Unifying the Nitrogen Reduction Activity of Anatase and Rutile TiO2 Surfaces

TiO2 is a model transition metal oxide that has been applied frequently in both photocatalytic and electrocatalytic nitrogen reduction reactions (NRR). However, the phase which is more NRR active still remains a puzzle. This work presents a theoretical study on the NRR activity of the (001), (100), (101), and (110) surfaces of both anatase and rutile TiO2 . We found that perfect surfaces are not active for NRR, while the oxygen vacancy can promote the reaction by providing excess electrons and low-coordinated Ti atoms that enhance the binding of the key intermediate (HNN*). The NRR activity of the eight facets can be unified into a single scaling line. The anatase TiO2 (101) and rutile TiO2 (101) surfaces were found to be the most and the second most active surfaces with a limiting potential of -0.91 V and -0.95 V respectively, suggesting that the TiO2 NRR activity is not very phase-sensitive. For photocatalytic NRR, the results suggest that the anatase TiO2 (101) surface is still the most active facet. We further found that the binding strength of key intermediates scale well with the formation energy of oxygen vacancy, which is determined by the oxygen coordination number and the degree of relaxation of the surface after the creation of oxygen vacancy. This work provides a comprehensive understanding of the activity of TiO2 surfaces. The results should be helpful for the design of more efficient TiO2 -based NRR catalysts.