Construction of copper-manganese based aminoclays with significant laccase-like activity and its prominent degradation performance towards bisphenol A

Abstract

In recent years, nanozymes have become promising alternatives to natural enzymes owing to their high catalytic efficiency, substrate specificity, and mild reaction conditions. The catalytic performance of nanozymes can be further improved by doping heterogeneous metals to provide high redox potentials. However, nanozymes for the degradation of endocrine-disrupting chemicals (EDCs) have been scarcely studied, and the degradation mechanisms remain unclear. Herein, a series of aminoclays (ACs) containing various metal dopants were prepared and employed for the degradation of phenolic compounds. The as-synthesized ACs with a Cu-Mn molar ratio of 1:7 (CuMnAC-1–7) showed excellent stability and superior activity for oxidizing bisphenol A (BPA) than natural laccases owing to the electron transport between Cu2+/Cu+ and Mn4+/Mn3+ in the nanozyme. The catalytic oxidation process of BPA consists of a non-free radical pathway mediated by Mn3+, as well as a free radical pathway facilitated by superoxide radicals (O2·-) and singlet oxygen (1O2). Specifically, Mn3+ deprived the electrons of the BPA benzene ring to form phenolic hydroxyl radicals, which were then polymerized to BPA dimers. Cu+ in the structure reduced Mn4+ to Mn3+, accelerating the electron deprivation of BPA and promoting the polymerization reaction. Finally, the high-charge-density region on the dimeric benzene ring tended to lose electrons and form free radicals, facilitating the polymerization into trimers and tetramers. The CuMnAC-1–7 could remove 95% of BPA at a concentration of 200 mg/L within 1 h under acidic conditions. This study provides a new strategy to design high-performance laccase nanozymes for EDCs degradation.