Issue 21, 2024

*H migration-assisted MvK mechanism for efficient electrochemical NH3 synthesis over TM–TiNO

Abstract

The electrochemical NH3 synthesis on TiNO is proposed to follow the Mars–van Krevelen (MvK) mechanism, offering more favorable N2 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 H2O 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 NH3 synthesis. The *H migration-assisted MvK mechanism demonstrates effective catalytic cycle performance in electrochemical N2 fixation and may have potential applicability to other hydrogenation reactions utilizing water as a proton source.

Graphical abstract: *H migration-assisted MvK mechanism for efficient electrochemical NH3 synthesis over TM–TiNO

Supplementary files

Article information

Article type
Paper
Submitted
22 Mar 2024
Accepted
08 May 2024
First published
09 May 2024

Phys. Chem. Chem. Phys., 2024,26, 15705-15716

*H migration-assisted MvK mechanism for efficient electrochemical NH3 synthesis over TM–TiNO

L. Cui, Z. Sun, Y. Wang, X. Jian, H. Li, X. Zhang, X. Gao, R. Li and J. Liu, Phys. Chem. Chem. Phys., 2024, 26, 15705 DOI: 10.1039/D4CP01207K

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