Unraveling the vital role of oxygen at the molecular level by regulating surface phosphorus vacancies for high-performance catalytic oxidation

The exploration of catalyst interfaces and surfaces, particularly vacancy engineering, has brought significant advancements in high-performance catalytic oxidation. Although vacancies capable of attracting oxygen atoms are believed to play a vital role in enhancing catalytic efficiency, the molecular-level mechanism of oxygen incorporation and its precise origin remain poorly understood. Here, we combined ab initio molecular dynamics (AIMD) simulations with in-situ Raman spectroscopy and ¹⁸O¹⁶O isotopologues to uncover the catalytic behavior of Pv-supported metal surfaces in peroxymonosulfate (PMS) activation systems. Our results reveal that Pv anchors PMS terminal O and attracts H₂O to participate in the reaction, elevating the oxidation rate from 0.214 to 1.113 min⁻¹. Potential future applications are demonstrated as the system exhibits exceptional stability, sustaining consistent performance over 200 h in a continuous water flow reactor. Predictive modeling validated its broad applicability for degrading uncharacterized pollutants. This work elucidates the pivotal role of defect engineering in reshaping interfacial molecular dynamics, offering transformative strategies for designing advanced catalytic systems tailored for environmental remediation.