Nitrate Reduction Reaction on Zr-Doped TiO2 (101) Surfaces Investigated by First-Principles Calculations

Abstract

Electrochemical nitrate reduction to ammonia is an efficient strategy for nitrate removal and ammonia production in ambient conditions. TiO2 is a promising electrocatalyst for such a reaction, but chemical doping is still needed to further improve the electrocatalytic properties of TiO2. Here, we investigated the effect of Zr-doping on the nitrate reduction reaction processes on the (101) surface of anatase TiO2 using first-principles calculations. Two models with different Zr-doping levels were built. The reaction pathways and the potential-determining steps were established based on a thorough investigation of the variation in Gibbs free energy of each possible elementary step. The results show that a high level of Zr doping was effective to lower the Gibbs free energy for nitrate adsorption; however, Zr doping may promote the competing hydrogen evolution reaction (HER) by reducing the adsorption Gibbs free energy of H. Moreover, Zr doping also increases the adsorption Gibbs free energies for the intermediate products NO2 and NO, which may result in an earlier termination of the reaction, by releasing the intermediates as the final products without producing ammonia. Therefore, Zr doping may decrease the Faradaic efficiency and selectivity of TiO2 for the reaction and should be treated with caution experimentally.