Self-Healing of Molecular Catalyst and Photosensitizer on Metal-Organic Framework: Robust Molecular System for Photocatalytic H2 Evolution from Water.

Inspired by self-repair mechanism of PSII in plants, we report a self-healing system which spontaneously repairs molecular catalyst and photosensitizer during photocatalytic H2 evolution. A bipyridine-embedded UiO-type metal-organic framework (MOF), namely Ptn_Ir_BUiO, which incorporated H2-evolving catalyst and photosensitizer, was synthesized and subject to photocatalytic H2 evolution reaction (HER). Impressively, HER with Pt0.1_Ir_BUiO showed very stable molecular photocatalysis without significant decrease in its activity and colloidal formation for 6.5 days at least; in the homogeneous counterpart, the molecular catalyst became a colloid just after 7.5 h. It was revealed that the arrangement of diimine sites which closely and densely surrounded the H2-evolving catalyst and photosensitizer in the MOF enabled such a highly efficient self-healing.