Mesoporous Atomically Dispersed Fe Catalysts with Enhanced Nonradical Pathways in Fenton-like Reactions: The Role of SiO2 Templates

Single-atom catalysts (SACs) are extensively applied in Fenton-like catalytic processes to treat water pollutants. However, the role of the porous structures of SACs supports in catalytic reactions is often overlooked despite its significant contribution to mass diffusion during the reaction. Herein, we adopted a hard-template-assisted approach to fabricate Fe-based SACs (Fe-SACs) featuring a mesoporous architecture. The SiO₂ template not only adjusts the pore architecture of the support but also facilitates the conversion of active sites from nanoscale sites to single-atom sites, thereby improving the selectivity for pollutant degradation via nonradical pathways (singlet oxygen and electron transfer mechanism). The experimental results demonstrated that using large-sized SiO₂ (∼200 nm) as a template leads to metal aggregation on its surface, forming Fe nanoparticles (Fe-NPs). Fe-NPs exhibit narrow pore structures that prevent peroxymonosulfate (PMS) from being activated, resulting in a slow degradation of pollutants primarily through radical pathways. In contrast, employing small-sized SiO₂ (∼10 nm) as a hard template not only produces supports with mesoporous structures but also promotes the building of single-atom active sites. The prepared Fe-SACs effectively activated PMS through nonradical pathways and removed contaminants at a rate k of 0.89 min^-1, 33 times faster than Fe-NPs. This template-assisted method sheds light on the synthesis of effective Fenton-like catalysts with porous structures that enhance the efficient breakdown of contaminants in wastewater.