Engineering Complex Molecular Intercalation for Efficient, Sustainable Exfoliation of Van Der Waals Layered Materials

ABSTRACT Intercalation‐based exfoliation offers a cost‐effective approach to producing 2D materials. While molecular intercalation surpasses ionic methods in preserving the crystallinity and intrinsic properties of 2D materials, its broader adoption is limited by weak driving forces and slow kinetics. To address these challenges, we propose an interlayer modulation strategy using H 3 PO 4 ‐amine complexes as mediators. Structural and molecular dynamics analyses demonstrate that these complexes regulate interlayer proton activity through strong hydrogen bonding, thereby optimizing interlayer dynamics to enable in situ PW 12 formation and efficient graphite exfoliation. The PW 12 intercalant shows excellent recyclability via simple alkaline hydrolysis and regeneration, establishing a sustainable route for graphene production. This work overcomes the barrier to molecular intercalation by rationally engineering complex molecular intercalation, achieving universal and high‐throughput exfoliation of van der Waals layered materials.