Structure–Activity Relationships in Bulk Polymeric and Sol–Gel-Derived Carbon Nitrides during Photocatalytic Hydrogen Production

Photocatalytic hydrogen evolution rates and structural properties as well as charge separation, electron transfer, and stabilization have been analyzed in advanced sol–gel-derived carbon nitrides (SG-CN) pyrolyzed at different temperatures (350–600 °C) and in bulk polymeric carbon nitride reference samples (CN) by XRD, XPS, FTIR, UV–vis, Raman, and photoluminescence as well as by in situ EPR spectroscopy. SG-CN samples show about 20 times higher H₂ production rates than bulk CN. This is due to their porous structure, partial disorder, and high surface area which favor short travel distances and fast trapping of separated electrons on the surface where they are available for reaction with protons. In contrast, most of the excited electrons in bulk polymeric CN return quickly to the valence band upon undesired emission of light, which is responsible for their low catalytic activity