Optimizing the Lattice Nitrogen Coordination to Break the Performance Limitation of Metal Nitrides for Electrocatalytic Nitrogen Reduction.

Yuan, Haiyang; Zhu, Chen; Hou, Yu; Yang, Hua Gui; Wang, Haifeng

Yuan, Haiyang; Zhu, Chen; Hou, Yu; Yang, Hua Gui; Wang, Haifeng.

Afiliación

Yuan H; Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Zhu C; Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Hou Y; Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Yang HG; Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Wang H; State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Center for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.

JACS Au ; 4(8): 3038-3048, 2024 Aug 26.

Article en En | MEDLINE | ID: mdl-39211580

ABSTRACT

ABSTRACT

Metal nitrides (MNs) are attracting enormous attention in the electrocatalytic nitrogen reduction reaction (NRR) because of their rich lattice nitrogen (Nlat) and the unique ability of Nlat vacancies to activate N2. However, continuing controversy exists on whether MNs are catalytically active for NRR or produce NH3 via the reductive decomposition of Nlat without N2 activation in the in situ electrochemical conditions, let alone the rational design of high-performance MN catalysts. Herein, we focus on the common rocksalt-type MN(100) catalysts and establish a quantitative theoretical framework based on the first-principles microkinetic simulations to resolve these puzzles. The results show that the Mars-van Krevelen mechanism is kinetically more favorable to drive the NRR on a majority of MNs, in which Nlat plays a pivotal role in achieving the Volmer process and N2 activation. In terms of stability, activity, and selectivity, we find that MN(100) with moderate formation energy of Nlat vacancy (E vac) can achieve maximum activity and maintain electrochemical stability, while low- or high-E vac ones are either unstable or catalytically less active. Unfortunately, owing to the five-coordinate structural feature of Nlat on rocksalt-type MN(100), this maximum activity is limited to a yield of NH3 of only â¼10-15 mol s-1 cm-2. Intriguingly, we identify a volcano-type activity-regulating role of the local structural features of Nlat and show that the four-coordinate Nlat can exhibit optimal activity and overcome the performance limitation, while less coordinated Nlat fails. This work provides, arguably for the first time, an in-depth theoretical insight into the activity and stability paradox of MNs for NRR and underlines the importance of reaction kinetic assessment in comparison with the prevailing simple thermodynamic analysis.

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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: JACS Au Año: 2024 Tipo del documento: Article País de afiliación: China Pais de publicación: Estados Unidos

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