Preparation of "dual-vacancy" Co/Mo high-activity interface catalysts based on d-Band regulation strategy and study...

This study employs large-sized phenolic resin-derived carbon (PC) as a precursor to fabricate a dual-vacancy interface catalyst, PC@Co₃O₄-MoS₂, rich in oxygen and sulfur vacancies, via a "self-assembly-pyrolysis-assembly" strategy that orderly anchors Co₃O₄ and MoS₂ within the carbon matrix. The catalyst demonstrates superior activation of PMS across a broad pH range, achieving complete removal of HMX (20 ppm) within 20 min, with a maximum degradation rate constant of 0.2562 min^-1. Synchrotron radiation and DFT calculations reveal that the synergistic electron transfer mechanism facilitated by oxygen and sulfur vacancies, combined with highly active interface sites formed by Co₃O₄-MoS₂, significantly enhances overall performance. Band structure analysis further indicates that Co-Mo synergy improves electron filling efficiency near the Fermi level, accelerating charge transport at the heterojunction interface. HMX degradation involves both free radical and non-free radical pathways, as confirmed by EPR and quenching experiments that quantify the contribution of ROS. MD simulations comprehensively analyze the adsorption-dissociation dynamics and bonding tendencies of PMS and HMX on the catalyst and monomer materials. HPLC-MS identifies intermediate products, proposing possible degradation pathways, while the T.E.S.T. program assesses intermediate toxicity and ecological impact. Flow column simulation experiments periodically evaluate catalytic activity. In summary, PC@Co₃O₄-MoS₂ exhibits promising potential for degrading emerging contaminants and environmental remediation.