Unraveling the “Black Box”: Challenges and Perspectives in Elucidating Catalytic Mechanisms of Metal–Biomass Carbon Hybrids for Persulfate Activation

In recent years, Metal–Biomass Carbon (M–BC) hybrids have been widely studied as promising, cost-effective, and sustainable catalysts for persulfate activation in the degradation of emerging organic contaminants. M–BC systems offer advantages such as good performance and the sustainable use of biomass waste. Despite the considerable attention they have received, significant uncertainty remains regarding their precise catalytic mechanisms. A primary concern is the inherent complexity of biomass precursors, which frequently render the resulting catalytic structures ill-defined or akin to a “black box”. To address this challenge, this review critically evaluates the current state of mechanistic research, focusing on the debate between radical and non-radical pathways. In this paper, five fundamental challenges to clear mechanistic understanding are identified, including interference of inherent inorganic species, lack of precursors standardization and inherent heterogeneity, ambiguous overlapping active sites, methodological limitations in chemical quenching due to competitive adsorption, and conductivity-related constraints on non-radical pathways. Among these, the interference from inherent inorganic species is of primary concern, as the available evidence suggests it frequently confounds reported synergistic effects. Additionally, the future research directions for improving the experimental standardization and mechanistic understanding of M–BC catalysts are proposed. This review enriches the field by providing a clear path toward rigorous mechanistic understanding and the rational design of M–BC catalysts for water remediation.