Different Atomic Terminations Affect the Photocatalytic Nitrogen Fixation of Bismuth Oxybromide: A First Principles Study

We have systematically investigated the electronic structures and activation capacities of BiOBr {001} facets with different atomic terminations by means of DFT methods. Our calculations reveal that oxygen vacancies (OVs) give a significant boost in band edges of the O-terminated BiOBr {001} facets, and excess electrons induced by OVs could exceed the reduction potentials of high-energy N₂ intermediates. Interestingly, the Bi-terminated BiOBr {001} facets may be good candidates for photocatalytic nitrogen fixation due to the stronger activation ability of N₂ molecules comparing with O-terminated BiOBr {001} facets with OVs. Moreover, the Bi-terminated BiOBr {001} facets may tend to yield NH₃ instead of N₂ H₄ .