Template-free preparation of carbon nitride hollow spheres with adjustable sizes for photocatalytic hydrogen generation

Carbon nitride hollow spheres (CNHS) with adjustable sizes were successfully fabricated via a template-free supramolecular pre-assembly strategy, in which melamine-cyanuric acid (MCA) hollow spheres were constructed through hydrogen bonds. A feasible formation mechanism was proposed, which coupled an inside-out Ostwald ripening with the supramolecular pre-assembly process. Interestingly, the sizes of MCA could be manipulated by changing the pre-assembly temperature. Consequently, the sizes of CNHS were adjustable. The optimal CNHS exhibited excellent photocatalytic hydrogen evolution rate (98.6 μmol/h) in the visible-light region, which was approximately 11 times higher than that of bulk carbon nitride calcined by melamine. The significantly improved performance was due to the contributions including: the unique architectures with remarkable light absorption ability, high electrical conductivity, relatively narrowed band gap, fast charge separation. This work provides a facile template-free supramolecular pre-assembly strategy to fabricate carbon nitride hollow spheres with adjustable sizes for the first time.