Heterogeneous Fenton-like reaction shows great potential for eliminating organic substances (e.g. emerging organic contaminants (EOCs)) in water, which has been widely explored in recent decades. However, the catalytic mechanisms reported in current studies are extremely complicated because multiple mechanisms coexist and contribute to the removal efficiencies. Most importantly, heterogeneous systems show selective oxidation properties, which are crucial for improving the efficiencies in the catalytic elimination of organic substances. Thus, this critical review summarizes and compares the diverse existing mechanisms (non-radical and radical pathways) in heterogeneous catalytic processes based on recent studies. The typical oxidation mechanisms during selective advanced oxidation of EOCs were systematically discussed based on the following sections, including the selective adsorption and generation of reactive oxygen species (ROS) in photo/electron-Fenton and Fenton-like systems. Moreover, the non-radical pathways are discussed in depth by the singlet oxygen, high-valent metal-oxo, electron transfer process, etc. Moreover, the direct oxidative transfer process for the removal of EOCs was introduced in recent studies. Finally, the cost, feasibility as well as the sustainability of heterogeneous Fenton-like catalysts are summarized. This review offers useful guidance for developing suitable strategies to develop materials for decomposing the organic substrates.

Single atom catalysts (SACs) have attracted great attention, yet the quest for highly-efficient catalysts is driven by the current obstacles of ambiguous structure-performance relationship. Here, we report a nature keratin-based Fe-S₁N₃ SACs with ultrathin two-dimensional (2D) porous carbon nanosheets structure, by controlling the active center through the precise coordination of sulfur and nitrogen. Compared with natural silk-based Fe-N₄ catalyst, the Fe-S₁N₃ SACs exhibit excellent Fenton-like oxidation degradation ability. X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) results confirm that S doping is conducive to electron transfer, to accurately generate ·OH with high oxidative degradation capacity at the active site. Therefore, the optimized Fe-S₁N₃ catalyst showed higher oxidation degradation activity for organic pollutant substrates (methylene blue (MB), Rhodamine B (RhB) and phenol), significantly superior to Fe-N₄ samples. This work is devoted to the treatment and application of natural fibers, which provides a novel method for the synthesis of SACs and the regulation of atomic coordination environment.