Exploiting the Fracture in Metal-Organic Frameworks: A General Strategy for Bifunctional Atom-Precise...

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.