Violet Antimony Phosphorus with Enhanced Photocatalytic Hydrogen Evolution

Abstract Violet phosphorus (VP), a recently confirmed layered elemental structure, is demonstrated to have unique photoelectric, mechanical, and photocatalytic properties. Element substitution plays a significant role in modifying the physical/chemical properties of semiconducting materials. Herein, antimony is adopted to substitute some phosphorus atoms in VP crystals to tune their physical and chemical properties, resulting in a significantly enhanced photocatalytic hydrogen evolution performance. The antimony‐substituted violet phosphorus single crystal (VP‐Sb) is synthesized and characterized by single crystal X‐ray diffraction (CSD‐2214937). The bandgap of VP‐Sb has been found to be lowered from that of VP by UV/vis diffuse reflectance spectroscopy and density‐functional theory (DFT) calculation, enhancing the optical absorption during photocatalytic reaction. The conducting band minimum of VP‐Sb is found to be upshifted from that of VP from measurements and calculation, enhancing its hydrogen reduction activity. The valance band maximum is found to be lowered to weaken its oxidation activity. The edge of VP‐Sb is calculated to have an excellent H^* adsorption–desorption performance and superior H₂ generation kinetics. The H₂ evolution rate of VP‐Sb is demonstrated to be significantly enhanced to be 1473 µmol h⁻¹ g⁻¹, about five times of that of pristine VP (299 µmol h⁻¹ g⁻¹) under the same experimental conditions.