Regulating the electronic structure of single-atom catalysts (SACs) to optimize catalytic activity remains a significant challenge. Here, we report an edge-confined Fe@MoS2 SAC featuring dual-channel electron modulation via dz2-p/π(dxz/dyz-p) synergistic coupling. Specifically, the adsorbed O atom directionally gives lone-pair electrons to the Fe active site, while Fe-d orbitals dynamically feed electrons back to CAr–O antibonding orbitals via d-π* hybridization. The dual-channel electron donation–feedback modulation strategy achieves selective activation of recalcitrant CAr–O bonds, outperforming conventional unidirectional electron-transfer catalysts. It offers a theoretical framework for designing high-performance SACs that efficiently activate CAr–O bonds in biomass conversion.
Wei et al. (Mon,) studied this question.