Intrinsic Mechanisms of Morphological Engineering and Carbon Doping for Improved Photocatalysis of 2D/2D Carbon Nitride Van Der Waals Heterojunction

Van der Waals (VDW) heterojunctions in a 2D/2D contact provide the highest area for the separation and transfer of charge carriers. In this work, a top-down strategy with a gas erosion process was employed to fabricate a 2D/2D carbon nitride VDW heterojunction in carbon nitride (g-C3N4) with carbon-rich carbon nitride. The created 2D semiconducting channel in the VDW structure exhibits enhanced electric field exposure and radiation absorption, which facilitates the separation of the charge carriers and their mobility. Consequently, compared with bulk g-C3N4 and its nanosheets, the photocatalytic performance of the fabricated carbon nitride VDW heterojunction in the water splitting reaction to hydrogen is improved by 8.6 and 3.3 times, respectively, while maintaining satisfactory photo-stability. Mechanistically, the finite element method (FEM) was employed to evaluate and clarify the contributions of the formation of VDW heterojunction to enhanced photocatalysis, in agreement quantitatively with experimental ones. This study provides a new and effective strategy for the modification and more insights to performance improvement on polymeric semiconductors in photocatalysis and energy conversion.

Automated summary

A 2D/2D van der Waals heterojunction of carbon-rich carbon nitride was successfully fabricated using a top-down strategy, resulting in improved photocatalytic performance for the water splitting reaction. The created semiconducting channel in the heterojunction exhibited enhanced electric field exposure and radiation absorption, leading to better charge carrier separation and mobility. Finite element method analysis confirmed the contribution of the heterojunction formation to the enhanced photocatalysis.