Nickel-doped red mud-based Prussian blue analogues heterogeneous activation of H2O2 for ciprofloxacin degradation: waste control by waste.

Abstract

Red mud (RM) is a typical bulk solid waste with Fe/Al/Si/Ca-rich characteristics that has been used to prepare various heterogeneous catalysts such as iron-based catalysts and supported catalysts. Prussian blue analogues (PBA) is a low-cost, environmentally friendly, and active site rich iron-based metal organic framework, but its catalytic properties are adversely affected by their easy aggregation. In this study, nickel-doped RM-based PBA (RM-Ni PBA) was synthesized by acid dissolution-coprecipitation method for the degradation of ciprofloxacin (CIP). The characterization showed that RM-Ni PBA was a material with excellent dispersibility, large specific surface area, and abundant active sites. The degradation results showed that the removal efficiency of CIP in the RM-Ni PBA/H2O2 system was 16.63, 1.78, and 1.81 times that of RM, RM-PB, and Ni PBA, respectively. It was found that 1O2 was the main reactive oxygen species (ROS) dominated the degradation process, and its formation was accompanied by the mutual conversion of Ni(II)/Fe(II) and Ni(III)/Fe(III). Notably, the degradation process maintained a satisfactory efficiency over a wide pH range (3-9) and exhibited strong anti-interference ability against impurities such as Cl-, SO42-, and NO3-. The components and contents of RM-Ni PBA remained relatively stable during the degradation process. In addition, the degradation intermediates of CIP were identified, and possible degradation pathways were proposed. This study is expected to provide theoretical basis and technical guidance for the application of RM-based heterogeneous catalyst in the treatment of antibiotic wastewater.