Carbon nitride coupled two-dimensional metal–organic framework core–shell catalyst for photo-enzymatic synergistic degradation of bisphenol A

Bisphenol A (BPA), as a typical endocrine disruptor, can cause serious harm to human health. In order to solve the limitation of biological enzyme method in the degradation of BPA in actual water, we successfully prepared a photo-enzyme-coupled catalyst CN-HRP@ZIP by in situ generation of a metal–organic skeleton coated with HRP on the carbon nitride surface. The photo-enzymatic synergy of the material and the low mass transfer resistance caused by the two-dimensional ZIP make CN-HRP@ZIP can achieve 100% degradation of BPA at 40 min. The degradation rate was 3.92 times that of CN and 1.65 times that of CN-HRP@ZIF, respectively. The immobilization of the enzyme broadened the degradation pathway and enhanced the resistance to anionic interference by enzyme specificity. The direct conversion of hydrogen peroxide by the enzyme and the indirect enhancement of photocatalytic superoxide radical production increased the concentration of superoxide radicals in the system, and CN-HRP@ZIP maintained a high degradation rate of more than 90% in five cycles. The stability of the enzymatic activity of the material was much higher than that of the free enzyme under extreme pH, high temperature, and organic solvent immersion. These studies provide a new reference for the application of photo-enzymatic synergistic degradation in industrial wastewater treatment.