Calcination‐regulated Microstructures of Donor‐Acceptor Polymers towards Enhanced and Stable Photocatalytic H2O2 Production in Pure Water

Regulating molecular structure of donor-acceptor (D-A) polymer is a promising strategy to improve photoactivity. Herein, a porous nanorod-like D-A polymer is synthesized via a strategy of supramolecular chemistry combined with subsequent calcination treatment. This polymer consists of benzene rings (D) and triazine (A) that are linked by amido bond (-CONH-). -CONH- further partially cracks into cyano groups (-C equivalent to N) (A) under calcination. The ratio of benzene to triazine could be tuned to adjust the -C equivalent to N content by varying the calcination atmosphere. Such regulation of molecular structure could modulate the band structure of D-A polymer and endow it with unique porous nanorod-like morphology, leading to the achievement of two-electron oxygen reduction and two-electron water oxidation and the improvement of exciton splitting, O-2 adsorption and activation. These merits synergistically ensure a highly efficient and stable photocatalytic H2O2 production in pure water.