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.