Exploiting the Fracture in Metal‐Organic Frameworks: A General Strategy for Bifunctional Atom‐Precise Nanocluster/ZIF‐8(300 °C) Composites

Atom-precise nanoclusters-metal-organic framework (APNC/MOF) composites, as bifunctional material with well-defined structures, have attracted considerable attention in recent years. Despite the progress made to date, there is an urgent need to develop a generic and scalable approach for all APNCs. Herein, the authors present the Exploiting Fracture Strategy (EFS) and successfully construct a super-stable bifunctional APNC/ZIF-8(300 °C) composite overcoming the limitations of previous strategies in selecting APNCs. The EFS utilizes the fracture of ZnN in ZIF-8 after annealing at 300 °C. This method is suitable for all kinds of S/P protected APNCs with different sizes, including uncharged clusters Au1 Ag39 , Ag40 , negatively charged Au12 Ag32 , positively charged Ag46 Au24 , Au4 Cu4 and P-ligand-protected Pd3 Cl. Importantly, the generated APNC/MOF show significantly improved performances, for example, the activities of Au12 Ag32 /ZIF-8(300°C), Au4 Cu4 /ZIF-8(300°C), and Au1 Ag39 /ZIF-8(300°C) in the corresponding reactions are higher than those of Au12 Ag32 , Au4 Cu4 , and Au1 Ag39 , respectively. In particular, Au12 Ag32 /ZIF-8(300 °C) shows higher activity than Au12 Ag32 @ZIF-8. Therefore, this work offers guidance for the design of bifunctional APNC/MOF composites with excellent optimization of properties and opens up new horizons for future related nanomaterial studies and nanocatalyst designs.