Defects‐Induced Single‐Atom Anchoring on Metal–Organic Frameworks for High‐Efficiency Photocatalytic Nitrogen Reduction

Aiming to improve the photocatalytic activity in N₂ fixation to produce ammonia, herein, we proposed a photochemical strategy to fabricate defects, and further deposition of Ru single atoms onto UiO-66 (Zr) framework. Electron-metal-support interactions (EMSI) were built between Ru single atoms and the support via a covalently bonding. EMSI were capable of accelerating charge transfer between Ru SAs and UiO-66, which was favorable for highly-efficiently photocatalytic activity. The photocatalytic production rate of ammonia improved from 4.57 μmol g⁻¹ h⁻¹ to 16.28 μmol g⁻¹ h⁻¹ with the fabrication of defects onto UiO-66, and further to 53.28 μmol g⁻¹ h⁻¹ with Ru-single atoms loading. From the DFT results, it was found that d-orbital electrons of Ru were donated to N₂ π✶-antibonding orbital, facilitating the activation of the N≡N triple bond. A distal reaction pathway was probably occurred for the photocatalytic N₂ reduction to ammonia on Ru₁ /d-UiO-66 (single Ru sites decorated onto the nodes of defective UiO-66), and the first step of hydrogenation of N₂ was the reaction determination step. This work shed a light on improving the photocatalytic activity via feasibly anchoring single atoms on MOF, and provided more evidences to understand the reaction mechanism in photocatalytic reduction of N₂ .