Designing Two-Dimensional Octuple-Atomic-Layer M$_2$A$_2$Z$_4$ as Promising Photocatalysts for Overall Water Splitting

Abstract: Two-dimensional (2D) materials have emerged as promising candidates as photocatalytic materials due to their large surface areas and tunable electronic properties. In this work, we systematically design and screen a series of octuple-atomic-layer M$_2$A$_2$Z$_4$ monolayers (M = Al, Ga, In; A = Si, Ge, Sn; Z = N, P, As) using first-principles calculations. 108 structures are constructed by intercalation approach, followed by a comprehensive evaluation of their thermodynamic and dynamic stability, band gaps, and band edge alignments to assess their potential for photocatalytic overall water splitting. Among them, eight candidates meet the criteria for overall water splitting under acidic condition (pH = 0), and Al$_2$Si$_2$N$_4$ and Al$_2$Ge$_2$N$_4$, further exhibit suitable band edge positions for photocatalysis under both acidic and neutral environments (pH = 0 and 7). Al$_2$Si$_2$N$_4$ and Al$_2$Ge$_2$N$_4$ also show pronounced visible-light absorption and structural stability in aqueous conditions. Importantly, the introduction of N vacancies on the surfaces of Al$_2$Si$_2$N$_4$ and Al$_2$Ge$_2$N$_4$ significantly enhances their catalytic activity for both hydrogen reduction and water oxidation reactions, further supporting their potential as photocatalysts for overall water splitting. Our study provides theoretical insights for the rational design of efficient and stable 2D photocatalysts for overall water splitting.