The peroxymonosulfate (PMS)-triggered radical and nonradical active species can synergistically guarantee selectively removing micropollutants in complex wastewater; however, realizing this on heterogeneous metal-based catalysts with single active sites remains challenging due to insufficient electron cycle. Herein, we design asymmetric Co–O–Bi triple-atom sites in Co-doped Bi 2 O 2 CO 3 to facilitate PMS oxidation and reduction simultaneously by enhancing the electron transfer between the active sites. We propose that the asymmetric Co–O–Bi sites result in an electron density increase in the Bi sites and decrease in the Co sites, thereby PMS undergoes a reduction reaction to generate SO 4 •- and •OH at the Bi site and an oxidation reaction to generate 1 O 2 at the Co site. We suggest that the synergistic effect of SO 4 •- , •OH, and 1 O 2 enables efficient removal and mineralization of micropollutants without interference from organic and inorganic compounds under the environmental background. As a result, the Co-doped Bi 2 O 2 CO 3 achieves almost 99.3% sulfamethoxazole degradation in 3 min with a k-value as high as 82.95 min −1 M −1 , which is superior to the existing catalysts reported so far. This work provides a structural regulation of the active sites approach to control the catalytic function, which will guide the rational design of Fenton-like catalysts.

The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO 2 @Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N 4 active sites were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. The AC-induced charge redistribution of single atoms (SAs) was verified, thus strengthening the interaction between SAs and PMS. In detail, the incorporation of ACs optimized the HSO 5 - oxidation and SO 5 ·−  desorption steps, accelerating the reaction progress. As a result, the Vis/TiFeAS/PMS system rapidly eliminated 90.81% of 45 mg/L tetracycline (TC) in 10 min. The reaction process characterization suggested that PMS as an electron donor would transfer electron to Fe species in TiFeAS, generating 1 O 2 . Subsequently, the h VB + can induce the generation of electron-deficient Fe species, promoting the reaction circulation. This work provides a strategy to construct catalysts with multiple atom assembly–enabled composite active sites for high-efficiency PMS-based advanced oxidation processes (AOPs).

Enhancing the peroxymonosulfate (PMS) activation efficiency to generate more radicals is vital to promote the Fenton-like reaction activity, however, how to promote the PMS adsorption and accelerate the interfacial electron transfer to boost its activation kinetics remains a great challenge. Herein, we prepared Cu-doped defect-rich In 2 O 3 (Cu-In 2 O 3 /O v ) catalysts containing asymmetric CuÀ O v À In sites for PMS activation in water purification. The intrinsic catalytic activity is that the side-on adsorption configuration of the OÀ O bond (CuÀ OÀ OÀ In) at the Cu-O v -In sites significantly stretches the OÀ O bond length. Meanwhile, the Cu-O v -In sites increase the electron density near the Fermi energy level, promoting more and faster electron transfer to the OÀ O bond for generating more SO 4 *À and * OH. The degradation rate constant of tetracycline achieved by Cu-In 2 O 3 /O v is 31.8 times faster than In 2 O 3 /O v , and it shows the possibility of membrane reactor for practical wastewater treatment.

Enhancing the peroxymonosulfate (PMS) activation efficiency to generate more radicals is vital to promote the Fenton‐like reaction activity, however, how to promote the PMS adsorption and accelerate the interfacial electron transfer to boost its activation kinetics remains a great challenge. Herein, we prepared Cu‐doped defect‐rich In2O3 (Cu‐In2O3/Ov) catalysts containing asymmetric Cu−Ov−In sites for PMS activation in water purification. The intrinsic catalytic activity is that the side‐on adsorption configuration of the O−O bond (Cu−O−O−In) at the Cu‐Ov‐In sites significantly stretches the O−O bond length. Meanwhile, the Cu‐Ov‐In sites increase the electron density near the Fermi energy level, promoting more and faster electron transfer to the O−O bond for generating more SO4⋅− and ⋅OH. The degradation rate constant of tetracycline achieved by Cu‐In2O3/Ov is 31.8 times faster than In2O3/Ov, and it shows the possibility of membrane reactor for practical wastewater treatment.