The Versatile Electronic,Magnetic and Photo-Electro Catalytic Activity of a New 2D MA2Z4 Family**

The recent successful growth of MoSi₂N₄ and WSi₂N₄ monolayers led to the discovery of a new class of the two-dimensional (2D) MA₂Z₄ materials with no known 3D layered allotropes, which renders great possibilities to integrate diverse properties by proper design of sandwiched “MZ₂” building blocks and “A?Z” passivation layers. In this work, the dynamic stability, electronic properties, and surface reactivity of the new MA₂Z₄ family, in which M is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, A refers to Si or Ge, and Z is N, P or As, is theoretically probed. Among the proposed 54 possible combinations, about 42 compositions are dynamically stable, which vary from non-magnetic, anti-ferromagnetic, to ferromagnetic semiconductors, metals and half-metals. In particular, the VB (V, Nb, Ta) MA₂Z₄ possesses robust intrinsic ferromagnetism that is essential for spintronics applications. In regard to surface activity, most MA₂Z₄, particularly N- or P-terminated IVB and VB MA₂Z₄, have high catalytic potential for hydrogen evolution, and the ?G_H of non-magnetic MA₂Z₄ is highly correlated to the highest occupied p electronic states of the surface Z atoms. The photocatalytic activity is also evaluated. MoSi₂N₄ and WSi₂N₄ within 4 % tensile strain are capable of photocatalytic overall water splitting. The findings indicate the new 2D MA₂Z₄ family has fascinating properties and possesses strong potential for applications but not limited to electronics, spintronics and catalysts, which will stimulate the interests of experimental synthesis.