Boosting High-Valent Fe═O Formation via Fe Electron Localization in Asymmetric FeMo Dual-Atom Catalyst for...

Area of Science:

• Environmental Chemistry
• Materials Science
• Catalysis

Background:

• High-valent iron-oxygen species are key in catalyst-activated peroxymonosulfate (PMS) oxidation for contaminant degradation.
• Understanding the link between catalyst electronic structure and high-valent Fe═O generation is crucial for designing effective catalysts.

Purpose of the Study:

• To construct and evaluate Fe-Mo dual-atom catalysts (FeMoNC) with N3Fe-O-MoN2 configurations for enhanced contaminant degradation.
• To elucidate the electronic origin of high-valent Fe═O generation in heteronuclear dual-atom catalysts.

Main Methods:

• Synthesis of Fe-Mo dual-atom catalysts (FeMoNC) with specific N3Fe-O-MoN2 configurations.
• Evaluation of sulfadiazine (SDZ) degradation activity.
• X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analysis.
• Density Functional Theory (DFT) calculations.

Main Results:

• FeMoNC catalysts demonstrated exceptional SDZ degradation activity (k = 0.92 min⁻¹), outperforming monometallic FeNC catalysts.
• Electron transfer from Mo to Fe upshifted the Fe d-band center, facilitating PMS activation and stabilizing high-valent Fe═O species.
• DFT calculations confirmed reduced energy barriers for PMS activation and promoted high-valent Fe═O formation.

Conclusions:

• Heteronuclear dual-atom catalysts offer a strategy to manipulate 3d-electron configurations for enhanced high-valent metal-oxo chemistry.
• The study provides insights into the electronic factors governing high-valent Fe═O generation in advanced oxidation processes.
• This work paves the way for designing high-performance catalysts for environmental remediation.