Enhancing the Photocatalytic Performance of MXenes via Stoichiometry Engineering of Their Electronic and Optical Properties

Combining both density functional theory and the cluster expansion method, we investigate 3 binary MXene alloy systems of semiconducting Ti2CO2, Zr2CO2, and Hf2CO2, where the transition metals substitute one another (i.e., Ti2(1–x)Zr2xCO2, Ti2(1–x)Hf2xCO2, and Zr2(1–x)Hf2xCO2). We show that this group of MXene alloys forms the solid-solution phase across all compositions. Special quasirandom structures are generated to model the solid-solution phase of these alloys, using which we demonstrate how their structural, mechanical, electronic, and optical properties are tuned via stoichiometry engineering. These alloys exhibit outstanding mechanical strength and stability. They possess indirect band gaps of 1.25–1.80 eV. For Ti2(1–x)Zr2xCO2 and Ti2(1–x)Hf2xCO2, they display higher absorbance in the solar spectrum than their constituent Zr2CO2 and Hf2CO2, respectively. Most of the MXene alloys also show appropriately aligned band edges for water splitting. We predict the Ti2(1–x)Zr2xCO2 alloy with x = 0.2778 to ...