Supermolecule Polymer Derived Porous Carbon Nitride Microspheres with Controllable Energy Band Structure for Photocatalytic Hydrogen Evolution Reaction

Abstract Porous graphitic carbon nitride microsphere with large specific surface area and controllable energy band structure is synthesized via a simple method with the supermolecule polymer of melamine‐cyanuric acid (MCA) as the intermediates. The energy band structure and morphology of carbon nitride are closely correlative to the calcination time. And the CN‐20 catalyst fabricated by calcination for 20 h exhibit superior photocatalytic activity of hydrogen evolution reaction (HER) under visible‐light (λ ≥ 420 nm) irradiation. The photocatalytic and photoelectrochemical test results indicate that Pt is the optimum cocatalyst candidate compared with Pd, Ru, and Ag. Meanwhile, the time‐dependent process of the intermediate pyrolysis to carbon nitride and the internal mechanism of photogenerated charge transfer between semiconductors and cocatalyst is investigated and supplemented by theoretical calculations. This work provides a novel and energy band structure controllable manufacture strategy for porous carbon nitride semiconductor with satisfying visible‐light photocatalytic reduction performance.