Neighboring effect in PtCuSnCo alloy catalysts for precisely regulating nitrate adsorption and deoxidation to achieve 100% faradaic efficiency in ammonia synthesis

doi:10.1016/S1872-2067(25)64705-X

Abstract

Abstract:

The electrochemical reduction of nitrate (NO₃⁻) to ammonia (NH₃) (NO₃RR) represents an environmentally sustainable strategy for NH₃ production while concurrently addressing water pollution challenges. Nevertheless, the intrinsic complexity of this multi-step reaction severely constrains both the selectivity and efficiency of NO₃RR. Copper-based electrocatalysts have been extensively investigated for NO₃RR but often suffer from nitrite (NO₂⁻) accumulation, which stems from insufficient NO₃⁻ adsorption strength. This limitation often leads to rapid catalyst deactivation, hindered hydrogenation pathways, and reduced overall efficiency. Herein, we report a one-step green chemical reduction method to synthesize PtCuSnCo quarternary alloy nanoparticles with homogeneously distributed elements. Under practical NO₃⁻ concentrations, the optimized catalyst exhibited an impressive Faradaic efficiency approaching 100% and an outstanding selectivity of 95.6 ± 2.9%. Mechanistic insights uncovered that SnCo sites robustly facilitated NO₃⁻ adsorption, complemented by the proficiency of PtCu sites in NO₃⁻ reduction. The synergistic spatial neighborhood effect between SnCo and PtCu sites efficiently stabilizes NO₃⁻ deoxygenation and suppresses NO₂⁻ accumulation. This tandem architecture achieves a finely tuned balance between adsorption strength and deoxygenation kinetics, enabling highly selective and efficient NO₃RR. Our findings emphasize the indispensable role of engineered multi-metallic catalysts in overcoming persistent challenges of NO₃RR, paving the way for advanced NH₃ synthesis and environmental remediation.

Key words: Neighboring effect, Quaternary alloy, Deoxidation, Ammonia synthesis, In situ Raman spectroscopy

Yun Ling, Hui Su, Ru-Yu Zhou, Qingyun Feng, Xuan Zheng, Jing Tang, Yi Li, Maosheng Zhang, Qingxiang Wang, Jian-Feng Li. Neighboring effect in PtCuSnCo alloy catalysts for precisely regulating nitrate adsorption and deoxidation to achieve 100% faradaic efficiency in ammonia synthesis[J]. Chinese Journal of Catalysis, 2025, 73: 347-357.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64705-X

https://www.cjcatal.com/EN/Y2025/V73/I6/347

Figures/Tables 6

Fig. 1. (a) SEM image of PtCuSnCo alloy. Insert is the size distribution of the nanoparticles. (b) EDX plot of PtCuSnCo alloy. Insert is the atomic ratio of alloy elements from ICP-OES. TEM (c) and HRTEM (f) images of PtCuSnCo alloy. (d,e,g,h) EDX elemental mapping images of Pt, Cu, Sn, and Co in PtCuSnCo alloy.

Fig. 2. XPS spectra of PtCuSnCo alloy in the Pt 4f (a), Cu 2p (b), Sn 3d (c), and Co 2p (d) regions before catalysis.

Fig. 3. Electrochemical NO3RR properties of PtCuSnCo alloy. (a) LSV curves in 0.1 mol L?1 Na2SO4 electrolyte with and without 100 ppm NaNO3. (b) Time-dependent current density curves, (c) NH3 yields and FE at different potentials. (d) NH3 and NO2? selectivity diagram of PtCuSnCo alloy at different NO3? concentrations. Comparison of NH3 yield and FE of PtCuSnCo alloy with different loadings (e) and different precursor concentrations (f).

Fig. 4. Validation of NH3 source and stability tests. (a) UV-vis absorption spectra under different conditions. (b) NH3 yield with NaNO3 and without NaNO3. (c) 1H NMR spectra of electrolytes with 15NO3? and 14NO3? as N sources, respectively. (d) Quantitative NH3 yields by different methods. Five-cycle test (e) and long-time stability (f).

Fig. 5. (a) NH3 yields and FE of different quaternary alloys. (b) NH3 yields and FE of different alloys.

Fig. 6. (a) In situ Raman spectra of PtCuSnCo during NO3RR at different potentials (V vs. RHE) in a mixed solution (100 ppm NaNO3 + 0.1 mol L?1 Na2SO4). (b) Top view of the structure models of various NO3RR intermediates on PtCuSnCo. (c) Free-energy diagram for nitrate-to-ammonia conversion over PtCuSnCo.

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