Constructing Layered Nanostructures from Non‐Layered Sulfide Crystals via Surface Charge Manipulation Strategy.

2D non‐layered metal sulfides possess intriguing properties, rendering them bright application prospects in energy storage and conversion, however, the synthesis of non‐layered metal sulfide nanosheets is still significantly challenging. Herein, a surface‐charge‐regulating strategy is developed to fabricate microsized 2D non‐layered metal sulfides via manipulation of the isoelectric point, which can easily modulate the manner of surface charge arrangement during the growth of crystal nuclei. The result of this strategy are materials that are completely assembled with a preferred orientation but comprise a large lateral size with maintaining atomic thickness. A series of modified sulfides are successfully synthesized, demonstrating that their microarchitectures are shifted in an expected manner. Then, one of these materials, In4SnS8, approaches a promising candidate for sodium storage by means of its structural integrity, boosted transfer kinetics, and abundant active sites. The proposed synthetic protocol can open up a new opportunity to explore 2D non‐layered materials for energy‐related applications. [ABSTRACT FROM AUTHOR]