Promising M₂CO₂/MoX₂ (M = Hf, Zr; X = S, Se, Te) Heterostructures for Multifunctional Solar Energy Applications

Two-dimensional van der Waals (vdW) heterostructures are potential candidates for clean energy conversion materials to address the global energy crisis and environmental issues. In this work, we have comprehensively studied the geometrical, electronic, and optical properties of M₂CO₂/MoX₂ (M = Hf, Zr; X = S, Se, Te) vdW heterostructures, as well as their applications in the fields of photocatalytic and photovoltaic using density functional theory calculations. The lattice dynamic and thermal stabilities of designed M₂CO₂/MoX₂ heterostructures are confirmed. Interestingly, all the M₂CO₂/MoX₂ heterostructures exhibit intrinsic type-II band structure features, which effectively inhibit the electron-hole pair recombination and enhance the photocatalytic performance. Furthermore, the internal built-in electric field and high anisotropic carrier mobility can separate the photo-generated carriers efficiently. It is noted that M₂CO₂/MoX₂ heterostructures exhibit suitable band gaps in comparison to the M₂CO₂ and MoX₂ monolayers, which enhance the optical-harvesting abilities in the visible and ultraviolet light zones. Zr₂CO₂/MoSe₂ and Hf₂CO₂/MoSe₂ heterostructures possess suitable band edge positions to provide the competent driving force for water splitting as photocatalysts. In addition, Hf₂CO₂/MoS₂ and Zr₂CO₂/MoS₂ heterostructures deliver a power conversion efficiency of 19.75% and 17.13% for solar cell applications, respectively. These results pave the way for exploring efficient MXenes/TMDCs vdW heterostructures as photocatalytic and photovoltaic materials.