Hydrogen generation from water using solar energy has grown into a promising approach for sustainable energy production. Over the last years, graphitic carbon nitrides (g-C3N4, CN), polymers based on the heptazine-group, have been widely applied as photocatalysts for H2 evolution. The poor charge separation efficiency of CN is considered the major drawback. Here, we investigated the effect of coupling CN with different types of carbon nanotubes on the charge transfer properties and the photocatalytic H2 evolution. We used carbon nanotubes (CNTs) of different wall number (single (SWCNTs), double (DWCNTs) and multi-walled (MWCNTs) CNTs) for the development of full-organic CN based composite photocatalysts. Photoactivity was drastically affected by the content but more importantly by the nature of the CNTs. The SWCNTs functionalized CN composites were the most active presenting approximately 2–5 times higher H2 evolution than the corresponding DWCNTs and MWCNTs functionalized CN under both solar and pure visible light irradiation. Photoactivity was primarily controlled by the improved electronic properties linked with the abundance and stability of photogenerated charges as evidenced by electron paramagnetic resonance spectroscopy. Transient absorption spectroscopy verified the transfer of reactive electrons from CN to CNTs. CNTs functioned as electron acceptors improving charge separation. The data suggest that charge transfer is inversely proportional to the wall number of the CNTs and that photoactivity is directly controlled by the size at the nanoscale of the CNTs used. In the CNTs/CN nanocomposites, photogenerated electrons are transferred more efficiently from CN when SWCNTs are used, providing more available electrons for H2 production.
