Liquid‐Phase Exfoliation of Nonlayered Non‐Van‐Der‐Waals Crystals into Nanoplatelets

For nearly 15 years, researchers have been using liquid‐phase exfoliation (LPE) to produce 2D nanosheets from layered crystals. This has yielded multiple 2D materials in a solution‐processable form whose utility has been demonstrated in multiple applications. It was believed that the exfoliation of such materials is enabled by the very large bonding anisotropy of layered materials where the strength of intralayer chemical bonds is very much larger than that of interlayer van der Waals bonds. However, over the last five years, a number of papers have raised questions about our understanding of exfoliation by describing the LPE of nonlayered materials. These results are extremely surprising because, as no van der Waals gap is present to provide an easily cleaved direction, the exfoliation of such compounds requires the breaking of only chemical bonds. Here the progress in this unexpected new research area is examined. The structure and properties of nanoplatelets produced by LPE of nonlayered materials are reviewed. A number of unexplained trends are found, not least the preponderance of isotropic materials that have been exfoliated to give high‐aspect‐ratio nanoplatelets. Finally, the applications potential of this new class of 2D materials are considered. Recent research progress on the use of liquid‐phase exfoliation beyond layered van der Waals (vdW) crystals is summarized. Questions remain unanswered on how these 3D strongly bonded nonlayered crystals exfoliate into nanoplatelets, and on the insight of the exfoliation mechanism. The answer to the questions helps in revealing the future direction of this newly grown sub‐family of 2D‐class of materials.