Structural band-gap tuning in g-C$_3$N$_4$

Abstract

g-C$_3$N$_4$ is a promising material for hydrogen production from water via photo-catalysis, if we can tune its band gap to desirable levels. Using a combined experimental and ab initio approach, we uncover an almost perfectly linear relationship between the band gap and structural aspects of g-C$_3$N$_4$, which we show to originate in a changing overlap of wave functions associated with the lattice constants. This changing overlap, in turn, causes the unoccupied $p_z$ states to experience a significantly larger energy shift than any other occupied state ($s$, $p_x$, or $p_y$), resulting in this peculiar relationship. Our results explain and demonstrate the possibility to tune the band gap by structural means, and thus the frequency at which g-C$_3$N$_4$ absorbs light.