Facile Construction of a Copper-Containing Covalent Bond for Peroxymonosulfate Activation: Efficient Redox Behavior of Copper Species via Electron Transfer Regulation

Heterogeneous catalysis can be enhanced through the construction of effective atom connection for rapid electron transport on the catalyst surface. Hence, this study proposed a new strategy for electron transfer regulation to facilitate redox cycle of Cu(II)/Cu(I). The objective was achieved by successful construction of copper-containing covalent bond through the in situ growth of porous g-C₃N₄ with oxygen dopants and nitrogen defects (O-CN_D) on CuAl_xO_y substrate (CuAl@O-CN_D). On the basis of X-ray absorption fine structure (XAFS) and other characterization results, the facilitated redox behavior of copper species by electron transfer regulation was ascribed to the formation of a C-O-Cu bond on the porous-rich superficial of the catalyst; these covalent C-O-Cu bonds shortened the migration distance of electrons between Cu(II) and Cu(I) via Cu(I)-O-C-O-Cu(II) bridge. The construction of copper-containing covalent bonds in the catalyst resulted in efficient PMS activation for a rapid redox cycle of Cu(II)/Cu(I), triggering a series of reactions involving the continuous production of three highly active species (SO₄^·-, ^·OH and ¹O₂). The rapid diffusion and transportation of the generated active species from porous structures directly attack typical pharmaceutically active compounds (PhACs), achieving superior catalytic performance. This study provides a new routine to construct a C-O-Cu bond for PMS activation by regulating the electron transfer to accelerate the redox behavior of copper species for environmental remediation.