Enhanced Selectivity in PMS Activation via Non-Metal Doping for Efficient 1 O 2 Generation in Emerging Organic Pollutants Degradation

The activation of peroxymonosulfate (PMS) to generate singlet oxygen ( 1 O 2 ) for the removal of emerging organic pollutants (EOPs) from complex aqueous environments has garnered widespread attention. However, the low efficiency and selectivity of current PMS activation for 1 O 2 generation result in suboptimal EOP degradation. To enhance the selectivity of PMS activation and promote the non-radical pathway, non-metal heteroatoms with varying electronegativities were introduced to disrupt the symmetrical coordination structure of Fe active sites in Fe single-atom catalysts. The results showed that, in the B-Fe 1 /GLCNs/PMS system, the pseudo-first-order kinetic rate for bisphenol A (BPA) degradation reached 4.435 min –1, which is 7.4 times higher than that of the unmodified control group. Experimental and theoretical calculations demonstrated that the doping of non-metal heteroatoms altered the electron density and distribution at the Fe active sites, thereby modulating the adsorption configuration of HSO 5 – and increasing the selectivity for PMS activation to generate 1 O 2 . Additionally, the degradation of EOPs by 1 O 2 produced intermediate products with lower biological toxicity, and 1 O 2 demonstrated strong anti-interference capability. The change in HSO 5 – morphology improved the rate of 1 O 2 generation. This study provides deep insights into designing high-performance PMS activation catalysts via non-metal doping to regulate the electronic structure of active sites for a selective non-radical pathway.