Design of an ocu-metal-organic framework for a photocatalysis reaction

Empowered by reticular chemistry, an ocu-metal-organic framework (MOF) catalyst has been created for the first time. The catalyst, SYD-1, was rationally designed and successfully synthesised by assembling 8-c prismatic zirconium oxo-clusters and 6-c octahedral Ru(bpy)₃²⁺-based metalloligands into a three-dimensional structure. Catalytically active metal sites were then attached to the coordinatively unsaturated sites on the Zr oxo-clusters postsynthetically via a sequential practice of solvent-assisted ligand exchange and metalation processes, giving rise to SYD-1-CuNi. SYD-1-CuNi was thoroughly characterised via an array of X-ray diffraction, 77 K N₂ sorption experiments, nuclear magnetic resonance measurements, microscopic analysis, optical absorption spectra analysis and electrochemical measurements to demonstrate the successful synthesis of the targeted SYD-1-CuNi and its potential in photocatalysis. The photocatalytic performance of SYD-1-CuNi was illustrated by driving a model reaction, namely photocatalytic CO₂ reduction reaction (yield of CH₄ 19.2 μmol g⁻¹ h⁻¹)/hydrogen evolution reaction (yield of H₂ 200.4 μmol g⁻¹ h⁻¹) concomitantly with oxidation of benzyl alcohol to benzaldehyde (286.6 μmol g⁻¹ h⁻¹). The present work highlights the power and potential of reticular chemistry in the at-will synthesis of MOF materials for a specific application.