First-principles investigation of β-Ge3N4 loaded with RuO2 cocatalyst for photocatalytic overall water splitting

Abstract

Abstract β-Ge3N4 loaded with nanoparticulate RuO2 as a cocatalyst is the first successful non-oxide photocatalyst for overall water splitting. To get an insight into the working mechanism of this particular photocatalytic system, we have calculated geometrical structures of low-index surfaces for β-Ge3N4. Analysis of surface energies indicates that the most preferentially exposed surface is (100). The band gap of surface is narrower than that of bulk due to the dangling bonds. Dissociative water adsorption on (100) surface is thermodynamically favorable. The adsorption behavior of (RuO2)n (n = 2, 3, and 4) clusters on the β-Ge3N4(100) surface has been explored. It is found that all the clusters bind to (100) surface strongly by forming interfacial bonds so that the adsorptions are exothermic processes. The calculation on density of states for β-Ge3N4(100) surface loaded with (RuO2)n clusters reveals that photo-induced electrons tend to accumulate on (RuO2)n clusters and holes tend to stay in β-Ge3N4. Based on the theoretical indication of Type-II staggered band alignment, we have proposed that in photocatalytic water splitting reaction, oxygen evolution reaction is inclined to occur on the surface of β-Ge3N4 while hydrogen evolution reaction is apt to occur on (RuO2)n clusters. In a word, loading RuO2 nanoparticles as a reduction cocatalyst benefits the charge separation in β-Ge3N4. Furthermore, attaching (RuO2)n clusters onto β-Ge3N4(100) surface results in the redshift of absorption edge and the increase of absorption intensity. Our calculations have reasonably explained the experimental observation on the decomposition of water into H2 and O2 after loading RuO2 cocatalyst in β-Ge3N4 photocatalyst.