An ultrathin porphyrin-based metal-organic framework for efficient photocatalytic hydrogen evolution under visible light

. Development of inorganic semiconductor photocatalysts for efficient photocatalytic production of clean and renewable hydrogen has long been attracting tremendous attentions. Herein, we report an ultrathin porphyrin-based metal-organic framework (PMOF) with Ti-oxo clusters, exhibiting a photocatalytic hydrogen evolution rate of as high as 8.52 mmol.g(-1).h(-1) in the presence of Pt as cocatalyst under a wide range of visible light irradiation up to 700 nm. The photocatalytic reaction over PMOF is a typical ligand-to-metal charge transfer (LMCT) process, i.e., the photoinduced electrons transfer from porphyrin-based ligands (light harvester) to Ti-oxo clusters (catalytic center), and thereby the charge carriers' separation is significantly enhanced. Moreover, the long-term course reaction confirms the excellent water-resistance and photo-stability of PMOF in photocatalytic hydrogen evolution.