Copper oxide/graphitic carbon nitride composite for bisphenol a degradation by boosted peroxymonosulfate activation: Mechanism of Cu-O covalency governs

Surface structure can govern heterogeneous catalysis, resulting in its critical role in nonradical reactions. Here, we explored whether Cu-O covalency plays a critical role in controlling the inherent properties of copper oxide/graphitic carbon nitride (CuO-CN). Experiments and theoretical calculations show that, in contrast to the traditional concept of low-valent metal control activity, surface modification enlarges Cu-O covalency, and high-valent copper species at the surface easily bind peroxymonosulfate (PMS, (HSO5-)) anions. Therefore, optimized CuO-CN corresponds to a 14.8-fold higher kinetic reaction rate (0.10392 min-1) for PMS activation and pollutant degradation over those of unoptimized CuO-CN. Based on two-dimensional Fourier transform infrared correlation spectroscopy (2D-FT-IR-COS), Cu-O was determined to be the main active site. Cu-O is more active than other groups and acts before other groups. Benefiting from this electron transfer mechanism, CuO-CN shows good environmental tolerance (pH, anions, humic acid and actual water bodies such as tap water and groundwater). The established