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

Abstract 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 Au 1 Ag 39 , Ag 40 , negatively charged Au 12 Ag 32 , positively charged Ag 46 Au 24 , Au 4 Cu 4 and P‐ligand‐protected Pd 3 Cl. Importantly, the generated APNC/MOF show significantly improved performances, for example, the activities of Au 12 Ag 32 /ZIF‐8(300°C), Au 4 Cu 4 /ZIF‐8(300°C), and Au 1 Ag 39 /ZIF‐8(300°C) in the corresponding reactions are higher than those of Au 12 Ag 32 , Au 4 Cu 4 , and Au 1 Ag 39 , respectively. In particular, Au 12 Ag 32 /ZIF‐8(300 °C) shows higher activity than Au 12 Ag 32 @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.