EDTA-dominated hollow tube-like porous graphitic carbon nitride towards enhanced photocatalytic hydrogen evolution

Graphite carbon nitride (g-C₃N₄) as metal-free photocatalyst has been widely studied recently in photocatalytic water reduction, which is considered as one of the promising routes to realizing the hydrogen energy-based society in the future. The generally used preparation process based on thermal polymerization of precursors easily brought the formation of aggregated nanosheets morphology, severely limiting its photocatalytic activity. Herein, the hollow tube-like morphology with porous surface was elaborately obtained by ethylene diamine tetraacetic acid (EDTA)-involved hydrothermal treatment of melamine precursor. The hollow and porous features shortened the migration distance of photo-generated carriers, trapped the incident lights, and provided more photocatalytic reactive sites, then realizing the enhanced photocatalytic H₂-evolution activity up to 7.1 times that of pristine g-C₃N₄. The presence of EDTA acted as the pivotal role to control the recrystallization process of melamine and its derivative, cyanuric acid, and thus to determine the framework formation of the hollow tube-like microstructure. Moreover, complete thermal decomposition of cyanuric acid during the thermal polymerization of precursors was responsible for the hollow and porous features. This work extends the morphology regulation cognition of g-C₃N₄ based on hydrothermal treatment of precursors, and is expected to bring deep understanding and feasible strategies to design morphology-dominated highly-efficient g-C₃N₄ photocatalysts.