Coupling silver dual atoms and nanoparticles on carbon support for efficient electroreduction N2 to ammonia

doi:10.1016/S1872-2067(25)64910-2

Abstract

Abstract:

Electrocatalytic N₂ reduction reaction (eNRR) is a green and sustainable approach for producing ammonia. Herein, we synthesized a Ag_2-Ag_NPs@C catalyst by coupling dual-atom Ag sites (Ag₂) and Ag nanoparticle (Ag_NPs) on the carbon support, which exhibits excellent eNRR performance, with a high NH₃ yield rate of 139.9 μg h^-1 mg^-1_cat. and an outstanding Faradaic Efficiency of 74.2%, which are superior to those of most reported eNRR catalysts. Density functional thoery calculations and in-situ infrared spectroscopy analysis demonstrate that in Ag₂-Ag_NPs@C catalyst, Ag_NPs facilitate water dissociation to produce H* intermediate that supplies to adsorbed *N₂ on the Ag₂ site for promoting the formation of *NNH key intermediate, thus lowering the Gibbs free energy of rate-determining step and substantially enhancing the eNRR performance. This work opens up new avenues for developing efficient electrocatalytic nitrogen reduction catalysts via synergistic effect.

Key words: Electrocatalytic N₂ reduction reaction, NH₃ production, Dual-atoms, Ag₂-Ag_NPs@C, Synergistic effect

Chang Liu, Mei Wang, Xiangming Liang, Tongbu Lu. Coupling silver dual atoms and nanoparticles on carbon support for efficient electroreduction N₂ to ammonia[J]. Chinese Journal of Catalysis, 2026, 82: 135-143.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64910-2

https://www.cjcatal.com/EN/Y2026/V82/I3/135

Figures/Tables 4

Fig. 1. (a) XRD pattern of Ag2-AgNPs@C. (b) HAADF-HRTEM image of Ag1-AgNPs@C. (c) HAADF-STEM image of Ag2-AgNPs@C. (d) HAADF-STEM image of Ag2-AgNPs@C. (e-g) HADDF-STEM elemental mapping images of Ag2-AgNPs@C.

Fig. 2. (a) XPS spectrum for Ag 3d of Ag2-AgNPs@C. (b) Ag K-edge XANES spectra of Ag2-AgNPs@C and reference samples. (c) FT-EXAFS curves, in which R and χ(k) denote the radial distance and the EXAFS oscillation function, respectively. (d-f) WT-EXAFS plots, in which k and (R + α) represent the electron wave vector and the interatomic distance without phase correction, respectively.

Fig. 3. (a) LSV curves of Ag2-AgNPs@C under Ar/N2. (b) Yields and FEs of Ag2-AgNPs@C at different applied potentials in 0.1 mol/L Na2SO4 solution. (c) 1H NMR spectra with 15N2 reaction. Yields and EFs of Ag1-AgNPs@C (d) and AgNPs@C (e) at different applied potentials in 0.1 mol/L Na2SO4 solution. (f) A comparison of the Yields and FEs of AgNPs@C, Ag1-AgNPs@C, and Ag2-AgNPs@C based on mg-1Ag. (g) Cycling tests of Ag2-AgNPs@C catalyst at -0.5 V vs. RHE. (h) A comparison of the Yields and FEs for Ag2-AgNPs@C with those of reported catalysts (see Table S3).

Fig. 4. The in-situ ATR-SEIRAS spectra of Ag2-AgNPs@C (a) and AgNPs@C (b) under different applied potentials with nitrogen as the feed gas. (c) Calculated free energy diagrams for N2 reduction on Ag2-AgNPs@C, Ag1-AgNPs@C, and AgNPs@C. (d) Calculated free energy diagrams for water dissociation on Ag2@C, Ag1@C, and AgNPs@C.

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Coupling silver dual atoms and nanoparticles on carbon support for efficient electroreduction N₂ to ammonia

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