Reactive sites rich porous tubular yolk-shell g-C3N4 via precursor recrystallization mediated microstructure engineering for photoreduction

Photoabsorption, charge separation efficiency and surface reactive catalytic sites are three critical factors in semiconductor photocatalytic process, which determine the photocatalytic activity. For bulk g-C3N4 derived from direct pyrolysis of C/N rich precursors, reactive sites distributed on the lateral edges are very scarce. In this work, we report the template-free preparation of three novel structured g-C3N4, namely, porous tubular (PT) g-C3N4, porous tubular yolk-shell (PTYS) g-C3N4, and porous split yolk-shell (PSYS) g-C3N4, by an unprecedented precursor microstructure regulation of melamine crystals in a gas-pressure mediated re-crystallization process. Enhanced photoabsorption, increased surface area, largely improved separation and migration efficiencies of photoinduced charge carriers are simultaneously realized in these g-C3N4 structures. Noticeably, selective photo deposition test uncovers that the porous outer-walls and inner-rods of PTYS g-C3N4 are enriched by abundant reductive reactive sites, which consumedly boost the photo-reduction activity. Collectively promoted by these advantages, PTYS g-C3N4 shows not only an efficient H-2 production activity with a high apparent quantum efficiency (AQE) of 11.8% at lambda = 420 +/- 15 nm, but also a superior CO2 reduction for CO production than bulk g-C3N4 by a factor 5.6, which is verified by the C-13 isotopic labeling. This work develops precursor microstructure engineering as a promising strategy for rational design of unordinary g-C3N4 structure for renewable energy production.