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

Abstract

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\u202fmin-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 empirical kinetic model shows a strong linear correlation with the experimental kinetic reaction rate (> 0.94). CuO-CN/PMS can degrade organic pollutants efficiently for up to 30\u202fdays in a filter reactor. This work provides an understanding of the key role of the surface electronic structure in the nonradical activation of PMS and may provide support for improving the design of PMS catalysts.