Boosting charge-transfer in tuned Au nanoparticles on defect-rich TiO₂ nanosheets for enhancing nitrogen...

The electrocatalytic nitrogen reduction reaction (eNRR) to ammonia (NH₃) has been recognized as an effective, carbon-neutral, and great-potential strategy for ammonia production. However, the conversion efficiency and selectivity of eNRR still face significant challenges due to the slow transfer kinetics and lack of effective N₂ adsorption and activation sites in this process. Herein, we designed and fabricated defect-rich TiO₂ nanosheets furnished with oxygen vacancies (OVs) and Au nanoparticles (Au/TiO_2-x) as the electrocatalyst for efficient N₂-fixing. The experimental results demonstrate that OVs act as active sites, which enable efficient chemisorption and activation of N₂ molecules. The Au nanoparticles loaded on the OVs-rich TiO₂ nanosheets not only accelerate charge transfer but also change the local electronic structure, thus enhancing N₂ adsorption and activation. In this work, the optimal Au/TiO_2-x electrocatalyst displays a considerable NH₃ yield activity of 12.5 μg h^-1 mg_cat.^-1 and a faradaic efficiency (FE) of 10.2 % at -0.40 V vs reversible hydrogen electrode (RHE). More importantly, the Au/TiO_2-x exhibits a stable N₂-fixing activity in cycling and it persists even after 80 h of consecutive electrolysis. Density functional theory (DFT) calculations reveal that the OVs serve as the active sites in TiO₂, while Au nanoparticles are crucial for improving N₂ chemisorption and lowering the reaction energy barrier by facilitating the charge transfer for eNRR with a distal hydrogenation pathway. This research offers a rational catalytic site design for modulating charge transfer of active sites on metal-supported defective catalysts to boost N₂ electroreduction to NH₃.