LAUSR

Significance The Fenton-like process based on peroxymonosulfate (PMS) has been widely investigated and recognized as a promising alternative in recent years for the degradation of persistent organic pollutants. However, the sluggish kinetics of PMS activation results in prohibitive costs and substantial chemical inputs, impeding its practical applications in water purification. This work demonstrates that tuning the electronic structure of single-atom sites at the atomic level is a powerful approach to achieve superior PMS activation kinetics. The Cu-based catalyst with the optimized electronic structure exhibits superior performance over most of the state-of-the-art heterogeneous Fenton-like catalysts, while homogeneous Cu(II) shows very poor activity. This work provides insights into the electronic structure regulation of metal centers and structure–activity relationship at the atomic level. Developing heterogeneous catalysts with atomically dispersed active sites is vital to boost peroxymonosulfate (PMS) activation for Fenton-like activity, but how to controllably adjust the electronic configuration of metal centers to further improve the activation kinetics still remains a great challenge. Herein, we report a systematic investigation into heteroatom-doped engineering for tuning the electronic structure of Cu-N4 sites by integrating electron-deficient boron (B) or electron-rich phosphorus (P) heteroatoms into carbon substrate for PMS activation. The electron-depleted Cu-N4/C-B is found to exhibit the most active oxidation capacity among the prepared Cu-N4 single-atom catalysts, which is at the top rankings of the Cu-based catalysts and is superior to most of the state-of-the-art heterogeneous Fenton-like catalysts. Conversely, the electron-enriched Cu-N4/C-P induces a decrease in PMS activation. Both experimental results and theoretical simulations unravel that the long-range interaction with B atoms decreases the electronic density of Cu active sites and down-shifts the d-band center, and thereby optimizes the adsorption energy for PMS activation. This study provides an approach to finely control the electronic structure of Cu-N4 sites at the atomic level and is expected to guide the design of smart Fenton-like catalysts.