Pairing a Zn 1 O 1 Monomer With Oxide Supports via Dual Interfacial Metal–Oxygen Bonding for Stable Conversion of Syngas to Light Olefins

ABSTRACT Atomically dispersed metal oxides on oxide supports have garnered significant attention for their exceptional catalytic activity and selectivity, yet their practical application is often limited by poor stability. Here, we demonstrate that unlike isolated metal atoms on oxide supports, the stability of oxide monomers (e.g., Zn 1 O 1 , a prototype motif for a variety of (de)hydrogenation reactions) on oxide supports (M'O' x ) tightly relies on delicate pairing of two interfacial bonds: Zn–O' and O–M'. Supports with too low oxygen vacancy formation energy ( E v ) fail to firmly anchor the O anion in Zn 1 O 1 , whereas those with excessively high E v bind weakly to the cationic Zn. Tetragonal ZrO 2 (100), possessing a moderate E v , was theoretically screened to enable simultaneous optimization of the dual interfacial bonding and was experimentally verified through the anchoring of high‐density Zn 1 oxo monomers (1.5 Zn·nm −2 ) with exceptional resistance to aggregation and volatilization under harsh reductive conditions. When integrated with SAPO‐34 zeolite for syngas conversion, this bifunctional catalyst achieves an unprecedented light olefins production rate (25.6 mmol·g cat −1 ·h −1 ) and sustains remarkable stability for over 200 h at 400 °C, outperforming all previously reported catalysts. The interfacial pairing principle provides a foundational guideline for designing highly stable and active atomically dispersed metal oxo catalysts.