High-entropy perovskites as new photocatalysts for cocatalyst-free water splitting (2510.15225v1)

Abstract: The photocatalytic water-splitting process is thermodynamically challenging and requires catalysts with suitable band structures, as well as the presence of supporting cocatalysts. By considering the unique charge carrier mobility in perovskites, this study introduces three new ABO3-type high-entropy perovskites (Ba1/2Sr1/2)(Ti1/3Zr1/3Hf1/3)O3, (Ba1/2Sr1/2)(Ga1/3In1/3Sn1/3)O3 and (Ba1/2Sr1/2)(Ti1/3Zr1/3Sn1/3)O3 for cocatalyst-free photocatalysis. The three catalysts, having a single-phase cubic structure, are designed by considering configurational entropy, tolerance factor, octahedral factor, ionic radius deviation and valence deviation of >1.5R (R: gas constant), 0.9-1.0, 0.4-0.8, >0.3 and >0.3, respectively. The perovskites exhibit similar valence band tops, while their bandgaps vary slightly depending on the composition at the B-site (slightly lower bandgap by including d10 cations). Additionally, all three materials demonstrate effective hydrogen generation without the need for added cocatalysts. This investigation confirms that high-entropy oxide perovskites can offer significant potential for cocatalyst-free photocatalytic reactions.