Supramolecular electrostatic self-assembly of mesoporous thin-walled graphitic carbon nitride microtubes for highly efficient visible-light photocatalytic activities

Abstract

For efficient solar energy conversion, the morphology engineering of hollow graphitic carbon nitride (g-C3N4) is one of the promising approachs benefiting from abundant exposed active sites and short photocarrier transport distances, but is difficult to control on account of easy structural collapse. Herein, a facile supramolecular electrostatic self-assembly strategy has been developed for the first time to fabricate mesoporous thin-walled g-C3N4 microtubes (mtw-CNT) with shell thickness of ca. 13 nm. The morphological control of g-C3N4 enhances specific surface area by 12 times, induces stronger optical absorption, widens bandgap by 0.18 eV, improves photocurrent density by 2.5 times, and prolongs lifetimes of charge carriers from bulk to surface, compared with those of bulk g-C3N4. As a consequence, the transformed g-C3N4 exhibits the optimum photocatalytic H2-production rate of 3.99 mmol·h−1·g−1 (λ > 420 nm) with remarkable apparent quantum efficiency of 8.7% (λ = 420 ± 15 nm) and long-term stability. Moreover, mtw-CNT also achieves high photocatalytic CO2-to-CO selectivity of 96% (λ > 420 nm), much better than those on the most previously reported porous g-C3N4 photocatalysts prepared by the conventional hard-templating and soft-templating methods.