversion and storage devices.

The weak van der Waals interactions enable ion‐intercalation‐type hosts to be ideal pseudocapacitive materials for energy storage. Here, a methodology for the preparation of hydrated vanadium dioxide nanoribbon (HVO) with moderate transport pathways is proposed. Out of the ordinary, the intercalation pseudocapacitive reaction mechanism is discovered for HVO, which powers high‐rate capacitive charge storage compared with the battery‐type intercalation reaction. The main factor is that the defective crystalline structure provides suitable ambient spacing for rapidly accommodating and transporting cations. As a result, the HVO delivers a fast Zn2+ ion diffusion coefficient and a low Zn2+ diffusion barrier. The electrochemical results with intercalation pseudocapacitance demonstrate a high reversible capacity of 396 mAh g−1 at 0.05 A g−1, and even maintain 88 mAh g−1 at a high current density of 50 A g−1.

In this article, a simple self-assembly strategy for fabricating van der Waals heterostructures from isolated two-dimensional atomic crystals is presented. Specifically, dopamine (DOPA), an excellent self-assembly agent and carbon precursor, was adsorbed on exfoliated MoS2 monolayers through electrostatic interaction, and the surface-modified monolayers self-assembled spontaneously into DOPA-intercalated MoS2. The subsequent in situ conversion of DOPA to highly conductive nitrogen-doped graphene (NDG) in the interlayer space of MoS2 led to the formation of a novel NDG/MoS2 nanocomposite with well-defined alternating structure. The NDG/MoS2 was then studied as an anode for lithium-ion batteries (LIBs). The results show that alternating arrangement of NDG and MoS2 triggers synergistic effect between the two components. The kinetics and cycle life of the anode are greatly improved due to the enhanced electron and Li(+) transport as well as the effective immobilization of soluble polysulfide by NDG. A reversible capacity of more than 460 mAh/g could be delivered even at 5 A/g. Moreover, the abundant voids created at the MoS2-NDG interface also accommodate the volume change during cycling and provide additional active sites for Li(+) storage. These endow the NDG/MoS2 heterostructure with low charge-transfer resistance, high sulfur reservation, and structural robustness, rendering it an advanced anode material for LIBs.