Friends not Foes: Exfoliation of Non-van der Waals Materials

ConspectusTwo-dimensional materials have been a focus of study for decades, resulting in the development of a library of nanosheets made by a variety of methods. However, many of these atomically thin materials are exfoliated from van der Waals (vdW) compounds, which inherently have weaker bonding between layers in the bulk crystal. Even though there are diverse properties and structures within this class of compounds, it would behoove the community to look beyond these compounds toward the exfoliation of non-vdW compounds as well. A particular class of non-vdW compounds that may be amenable to exfoliation are the ionically bonded layered materials, which are structurally similar to vdW compounds but have alkali ions intercalated between the layers. Although initially they may have been more difficult to exfoliate due to a lack of methodology beyond mechanical exfoliation, many synthesis techniques have been developed that have been used successfully in exfoliating non-vdW materials. In fact, as we will show, in some cases it has even proven to be advantageous to start the exfoliation from a non-vdW compound.The method we will highlight here is chemical exfoliation, which has developed significantly and is better understood mechanistically compared to when it was first conceived. Encompassing many methods, such as acid/base reactions, solvent reactions, and oxidative extractions, chemical exfoliation can be tailored to the delamination of non-vdW materials, which opens up many more possibilities of compounds to study. In addition, beginning with intercalated analogues of vdW materials can even lead to more consistent and higher quality results, overcoming some challenges associated with chemical exfoliation in general. To exemplify this, we will discuss our group's work on the synthesis of a 1T'-WS₂ monolayer ink. By starting with K_0.5WS₂, the exfoliated 1T'-WS₂ nanosheets obtained were larger and more uniform in thickness than those from previous syntheses beginning with vdW materials. The crystallinity of the nanosheets was high enough that films made from this ink were superconducting. We will also show how soft chemical methods can be used to make new phases from existing compounds, such as HCrS₂ from NaCrS₂. This material was found to have alternating amorphous and crystalline layers. Its biphasic structure improved the material's performance as a battery electrode, enabling reversible Cr redox and faster Na-ion diffusion. From these and other examples, we will see how chemical exfoliation of non-vdW materials compares to other methods, as well as how this technique can be further extended to known compounds that can be deintercalated electrochemically and to quasi-one-dimensional crystals.