Regulating the Local Electronic Structure of Copper Single Atoms with Unsaturated B,O-Coordination for Selective <sup>1</sup>O<sub>2</sub> Generation
Peizhen Yang, Zhenhua Cao, Yuhan Long, Dongfang Liu, Wenli Huang, Sihui Zhan, Miao Li
Abstract
Generating singlet oxygen ( 1 O 2 ) on single atom catalysts (SACs) in peroxymonosulfate (PMS)-based Fenton-like reactions exhibits great potential for selective degradation of contaminants in complex wastewater. Clarifying the structure–activity relationship between the electronic structure of SACs and the 1 O 2 generation selectivity is crucial for the precise design of efficient Fenton-like catalysts, but it is challenging. Herein, the generation selectivity of 1 O 2 on Cu SACs with different electronic structures (namely, Cu–O 2 X, where X = N, S, B, P, and O) is investigated by density functional theory calculations using the adsorption selectivity of terminal oxygen atoms in PMS as an activity descriptor. Significantly, the selectivity of 1 O 2 generation is affected by the electronic structure of the Cu center in which the electron-depleted Cu-O 2 B site exhibits a higher selectivity for the adsorption of terminal oxygen atoms. Experimentally, the Cu-O 2 B moiety exhibits superior catalytic activity for PMS activation, showing nearly 100% selectivity for 1 O 2 generation and a ciprofloxacin degradation rate of 0.2250 min –1, outperforming those of the other counterparts. The high catalytic activity is attributed to the asymmetric Cu-O 2 B site accelerating faster electron transfer and O–O bond stretching, lowering the energy barrier of key intermediates toward 1 O 2 generation. This work provides a broader perspective for regulating the electronic structure of single Cu sites at the atomic level and for the precise design of efficient Fenton-like catalysts.