Modulating Electronic Structure Engineering of Atomically Dispersed Cobalt Catalyst in Fenton-like Reaction for Efficient Degradation of Organic Pollutants

Currently, the lack of model catalysts limits the understanding of the catalytic essence. Herein, we report the functional group modification of model single atom catalysts (SACs) with an accurately regulated electronic structure for accelerating the sluggish kinetics of the Fenton-like reaction. The amino-modified cobalt phthalocyanine anchored on graphene (CoPc/G-NH₂) shows superior catalytic performance in the peroxymonosulfate (PMS) based Fenton-like reaction with Co mass-normalized pseudo-first-order reaction rate constants (k_obs, 0.2935 min^-1), which is increased by 4 and 163 times compared to those of CoPc/G (0.0737 min^-1) and Co₃O₄/G (0.0018 min^-1). Density functional theory (DFT) calculations demonstrate that the modification of the −NH₂ group narrows the gap between the d-band center and the Fermi level of a single Co atom, which strengthens the charge transfer rate at the reaction interface and reduces the free energy barrier for the activation of PMS. Moreover, the scale-up experiment realizes 100% phenol removal at 7200-bed volumes during 240 h continuous operation without obvious decline in catalytic performance. This work provides in-depth insight into the catalytic mechanism of Fenton-like reactions and demonstrates the electronic engineering of SACs as an effective strategy for improving the Fenton-like activity to achieve the goal of practical application. © 2023 American Chemical Society.