Mechanocatalytic Synthesis of Ammonia by Titanium Dioxide with Bridge‐Oxygen Vacancies: Investigating Mechanism from the Experimental and First‐Principle Approach

Mechanochemical ammonia (NH3) synthesis is an emerging mild approach derived from nitrogen (N2) gas and hydrogen (H) source. The gas‐liquid phase mechanochemical process utilizes water (H2O), rather than conventional hydrogen (H2) gas, as H sources, thus avoiding carbon dioxide (CO2) emission during H2 production. However, ammonia yield is relatively low to meet practical demand due to huge energy barriers of N2 activation and H2O dissociation. Here, six transition metal oxides (TMO) such as titanium dioxide (TiO2), iron(III) oxide (Fe2O3), copper(II) oxide (CuO), niobium(V) oxide(Nb2O5), zinc oxide (ZnO), and copper(I) oxide (Cu2O) are investigated as catalysts in mechanochemical N2 fixation. Among them, TiO2 shows the best mechanocatalytic effect and the optimum reaction rate constant is 3.6‐fold higher than the TMO‐free process. The theoretical calculations show that N2 molecules prefer to side‐on chemisorb on the mechano‐induced bridge‐oxygen vacancies in the (101) crystal plane of TiO2 catalyst, while H2O molecules can dissociate on the same sites more easily to provide free H atoms, enabling an alternative‐way hydrogeneration process of activated N2 molecules to release NH3 eventually. This work highlights the cost‐effective TiO2 mechanocatalyst for ammonia synthesis under mild conditions and proposes a defect‐engineering‐induced mechanocatalytic mechanism to promote N2 activation and H2O dissociation. This work not only first reports on the mechanocatalytic performance and mechanism of TiO2(101) surface for efficient mechanochemical ammonia synthesis by using N2 and H2O as reactants, but also highlights the criterion for selecting specific mechanocatalysts by evaluating the ability of N2 chemisorption and activation and H2O dissociation on the surface of mechanocatalysts.