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TiO 2 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 TiO 2 . 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 TiO 2 (101) and rutile TiO 2 (101) surfaces were found to be the most and the second most active surfaces with a limiting potential of À 0.91 V and À 0.95 V respectively, suggesting that the TiO 2 NRR activity is not very phase-sensitive. For photocatalytic NRR, the results suggest that the anatase TiO 2 (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 TiO 2 surfaces. The results should be helpful for the design of more efficient TiO 2 -based NRR catalysts.

Electrocatalytic nitrogen reduction reaction (eNRR) has been attracting intensive scientific attention as a potential alternative to the industrial Haber-Bosch process for ammonia production. Though many materials have been investigated, optimal...

Electrocatalytic nitrogen reduction reactions (NRR) have attracted intensive scientific attention, and boron in various forms has been shown promising for the activation of N2. In this work, we accessed the...