The
green and sustainable photocatalytic nitrogen reduction reaction
(NRR) for ammonia generation under ambient conditions holds great
promise. One of the most serious challenges is to improve the efficiency
of catalysts. In this study, an effective photocatalytic NRR has been
developed by using density functional theory (DFT) calculations, in
which a two-dimensional Cs3Bi2Br9–CdS van der Waals heterostructure is applied as the photocatalyst
and functioned under external control strategies. The calculated results
show that the heterojunction has a type-II band alignment, and the
unique built-in electric field lowers the band gap, enhances the light
absorption, and decreases the effective mass compared to those of
a single component. In addition, when applying an external electric
field up to 0.27 V/Å, the normal type-II band alignment is transformed
into type-Z band alignment, thus improving carrier separation and
maintaining high redox potential. From the exploration of surface
catalytic performance, it was found that the nitrogen–nitrogen
bond is activated by the strong nitrogen adsorption and electron transfer,
and the lower overpotential theoretically indicates an excellent catalytic
performance. This work not only provides a feasible strategy for improving
the NRR performance of photocatalysts, but also interprets the reaction
mechanism at the electronic level.