Spinel cobaltites are widely presented as promising pseudocapacitive materials, however, a fundamental understanding of their structure–property relationship at an atomic level remains vague. Herein, their geometrical‐site‐dependent charge storage capability is investigated by substituting Co with inactive Zn and redox‐active Mn. Experimental and theoretical analyses reveal that redox‐active cations in octahedral sites contribute to enhanced capacitance, intrinsically determined by the covalency competition between tetrahedral and octahedral sites. The Zn2+ incorporation leads to increased occupancy of Co in octahedral sites and 2.9× increased capacitance at 1 A g−1 current density, whereas the substituted Mn cations mainly sit in octahedral sites which can react with OH− upon cycling and separate on the spinel surface to reconstruct into δ‐MnO2 nanosheets, leading to 4× increased capacitance at 1 A g−1 current density with a detected K+ ion intercalation. Thus, the exposure of redox‐active cations in octahedral sites and their intrinsic properties are influential in determining spinel oxides’ pseudocapacitive properties. This work provides a general principle to optimize the pseudocapacitive properties of spinel cobaltites by deliberately selecting cations for substitution and controlling their distribution in octahedral/tetrahedral sites. It also offers a fundamental understanding of geometrical‐site‐dependent activity, and can effectively guide the development of spinel oxides for enhanced pseudocapacitance.

The layer-by-layer assembly of 2D transition metal dichalcogenide monolayer blocks to form a 3D stack, with a precisely chosen sequence/angle, is the newest development for these materials. In this way, one can create "van der Waals heterostructures (HSs)," opening up a new realm of materials engineering and novel devices with designed functionalities. Herein, a detailed systematic review of transition metal dichalcogenide stacking-engineered heterostructures, from controllable fabrication to typical characterization, and stacking-correlated physical behaviors is presented. Furthermore, recent advances in stacking design, such as stacking sequence, twist angles, and moiré superlattice heterojunctions, are also comprehensively summarized. Finally, the remaining challenges and possible strategies for using stacking engineering to tune the properties of 2D materials are also outlined.

Ultrathin 1T phase VS2 nanosheets were self-assembled on a flexible carbon cloth to form a binder-free electrode. The electrode exhibited a typical solid solution reaction, which is of great help in inhibiting the structural transition.

In article number 2005735, Jiaxu Yan, Wei Huang, and co‐workers systematically review the progress of stacking engineering of transition metal dichalcogenide hetero‐bilayers: from controllable fabrication methods to routine characterization, then to the dependence of interlayer coupling on stacking configurations/angles, and lastly the current challenges and possible future strategies.