Electronic cooperativity in MOF-confined single-atom alloys: A DFT-guided strategy for dual-functional catalysis towards simultaneous VOCs oxidation and CO resistance

Designing multifunctional catalysts for low-temperature co-oxidation of volatile organic compounds (VOCs) and CO is challenging, as conventional catalysts cannot simultaneously achieve VOCs activation and CO poisoning resistance below 200 °C—where CO preferentially adsorbs and severely inhibits VOCs oxidation. Herein, we proposed a density functional theory (DFT)-guided atomic engineering strategy integrating d-band center modulation and adsorption energy screening to construct metal-organic frameworks (MOFs)-hosted Au-Pt single-atom alloys (SAAs). By leveraging the coordination confinement of UiO-66 to stabilize Au-Pt SAAs sites, the optimized Au-Pt SAAs/UiO-66 catalyst achieved exceptional performance in co-oxidation of toluene and CO, attaining 90 % toluene conversion at 160 °C with robust stability under CO-poisoning conditions. Mechanistic studies and DFT calculations revealed that atomically dispersed Au sites induced Pt δ− -Au δ+ charge polarization on Pt nanoparticles charge polarization via interfacial electron transfer, weakening CO adsorption while enhancing toluene activation through dual-pathway mechanisms (Eley-Rideal and Langmuir-Hinshelwood) mechanisms. This synergy decouples the traditional trade-offs between activity and stability, offering a 4.7-fold higher turnover frequency than conventional Pt catalysts. Our work established a paradigm for electronic cooperativity in MOF-hosted SAAs, providing atomic-level insights into the design of multifunctional catalysts for environmental remediation.