Controlled synthesis of Cu,Fe dual-atom catalysts restrained on metal–organic frameworks for efficient O2 activation

Abstract

Supported bimetallic dual-atom catalysts (DACs) have been regarded as a promising class of materials for small molecule activation, despite their challenging syntheses. We have successfully synthesised supported Cu,Fe dual-atom catalysts (DACs) on the Zr₆O₄ secondary building units of UiO-66-NH₂, enabling efficient activation of O₂. Our model photocatalytic styrene oxidation reaction achieved remarkably high product selectivity (>92%) towards benzaldehyde. This superior reactivity is attributed to the well-balanced synergy between the electronic and steric characteristics, enabling efficient O₂ activation by the sterically restrained Cu and Fe sites in proximity for the formation of the bridging peroxy group. This group facilitates the selective oxidation of styrene similar to many peroxide-based oxidants. The confined microporous environment allows for control of the electronic and geometric properties of the DACs, shedding light towards more precise atomistic engineering that approaches the conventional inorganic metal(s)-complex counterparts. Overall, supported bimetallic dual-atom catalysts (DACs) are a promising class of materials for small molecule activation, despite their challenging syntheses.