Spontaneous Formation of Low Valence Copper on Red Phosphorus to Effectively Activate Molecular Oxygen for Advanced Oxidation Process

Efficient spontaneous molecular oxygen (O₂) activation is an important technology in advanced oxidation processes. Its activation under ambient conditions without using solar energy or electricity is a very interesting topic. Low valence copper (LVC) exhibits theoretical ultrahigh activity toward O₂. However, LVC is difficult to prepare and suffers from poor stability. Here, we first report a novel method for the fabrication of LVC material (P-Cu) via the spontaneous reaction of red phosphorus (P) and Cu²⁺. Red P, a material with excellent electron donating ability and can directly reduce Cu²⁺ in solution to LVC via forming Cu-P bonds. With the aid of the Cu-P bond, LVC maintains an electron-rich state and can rapidly activate O₂ to produce ·OH. By using air, the ·OH yield reaches a high value of 423 μmol g⁻¹ h⁻¹, which is higher than traditional photocatalytic and Fenton-like systems. Moreover, the property of P-Cu is superior to that of classical nano-zero-valent copper. This work first reports the concept of spontaneous formation of LVC and develops a novel avenue for efficient O₂ activation under ambient conditions.