Hydrogenated TiO2 Nanoparticles Loaded with Au Nanoclusters Demonstrating Largely Enhanced Performance for Electrochemical Reduction of Nitrogen to Ammonia

Abstract

Pristine TiO2/Au (P-TiO2/Au) is modified by hydrogen plasma (H-TiO2/Au) or hydrogen and oxygen plasma (H-O-TiO2/Au) treatment, and then used as electrochemical catalysts for nitrogen reduction reaction (NRR). H-TiO2/Au shows enhanced performance for the NRR process compared with both P-TiO2/Au and H-O-TiO2/Au. After hydrogenation treatment, some disordered regions on the surface of TiO2 nanoparticles are formed, and a large number of oxygen vacancies are incorporated into the TiO2 crystalline structures. When the samples are used as catalysts for electrochemical NRR, the yield of NH3 of H-TiO2/Au is about ten times compared to that of P-TiO2/Au and about three times that of H-O-TiO2/Au, while the highest Faradaic efficiency of 2.7% is also obtained at the potential of −0.1 V for the H-TiO2/Au catalyst. The density functional theory (DFT) calculation results confirm that H-TiO2/Au with oxygen vacancies and the disordered surface layer is much preferred energetically for the NRR process. It proves that enhanced adsorption of N2 molecules on the catalyst and reduced reaction barriers due to the presence of defects play an important role in improving catalysts’ performances. The results show that the plasma hydrogenation technique can be used as an efficient method to modify catalysts for electrochemical NRR processes.