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

Mechanochemical ammonia (NH) synthesis is an emerging mild approach derived from nitrogen (N) gas and hydrogen (H) source. The gas-liquid phase mechanochemical process utilizes water (HO), rather than conventional hydrogen (H) gas, as H sources, thus avoiding carbon dioxide (CO) emission during H production. However, ammonia yield is relatively low to meet practical demand due to huge energy barriers of N activation and HO dissociation. Here, six transition metal oxides (TMO) such as titanium dioxide (TiO), iron(III) oxide (FeO), copper(II) oxide (CuO), niobium(V) oxide(NbO), zinc oxide (ZnO), and copper(I) oxide (CuO) are investigated as catalysts in mechanochemical N fixation. Among them, TiO 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 N molecules prefer to side-on chemisorb on the mechano-induced bridge-oxygen vacancies in the (101) crystal plane of TiO catalyst, while HO molecules can dissociate on the same sites more easily to provide free H atoms, enabling an alternative-way hydrogeneration process of activated N molecules to release NH eventually. This work highlights the cost-effective TiO mechanocatalyst for ammonia synthesis under mild conditions and proposes a defect-engineering-induced mechanocatalytic mechanism to promote N activation and HO dissociation.