Catalytic Removal of Aqueous Contaminants on N‑Doped Graphitic Biochars: Inherent Roles of Adsorption and Nonradical Mechanisms

Environmentally friendly and low-cost catalysts are important for the rapid mineralization of organic contaminants in powerful advanced oxidation processes (AOPs). In this study, we reported N-doped graphitic biochars (N-BCs) as low-cost and efficient catalysts for peroxydisulfate (PDS) activation and the degradation of diverse organic pollutants in water treatment, including Orange G, phenol, sulfamethoxazole, and bisphenol A. The biochars at high annealing temperatures (>700 °C) presented highly graphitic nanosheets, large specific surface areas (SSAs), and rich doped nitrogen. In particular, N-BC derived at 900 °C (N-BC900) exhibited the highest degradation rate, which was 39-fold and 6.5-fold of that on N-BC400 and pristine biochar, respectively, and the N-BC900 surpassed most popular metal or nanocarbon catalysts. Different from the radical-based oxidation in N-BC400/PDS via the persistent free radicals (PFRs), singlet oxygen and nonradical pathways (surface-confined activated persulfate–carbon complexes) were discovered to dominate the oxidation processes in N-BC900/PDS. Moreover, the adsorption of organics was determined to be the key step determining reaction rate, revealing that the pre-adsorption of reactants significantly accelerated the nonradical oxidation pathway. This study not only provides robust and cheap carbonaceous materials for environmental remediation but also enables the first insight into the graphitic biochar-based nonradical catalysis

Magnetic Nanoscale Zerovalent Iron Assisted Biochar: Interfacial Chemical Behaviors and Heavy Metals Remediation Performance

It has been reported that zerovalent iron can help biochar improve efficiency in heavy metal (HM) absorption, but the surface chemical behaviors and HM removal mechanisms remain unclear. We successfully synthesized the magnetic nanoscale zerovalent iron assisted biochar (nZVI-BC). The porosity, crystal structure, surface carbon/iron atom state, and element distribution were comprehensively investigated to understand nZVI-BC’s interfacial chemical behaviors and HM removal mechanisms. We clearly revealed the formation of a nanoscale Fe⁰ core–Fe₃O₄ shell on the surface/pores/channels of biochar. With the combination of iron nanoparticles and biochar, C–O/COOH groups were cracked with the formation of CO/CC, indicating the C–O–Fe acted as an electron acceptor during the reduction reaction. We also demonstrated that the stabilization was dramatically improved in the nZVI-BC, while more reduced iron and better homogeneity were observed. These results, showing the surface chemical behaviors of nZVI-BC, would help increase our understanding of the HM removal mechanisms. Moreover, our demonstration of the superior removal ability of multiple HM (Pb²⁺, Cd²⁺, Cr⁶⁺, Cu²⁺, Ni²⁺, Zn²⁺) from a solution can provide a breakthrough in making a feasible material for removing HM from polluted water resources