The Feasibility of Using Electrostatic Interactions for Immobilizing Ru-bda Catalysts in Covalent Organic Framework:...

Heterogenization of molecular catalysts effectively resolves the separation issues of homogeneous catalysts and expands their application scenarios. In recent years, more and more studies have been using non-covalent interactions to achieve the heterogenization of molecular catalysts. Herein, electrostatic attraction was used to immobilize molecular catalysts, Ru-bda small molecular catalysts in COF materials, where the charged Ru-bda catalysts were immobilized in the oppositely charged COF with a high [Ru] loading content of ~0.2 mmol [Ru] g^-1 COF. The leakage experiment verified that the immobilization of Ru-bda catalysts in COF by electrostatic interactions is stable in 0.1 M HClO₄ and less than 5 % of molecular Ru-bda catalysts were leached into the solution in 2 hours. The chemical water oxidation experiment was conducted as a model catalysis reaction to verify the feasibility of using electrostatic interactions for immobilizing Ru-bda catalysts in COFs. The prepared Ru(bda)@COFs demonstrate a high catalytic activity of 268 μmol L^-1 s^-1 O₂ for chemical water oxidation, illustrating the electrostatic attractions between COF and small molecules that can be used to immobilize homogeneous catalysts in heterogeneous materials. However, the robustness of COF material itself under catalytic conditions should be considered in practical applications.