One-step preparation of a novel graphitic biochar/Cu0/Fe3O4 composite using CO2-ambiance pyrolysis to activate peroxydisulfate for dye degradation

Abstract

Herein, a one-step co-pyrolysis protocol was adopted for the first time to prepare a novel pyrogenic carbon-Cu0/Fe3O4 heteroatoms (FCBC) in CO2 ambiance to discern the roles of each component in PDS activation. During co-pyrolysis, CO2 catalyzed formation of reducing gases by biomass which facilitated reductive transformation of Fe3+ and Cu2+ to Cu0 and Fe3O4, respectively. According to the analysis, the resulting metal (oxide) catalyzed graphitization of biocharand decomposition of volatile substances resulting in an unprecedented surface area (1240 m2/g). The resulting FCBC showed greater structural defects and less electrical impedance. Batch experiments indicated that Rhodamine B (RhB) degradation by FCBC (100%) was superior to Fe3O4 (50%) and Cu0/Fe3O4 (76.4%) in persulfate (PDS) system, which maintained reasonable efficiency (75.6%-63.6%) within three cycles. The reactive oxygen species (ROS) associated with RhB degradation was identified by an electron paramagnetic resonance and confirmed by scavenging experiments. RhB degradation invoked both (sulfate and dominantly hydroxyl) radical and non-radical (singlet oxygen, 1O2) pathways. Regarding FCBC, Cu0 can continuously react with Fe3+ in Fe3O4 to generate larger quantities of Fe2+, and both Cu0 and Fe2+ activated PDS to yield sulfate radicals which was quickly converted to hydroxyl radical. Besides, Cu0/Cu2+ could complex with PDS to form a metastable complex, which particularly contributed to 1O2 generation. These cascade reactions by FCBC were reinforced by carbonyl group of biochar and favorable electron transfer ability. This work highlighted a new approach to prepare a magnetic and environment-benign heterogonous catalyst to remove organic pollutants in water.