Unified electronic-geometric descriptor deciphers peroxymonosulfate activation using Fe-based dual-atom catalysts.

Wang, Yifei; Liu, Dongyue; Wang, Hao; Ma, Yuqing; Sun, Xuedi; Wu, Yiyang; Liu, Meng; Peng, Yongzhen et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

The rational design of high-efficiency Fenton-like catalysts remains hindered by insufficient understanding of electronic-geometric synergy in peroxymonosulfate (PMS) activation. We transcend classical d-band theory by proposing a machine learning-decoded binary descriptor (BD) unifying orbital electronic structure (I<sub>OES</sub>) and orbital geometric structure (I<sub>OGS</sub>) indices to predict PMS activation pathways across diverse coordination environments. This BD framework quantifies antibonding orbital occupancy (via d-p hybridization) and geometric constraints (interatomic distance/O-H elongation), enabling precise screening of Fe-based dual-atom catalysts (DACs). Among FeM DACs (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu), FeMn DACs with optimal BD values (I<sub>OES</sub> = 0.86, I<sub>OGS</sub> = 0.40) achieved 94.2% <sup>1</sup>O<sub>2</sub> yield and fast kinetics (k<sub>obs</sub> = 1.2 min⁻<sup>1</sup>) toward sulfadiazine degradation. Crucially, a flow-through reactor demonstrated >90% pollutant removal for 30 days at industrial flux (122.3 L m⁻<sup>2</sup> h⁻<sup>1</sup>). This work establishes universal orbital-level design principles for sustainable water remediation, bridging atomic-scale insights to engineering-scale implementation.