Two-dimensional ultrathin nanosheets over mackinawite FeS for efficient electrochemical N₂ reduction

Abstract

Electrocatalytic N₂ reduction reaction (NRR) has been considered as a promising and alternative strategy for the synthesis of NH₃, which will contribute to the goal of carbon neutrality and sustainability. However, this process often suffers from the barrier for N₂ activation and competitive reactions, resulting in poor NH₃ yield and low Faraday efficiency (FE). Here, we report a two-dimensional (2D) ultrathin FeS nanosheets with high conductivity through a facile and scalable method under mild condition. The synthesized FeS catalysts can be used as the work electrode in the electrochemical NRR cell with N₂-saturated Na₂SO₄ electrolyte. Such a catalyst shows a NH₃ yield of 9.0 µg·h⁻¹·mg⁻¹ (corresponding to 1.47 × 10⁻⁴ µmol·s⁻¹·cm⁻²) and a high FE of 12.4%, which significantly outperformed the other most NRR catalysts. The high catalytic performance of FeS can be attributed to the 2D mackinawite structure, which provides a new insight to explore low-cost and high-performance Fe-based electrocatalysts, as well as accelerates the practical application of the NRR.

Keywords

electrocatalysis / electrocatalytic nitrogen reduction reaction / FeS nanosheets / faraday efficiency

References

[1] B.C. Xu, D.L. Li, Q.Q. Zhao, S. Feng, X. Peng, and P.K. Chu, Electrochemical reduction of nitrate to ammonia using non-precious metal-based catalysts, Coord. Chem. Rev., 502(2024), art. No. 215609.

[2] S. Zhang, J.H. Wu, M.T. Zheng, et al., Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia, Nat. Commun., 14(2023), art. No. 3634.

[3] ChenSM, PerathonerS, AmpelliC, MebrahtuC, SuDS, CentiG. Room-temperature electrocatalytic synthesis of NH₃ from H₂O and N₂ in a gas–liquid–solid three-phase reactor. ACS Sustainable Chem. Eng., 2017, 5(8): 7393

[4] ZhangSY, ZhangBL, WuBY, LiuB, ZhangSG. Effect of samarium on the N₂ selectivity of Sm_xMn_0.3−xTi catalysts during selective catalytic reduction of NO_x with NH₃. Int. J. Miner. Metall. Mater., 2023, 30(4): 642

[5] LiuY, ZhuXR, ZhangQH, et al.. Engineering Mo/Mo₂C/MoC hetero-interfaces for enhanced electrocatalytic nitrogen reduction. J. Mater. Chem. A, 2020, 8(18): 8920

[6] GuoJJ, Tadesse TsegaT, Ul IslamI, IqbalA, ZaiJT, QianXF. Fe doping promoted electrocatalytic N₂ reduction reaction of 2H MoS₂. Chin. Chem. Lett., 2020, 31(9): 2487

[7] S. Mahmood, H.Y. Wang, F. Chen, Y.J. Zhong, and Y. Hu, Recent progress and prospects of electrolytes for electrocatalytic nitrogen reduction toward ammonia, Chin. Chem. Lett., 35(2024), No. 4, art. No. 108550.

[8] D.F. Qi, F. Lv, T.R. Wei, et al., High-efficiency electrocatalytic NO reduction to NH₃ by nanoporous VN, Nano Res. Energy, 1(2022), art. No. e9120022.

[9] WangYH, DongJH, TanZQ, WangXF, SongXZ. The journey of iron-based electrocatalytic materials for nitrogen reduction reaction: From current status to future prospects. J. Mater. Chem. A, 2023, 11(21): 11048

[10] LongJ, ChenSM, ZhangYL, et al.. Direct electrochemical ammonia synthesis from nitric oxide. Angew. Chem. Int. Ed, 2020, 59(24): 9711

[11] LiuHM, TimoshenkoJ, BaiLC, et al.. Low-coordination rhodium catalysts for an efficient electrochemical nitrate reduction to ammonia. ACS Catal., 2023, 13(2): 1513

[12] LiLL, JiangYF, ZhangTH, et al.. Size sensitivity of supported Ru catalysts for ammonia synthesis: From nanoparticles to subnanometric clusters and atomic clusters. Chem, 2022, 8(3): 749

[13] SongPF, WangH, CaoXM, LiuN, WangQ, WangRM. Ambient electrochemical N₂ reduction to NH₃ on nitrogen and phosphorus Co-doped porous carbon with trace iron in alkaline electrolytes. ChemElectroChem, 2020, 7(1): 212

[14] RenX, ZhaoJX, WeiQ, et al.. High-performance N₂-to-NH₃ conversion electrocatalyzed by Mo₂C nanorod. ACS Cent. Sci., 2019, 5(1): 116

[15] ChenSM, PerathonerS, AmpelliC, MebrahtuC, SuDS, CentiG. Electrocatalytic synthesis of ammonia at room temperature and atmospheric pressure from water and nitrogen on a carbon-nanotube-based electrocatalyst. Angew. Chem. Int. Ed, 2017, 56(10): 2699

[16] ZhongHX, ZhangHM, LiuSS, DengCW, WangMR. Nitrogen-enriched carbon from melamine resins with superior oxygen reduction reaction activity. ChemSusChem, 2013, 6(5): 807

[17] ZhangXX, WuTW, WangHB, et al.. Boron nanosheet: An elemental two-dimensional (2D) material for ambient electrocatalytic N₂-to-NH₃ fixation in neutral media. ACS Catal., 2019, 9(5): 4609

[18] AbghouiY, SigtryggssonSB, SkúlasonE. Biomimetic nitrogen fixation catalyzed by transition metal sulfide surfaces in an electrolytic cell. ChemSusChem, 2019, 12(18): 4265

[19] V. Ellingsson, A. Iqbal, E. Skúlason, and Y. Abghoui, Nitrogen reduction reaction to ammonia on transition metal carbide catalysts, ChemSusChem, 16(2023), No. 22, art. No. e202300947.

[20] Y. Abghoui, A. Iqbal, and E. Skúlason, The role of overlayered nitride electro-materials for N₂ reduction to ammonia, Front. Catal., 2(2023), art. No. 1096824.

[21] IqbalA, SkúlasonE, AbghouiY. Are (100) facets of transition metal carbonitrides suitable as electrocatalysts for nitrogen reduction to ammonia at ambient conditions?. Int. J. Hydrogen Energy, 2024, 64: 744

[22] WangTY, GuoZY, ZhangXL, et al.. Recent progress of iron-based electrocatalysts for nitrogen reduction reaction. J. Mater. Sci. Technol., 2023, 140: 121

[23] LiB, XuePF, QiaoM, TangYJ, ZhuDD. Cu doping in FeP enabling efficient electrochemical nitrate reduction to ammonia in neutral media. Chem. Commun., 2023, 59(91): 13611

[24] ZhuHD, RenXF, YangXX, LiangXY, LiuAM, WuG. Fe-based catalysts for nitrogen reduction toward ammonia electrosynthesis under ambient conditions. SusMat, 2022, 2(3): 214

[25] ZhuXJ, LiuZC, LiuQ, et al.. Efficient and durable N₂ reduction electrocatalysis under ambient conditions: β-FeOOH nanorods as a non-noble-metal catalyst. Chem. Commun., 2018, 54(80): 11332

[26] XieT, CaiZW, LiuXW, et al.. Fe₃O₄ nanoparticle-decorated 3D pinewood-derived carbon for high-efficiency electrochemical nitrate reduction to ammonia. Chem. Commun., 2023, 59(82): 12322

[27] WangM, LiFF, LiuJ. For N₂ fixation. RSC Adv., 2020, 10(49): 29575

[28] LiuQ, ZhangXX, ZhangB, et al.. Ambient N2 fixation to NH3 electrocatalyzed by a spinel Fe₃O₄ nanorod. Nanoscale, 2018, 10(30): 14386

[29] CuiXY, TangC, LiuXM, WangC, MaWJ, ZhangQ. Highly selective electrochemical reduction of dinitrogen to ammonia at ambient temperature and pressure over iron oxide catalysts. Chemistry, 2018, 24(69): 18494

[30] HuL, KhaniyaA, WangJ, ChenG, KadenWE, FengXF. Ambient electrochemical ammonia synthesis with high selectivity on Fe/Fe oxide catalyst. ACS Catal., 2018, 8(10): 9312

[31] KongJM, LimA, YoonC, et al.. Electrochemical synthesis of NH₃ at low temperature and atmospheric pressure using a γ-Fe₂O₃ catalyst. ACS Sustainable Chem. Eng., 2017, 5(11): 10986

[32] ChenX, YinHF, YangXY, et al.. Co-doped Fe₃S₄ nanoflowers for boosting electrocatalytic nitrogen fixation to ammonia under mild conditions. Inorg. Chem., 2022, 61(49): 20123

[33] GaoLF, GuoCY, ZhaoMZ, et al.. Electrocatalytic N₂ reduction on FeS₂ nanoparticles embedded in graphene oxide in acid and neutral conditions. ACS Appl. Mater. Interfaces, 2021, 13(42): 50027

[34] DuH, YangCZ, PuWH, ZengLY, GongJY. Enhanced electrochemical reduction of N₂ to ammonia over pyrite FeS₂ with excellent selectivity. ACS Sustainable Chem. Eng., 2020, 8(28): 10572

[35] XiongW, GuoZ, ZhaoSJ, WangQ, XuQY, WangXW. Facile, cost-effective plasma synthesis of self-supportive FeS_x on Fe foam for efficient electrochemical reduction of N₂ under ambient conditions. J. Mater. Chem. A, 2019, 7(34): 19977

[36] WattGW, ChrispJD. Spectrophotometric method for determination of hydrazine. Anal. Chem., 1952, 24(12): 2006

[37] ZouXX, WuYY, LiuYP, et al.. In situ generation of bifunctional, efficient Fe-based catalysts from mackinawite iron sulfide for water splitting. Chem, 2018, 4(5): 1139

[38] S. Niu, W.J. Jiang, T. Tang, L.P. Yuan, H. Luo, and J.S. Hu, Autogenous growth of hierarchical NiFe(OH)_x/FeS nanosheet-on-microsheet arrays for synergistically enhanced high-output water oxidation, Adv. Funct. Mater., 29(2019), No. 36, art. No. 1902180.

[39] RickardD, LutherGW. Chemistry of iron sulfides. Chem. Rev., 2007, 107(2): 514

[40] DuanYF, LiQ, HePP, et al.. Ultrathin FeS nanosheets with high chemodynamic activity for sensitive colorimetric detection of H₂O₂ and glutathione. Chin. Chem. Lett., 2022, 33(6): 3217

[41] Y. Sun, M. Danish, M. Ali, et al., Trichloroethene degradation by nanoscale CaO₂ activated with Fe(II)/FeS: The role of FeS and the synergistic activation mechanism of Fe(II)/FeS, Chem. Eng. J., 394(2020), art. No. 124830

[42] YangDS, ChenT, WangZJ. Electrochemical reduction of aqueous nitrogen (N₂) at a low overpotential on (110)-oriented Mo nanofilm. J. Mater. Chem. A, 2017, 5(36): 18967-18971

[43] ShiMM, BaoD, LiSJ. Anchoring PdCu amorphous nanocluster on graphene for electrochemical reduction of N₂ to NH₃ under ambient conditions in aqueous solution. Adv. Energy Mater., 2018, 8(21): 1800124

[44] ZhaoXH, LanX, YuDK, FuH, LiuZM, MuTC. Deep eutectic-solvothermal synthesis of nanostructured Fe₃S₄ for electrochemical N₂ fixation under ambient conditions. Chem. Commun., 2018, 54(92): 13010

[45] YaoY, ZhuSQ, WangHJ, et al.. A spectroscopic study on the nitrogen electrochemical reduction reaction on gold and platinum surfaces. J. Am. Chem. Soc., 2018, 140(4): 1496-1501

[46] ZhuD, ZhangLH, RutherRE, HamersRJ. Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. Nat. Mater., 2013, 12(9): 836

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