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. Photocatalysis: A new ocu‐metal‐organic framework (MOF) catalyst, SYD‐1‐CuNi, was rationally designed and successfully synthesised. Catalytically active CuNi sites in SYD‐1‐CuNi were attached to coordinatively unsaturated sites on the Zr oxo‐clusters postsynthetically via a sequential practice of a solvent‐assisted ligand exchange and metalation processes. SYD‐1‐CuNi catalyses a photocatalytic CO2 reduction/hydrogen evolution reaction concomitantly with oxidation of benzyl alcohol to benzaldehyde.