H migration-assisted MvK mechanism for efficient electrochemical NH 3 synthesis over TM-TiNO

• Published in: Physical chemistry chemical physics : PCCP 2024-05, Vol.26 (21), p.15705-15716
• Main Authors: Cui, Luyao, Sun, Zijun, Wang, Yawen, Jian, Xuan, Li, Houfen, Zhang, Xiao, Gao, Xiaoming, Li, Rui, Liu, Jianxin
• Format: Article
• Language: English
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/D4CP01207K

The electrochemical NH synthesis on TiNO is proposed to follow the Mars-van Krevelen (MvK) mechanism, offering more favorable N adsorption and activation on the N vacancy (Nv) site, compared to the conventional associative mechanism. The regeneration cycle of Nv represents the rate-determining step in this process. This study investigates a series of TM (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt)-TiNO to explore the *H migration (from TM to TiNO)-promoted Nv cycle. The screening results indicate that Ni-TiNO exhibits strong H O decomposition for *H production with 0.242 eV and low *H migration resistance with 0.913 eV. Notably, *H migration from Ni to TiNO significantly reduces the Nv formation energy to 0.811 eV, compared to 1.387 eV on pure TiNO. Meanwhile, in the presence of *H, Nv formation takes precedence over Tiv and Ov. Lastly, electronic performance calculations reveal that the collaborative function provided by Ni and Nv enables highly stable and efficient NH synthesis. The *H migration-assisted MvK mechanism demonstrates effective catalytic cycle performance in electrochemical N fixation and may have potential applicability to other hydrogenation reactions utilizing water as a proton source.