Designing non-Van der Waals two-dimensional materials via a layer-intercalation strategy with tailorable ferroelectric, magnetic, and photocatalytic properties

Non-van der Waals (non-vdW) two-dimensional (2D) materials, characterized by strong interlayer bonding, unlock diverse structural motifs and provide a fertile platform for functionalities beyond those of conventional vdW sheets. However, most reported non-vdW 2D materials remain confined to a few atomic layers, and strategies to design thicker, multifunctional sheets remain scarce. Here we present a general layer-intercalation strategy, based on anti-MoS2-type layers, that enables the construction of unusually thick non-vdW 2D sheets. As a demonstration, we realize a nine-atomic-layer structure comprising an anti-MoS2-type core confined between two MoS2-type sublayers. By varying transition-metal elements (Sc, Ti, V, Cr) and coordination geometries, we identify 76 dynamically stable structures spanning ferromagnetic, ferrimagnetic, and antiferromagnetic orders, together with diverse electronic behaviors including metals, semimetals, half-metals, and semiconductors. These sheets further host distinct electronic correlations and physical phenomena such as Dirac/Weyl fermions and floating bands. Twisting and sliding of sublayers give rise to tunable ferroelectricity, robust magnetism, and efficient photocatalytic water-splitting activity. Our work establishes layer intercalation as a versatile and generalizable strategy for designing thick non-vdW 2D materials, opening new avenues for spintronics, non-volatile memory, sensing, and energy conversion applications beyond the reach of traditional vdW sheets.