Z-scheme WOx/Cu-g-C3N4 heterojunction nanoarchitectonics with promoted charge separation and transfer towards efficient full solar-spectrum photocatalysis

Abstract

Construction of Z-scheme heterojunctions has been considered one superb method in promoting solar-assisted charge carrier separation of carbon-based materials to achieve efficient utilization of solar energy in hydrogen production and CO₂ reduction. One interesting concept in nanofabrication that has become trend recent years is nanoarchitectonics. A heterostructure photocatalyst constructed based on the idea of nanoarchitectonics using the combination of g-C₃N₄, metal and an additional semiconducting nanocomposite is investigated in this paper. Z-scheme tungsten oxide incorporated copper modified graphitic carbon nitride (WO_x/Cu-g-C₃N₄) heterostructures are fabricated via immobilization of WO_x on Cu nanoparticles modified superior thin g-C₃N₄ nanosheets. Mechano-chemical pre-reaction and a two-step high-temperature thermal polymerization process are the keys in attaining homogeneous distribution of Cu nanoparticles in g-C₃N₄ nanosheets. The horizontal growth of homogeneously distributed WO_x nanobelts on Cu modified g-C₃N₄ (Cu-g-C₃N₄) base via solvothermal synthesis is achieved. The photocatalytic performances of the heterostructures are evaluated through water splitting and CO₂ photoreduction measurements in full solar spectrum irradiation condition. The presence of Cu nanoparticles in the composite system improves charge transport between g-C₃N₄ and WO_x and thus enhances the photocatalytic performances (H₂ generation and CO₂ photoreduction) of the composite material, while the presence of WO_x nanocomposites enhances light absorption of the composite material in the near infrared range. The synthesized heterostructure with optimized WO_x to Cu-g-C₃N₄ ratio and in case of no co-catalyst addition exhibits enhanced photocatalytic H₂ evolution (4560 μmolg^-1h^-1) as well as excellent CO₂ reduction rate (5.89 μmolg^-1h^-1 for CO generation).