摘要
Crystal field splitting energy governed the doping-induced d-band shift. • Anti-bonding orbital activation mechanism for O 3 , H 2 O 2 and PS was proposed. • Molecular dipole moment was the dominant factor for pollutant degradation. Modulating the d-band center of transition metals by doping engineering is an efficient strategy to enhance their catalytic efficiency. However, there remains a lack of systematic theoretical explanation for how doping engineering modulates the d-band center and activates antibonding orbitals at the electronic structure scale. Herein, using α-Fe 2 O 3 (αFO) as a model transition metal, machine learning, density functional theory calculations and experimental characterization were integrated to elucidate the doping induced d-band center shifts. The results reveal that dopants modulated the crystal field splitting energy of transition metals, which in turn tailors the d-band center, thereby enhancing the catalyst's ability to activate the antibonding orbitals of reactive species. This mechanism rationalized the efficient degradation of metronidazole observed in the Cu-αFO/DBD/persulfate process. Furthermore, to elucidate the degradation mechanism at the molecular level, this study investigated the structure-activity relationship, specifically how the molecular structure of the pollutants and the catalytic system influence the degradation efficiency. The data revealed the correlation between molecular properties (e.g., dipole moment and energy of the lowest unoccupied molecular orbital) and degradation kinetics. The proposed d-band center modulation and antibonding orbital activation mechanism provides both a theoretical foundation and a practical pathway for the rational design of high performance transition metal catalysts. Download: Download high-res image (388KB) Download: Download full-size image
危险品化学品经营许可证（带存储）