Theoretical insights into heteronuclear dual metals on non-metal doped graphene for nitrogen reduction reaction

doi:10.1016/S1872-2067(23)64500-0

Abstract

Abstract:

Electrochemical nitrogen reduction reaction (eNRR) is a promising strategy for sustainable ammonia production. To achieve high yield and energy efficiency, single-atom dispersion on nitrogen-doped graphene nanosheets has been extensively explored as an electrocatalyst for eNRR. However, challenges remain owing to the high overpotentials arising from unitary active sites and unabundant ligands. In this study, heteronuclear dual-metal catalysts with different non-metals doped in a graphene frame were computationally designed. After a two-step scanning based on density functional theory calculations, five candidates, namely FeMo-S, RuMo-B, RuMo-P, RuMo-S, and RuW-S, were identified as promising catalysts with calculated onset potentials of -0.18, -0.25, -0.27, -0.29, and -0.24 V, respectively. These catalysts can also effectively suppress the competitive hydrogen evolution reaction during NRR. Such excellent catalytic performance origins from two synergetic effects: (1) the cooperation of heteronuclear metals contribute to the electron transfer from active sites to the anti-bonding orbitals of N₂ molecules adsorbed on catalysts to effectively activate N≡N bonds; (2) metal-ligands (non-metals) interactions moderate the binding strength of intermediates to slab, which is one of reasons for low NRR onset potential and high NH₃ selectivity. The present study provides a theoretical understanding of the NRR mechanism of dual-metal catalysts, offering useful guidance for the rational design of catalysts with high selectivity and activity for NRR.

Key words: Electrocatalysis, Dual-atom catalyst, Graphene, Nitrogen reduction reaction, First principle theory

Ji Zhang, Aimin Yu, Chenghua Sun. Theoretical insights into heteronuclear dual metals on non-metal doped graphene for nitrogen reduction reaction[J]. Chinese Journal of Catalysis, 2023, 52: 263-270.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64500-0

https://www.cjcatal.com/EN/Y2023/V52/I9/263

Figures/Tables 7

Fig. 1. DAC model and reaction process of NRR. (a) Two types of transition metal atoms bounded to the defective graphene matrix along with six nitrogen atoms and another non-metallic atom as its ligands. (b) Schematic representation of NRR mechanisms, including alternating, distal, and enzymatic processes.

Fig. 2. Calculated Gibbs free energy changes for the first and last hydrogenation steps of NRR on M1M2-X catalysts. The dash line represents the value at 0.50 eV. The cyan area encompasses the most promising candidates for NRR.

Fig. 3. NRR and HER selective analysis. NRR is dominant within the bottom right region, while HER is dominant within the top left region.

Fig. 4. Calculated Gibbs free energy changes for the first and last steps of the NRR process on M1M2-X catalysts and their corresponding M-X SACs.

Fig. 5. Free energy profiles for NRR through enzymatic mechanism on FeMo-S (a), RuMo-P (b), RuMo-B (c), RuMo-S (d), and RuW-S (e).

Fig. 6. Study of N2 activation. (a) Optimized configurations of each intermediate adsorbed on the RuMo-B surface for NRR along with the enzymatic pathway under side-on configuration. (b) Diagrams of charge density differences in RuMo-B with N2 adsorption under side-on configuration (the charge density accumulation and depletion areas are displayed in yellow and cyan). (c) projected crystal orbital Hamilton populations (pCOHP) for N-N bonded to Ru-B, Mo-B, and RuMo-B under side-on configuration, respectively; PDOS before (d) and after (e) N2 was adsorbed on Ru-B, Mo-B, and RuMo-B, respectively (the d orbital of the metal atom is represented by the black line, and the N-2p orbital is represented by gray areas).

Fig. 7. Schematic diagram of dual-atom synergistic effect between Ru and Mo atoms, which enhance the NRR activity via moderation of the d-band center of catalysts, shown at the middle of the graph.

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