Recent advances and challenges of nitrogen/nitrate electro catalytic reduction to ammonia synthesis

Abstract

The Haber-Bosch process is the most widely used synthetic ammonia technology at present. Since its invention, it has provided an important guarantee for global food security. However, the traditional Haber-Bosch ammonia synthesis process consumes a lot of energy and causes serious environmental pollution. Under the serious pressure of energy and environment, a green, clean, and sustainable ammonia synthesis route is urgently needed. Electrochemical synthesis of ammonia is a green and mild new method for preparing ammonia, which can directly convert nitrogen or nitrate into ammonia using electricity driven by solar, wind, or water energy, without greenhouse gas and toxic gas emissions. Herein, the basic mechanism of the nitrogen reduction reaction (NRR) to ammonia and nitrate reduction reaction ({\text{NO}}_3^{-} RR) to ammonia were discussed. The representative approaches and major technologies, such as lithium mediated electrolysis and solid oxide electrolysis cell (SOEC) electrolysis for NRR, high activity catalyst and advanced electrochemical device fabrication for {\text{NO}}_3^{-} RR and electrochemical ammonia synthesis were summarized. Based on the above discussion and analysis, the main challenges and development directions for electrochemical ammonia synthesis were further proposed.

Graphical abstract

Keywords

electrochemical ammonia synthesis / nitrogen / nitrate / nitrogen reduction reaction (NRR) to ammonia / nitrate reduction reaction (NO^–3 RR)

References

[1] Chen J G, Crooks R M, Seefeldt L C. . Beyond fossil fuel–driven nitrogen transformations. Science, 2018, 360(6391): eaar6611

[2] Gilbert N. African agriculture: Dirt poor. Nature, 2012, 483(7391): 525–527

[3] Suryanto B H R, Du H, Wang D. . Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia. Nature Catalysis, 2019, 2(4): 290–296

[4] Wang L, Xia M, Wang H. . Greening ammonia toward the solar ammonia refinery. Joule, 2018, 2(6): 1055–1074

[5] Qing G, Ghazfar R, Jackowski S T. . Recent advances and challenges of electrocatalytic N₂ reduction to ammonia. Chemical Reviews, 2020, 120(12): 5437–5516

[6] Zhan C, Nichols J A, Dixon D A. Ionization potential, electron affinity, electronegativity, hardness, and electron excitation energy: Molecular properties from density functional theory orbital energies. Journal of Physical Chemistry A, 2003, 107(20): 4184–4195

[7] Cui X, Tang C, Zhang Q. A review of electrocatalytic reduction of dinitrogen to ammonia under ambient conditions. Advanced Energy Materials, 2018, 8(22): 1800369

[8] Shilov A E. Catalytic reduction of molecular nitrogen in solutions. Russian Chemical Bulletin, International Edition, 2003, 12(52): 2555–2562

[9] Foster S L, Bakovic S I P, Duda R D. . Catalysts for nitrogen reduction to ammonia. Nature Catalysis, 2018, 1(7): 490–500

[10] Nagaoka K, Eboshi T, Takeishi Y. . Carbon-free H₂ production from ammonia triggered at room temperature with an acidic RuO₂/g-Al₂O₃ catalyst. Science Advances, 2017, 3(4): e1602747

[11] van der Ham C J, Koper M T, Hetterscheid D G. Challenges in reduction of dinitrogen by proton and electron transfer. Chemical Society Reviews, 2014, 43(15): 5183–5191

[12] Jia H P, Quadrelli E A. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: Relevance of metal hydride bonds and dihydrogen. Chemical Society Reviews, 2014, 43(2): 547–564

[13] Wang K, Smith D, Zheng Y. Electron-driven heterogeneous catalytic synthesis of ammonia: Current states and perspective. Carbon Resources Conversion, 2018, 1(1): 2–31

[14] Erisman J W, Sutton M A, Galloway J. . How a century of ammonia synthesis changed the world?. Nature Geoscience, 2008, 1(10): 636–639

[15] Guo W, Zhang K, Liang Z. . Electrochemical nitrogen fixation and utilization: Theories, advanced catalyst materials and system design. Chemical Society Reviews, 2011, 40(1): 15–18

[16] Wang J, Cai C, Wang Y. . Electrocatalytic reduction of nitrate to ammonia on low-cost ultrathin CoO_x nanosheets. ACS Catalysis, 2021, 11(24): 15135–15140

[17] Badea G E. Electrocatalytic reduction of nitrate on copper electrode in alkaline solution. Electrochimica Acta, 2009, 54(3): 996–1001

[18] Wang Y, Zhou W, Jia R. . Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia. Angewandte Chemie International Edition, 2020, 59(13): 5350–5354

[19] MacFarlane D R, Cherepanov P V, Choi J. . A roadmap to the ammonia economy. Joule, 2020, 4(6): 1186–1205

[20] Martín A J, Shinagawa T, Pérez-Ramírez J. . Electrocatalytic reduction of nitrogen: From Haber-Bosch to ammonia artificial leaf. Chem, 2019, 5(2): 263–283

[21] Chen W, Yang X, Chen Z. . Emerging applications, developments, prospects, and challenges of electrochemical nitrate-to-ammonia conversion. Advanced Functional Materials, 2023, 33(29): 2300512

[22] Liu Q, Xu T, Luo Y. . Recent advances in strategies for highly selective electrocatalytic N₂ reduction toward ambient NH₃ synthesis. Current Opinion in Electrochemistry, 2021, 29: 100766

[23] Ouyang L, Liang J, Luo Y. . Recent advances in electrocatalytic ammonia synthesis. Chinese Journal of Catalysis, 2023, 50: 6–44

[24] Liang J, Li Z, Zhang L. . Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction. Chem, 2023, 9(7): 1768–1827

[25] Song W, Yue L, Fan X. . Recent progress and strategies on design of catalysts for electrochemical ammonia synthesis from nitrate reduction. Inorganic Chemistry Frontiers, 2023, 10(12): 3489

[26] Ma X, Liu J, Xiao H. . Surface single-cluster catalyst for N₂-to-NH₃ thermal conversion. Journal of the American Chemical Society, 2018, 140(1): 46–49

[27] Honkala K, Hellman A, Remediakis I N. . Ammonia synthesis from first-principles calculations. Science, 2005, 307(5709): 555–558

[28] Wang S, Ichihara F, Pang H. . Nitrogen fixation reaction derived from nanostructured catalytic materials. Advanced Functional Materials, 2018, 28(50): 1803309

[29] Imamura K, Kubota J. Electrochemical membrane cell for NH₃ synthesis from N₂ and H₂O by electrolysis at 200 to 250 °C using a Ru catalyst, hydrogen-permeable Pd membrane and phosphate-based electrolyte. Sustainable Energy & Fuels, 2018, 2(6): 1278–1286

[30] Kyriakou V, Garagounis I, Vasileiou E. . Progress in the electrochemical synthesis of ammonia. Catalysis Today, 2017, 286: 2–13

[31] Kim K, Kim J, Yoon H C. . Effect of electrode material on the electrochemical reduction of nitrogen in a molten LiCl–KCl–CsCl system. International Journal of Hydrogen Energy, 2015, 40(16): 5578–5582

[32] Licht S, Cui B, Wang B. . Ammonia synthesis by N₂ and steam electrolysis in molten hydroxide suspensions of nanoscale Fe₂O₃. Science, 2020, 369(6505): 780–781

[33] Ma X, Li M, Lu J. . Recent developments of dinitrogen activation on metal complexes and clusters. Chinese. Journal of Structural Chemistry, 2022, 41(12): 2212080–2212088

[34] LvZLiZ LiuH, . Simultaneously enhancing adsorbed hydrogen and dinitrogen to enable efficient electrochemical NH₃ synthesis on Sm(OH)₃. Small Structures, 2023, online, https://doi.org/10.1002/sstr.202300158

[35] Xu T, Ma B, Liang J. . Recent progress in metal-free electrocatalysts toward ambient N₂ reduction reaction. Acta Physico-Chimica Sinica, 2020, 37(7): 2009043

[36] Lan R, Irvine J T S, Tao S. Synthesis of ammonia directly from air and water at ambient temperature and pressure. Scientific Reports, 2013, 3(1): 1145

[37] Zhang X, Wang Y, Liu C. . Recent advances in non-noble metal electrocatalysts for nitrate reduction. Chemical Engineering Journal, 2021, 403: 126269

[38] Shahid M, Javed H M A, Ahmad M I. . A brief assessment on recent developments in efficient electrocatalytic nitrogen reduction with 2D non-metallic nanomaterials. Nanomaterials, 2022, 12(19): 3413

[39] Yang X, Mukherjee S, O’Carroll T. . Achievements, challenges, and perspectives on nitrogen electrochemistry for carbon-neutral energy technologies. Angewandte Chemie International Edition, 2023, 62: e2022159

[40] Utomo W P, Wu H, Ng Y H. Modulating the active sites of oxygen-deficient TiO₂ by copper loading for enhanced electrocatalytic nitrogen reduction to ammonia. Small, 2022, 18(25): 2270131

[41] Tian Y, Liu Y, Wang H. . Electrocatalytic reduction of nitrogen to ammonia in ionic liquids. ACS Sustainable Chemistry & Engineering, 2022, 10(14): 4345–4358

[42] Paul S, Sarkar S, Adalder A. . Strengthening the metal center of Co−N₄ active sites in a 1D–2D heterostructure for nitrate and nitrogen reduction reaction to ammonia. ACS Sustainable Chemistry & Engineering, 2023, 11(16): 6191–6200

[43] Wang S, Huang X, Pei L. . Synergistic removal of ammonia nitrogen by UV photo-electrocatalytic process: Heterogeneous reaction pathways and mechanism. Journal of Cleaner Production, 2023, 384: 135515

[44] Yang Y, Zhang W, Tan X. . Atomic-level reactive sites for electrocatalytic nitrogen reduction to ammonia under ambient conditions. Coordination Chemistry Reviews, 2023, 489: 215196

[45] Zhao X, Hu G, Chen G F. . Comprehensive understanding of the thriving ambient electrochemical nitrogen reduction reaction. Advanced Materials, 2021, 33(33): 2007650

[46] Zhang M, Choi C, Huo R. . Reduced graphene oxides with engineered defects enable efficient electrochemical reduction of dinitrogen to ammonia in wide pH range. Nano Energy, 2020, 68: 104323

[47] Ren T, Sheng Y, Wang M. . Recent advances of Cu-based materials for electrochemical nitrate reduction to ammonia. Chinese Journal of Structural Chemistry, 2022, 41(12): 2212089–2212106

[48] Iqbal M S, Yao Z, Ruan Y. . Single-atom catalysts for electrochemical N₂ reduction to NH₃. Rare Metals, 2023, 42(4): 1075–1097

[49] Basu J, Ganguly S. Electrocatalytic nitrogen reduction reaction (NRR), a probable alternative to Haber-Bosch process (HBP). Resonance, 2023, 28(2): 279–291

[50] Wang D, Chen C, Wang S. Defect engineering for advanced electrocatalytic conversion of nitrogen-containing molecules. Science China. Chemistry, 2023, 66(4): 1052–1072

[51] Tao L, Huang L, Pang K. . Fe-doped Mo₂C for boosting electrocatalytic N₂ reduction. Inorganic Chemistry Communications, 2022, 145: 110003

[52] Yao Z, Liu S, Liu H. . Pre-adsorbed H-assisted N₂ activation on single-atom cadmium-O₅ decorated In₂O₃ for efficient NH₃ electrosynthesis. Advanced Functional Materials, 2023, 33(5): 2209843

[53] Ali T, Muhammad N, Qian Y. . Recent advances in material design and reactor engineering for electrocatalytic ambient nitrogen fixation. Materials Chemistry Frontiers, 2022, 33(5): 843−879

[54] Hirakawa H, Hashimoto M, Shiraishi Y. . Selective nitrate-to-ammonia transformation on surface defects of titanium dioxide photocatalysts. ACS Catalysis, 2017, 7(5): 3713–3720

[55] TugaoenH OGarcia-Segura SHristovskiK, . Challenges in photocatalytic reduction of nitrate as a water treatment technology. Science of the Total Environment, 2017, 599–600: 599-600

[56] Garcia-Segura S, Lanzarini-Lopes M, Hristovski K. . Electrocatalytic reduction of nitrate: Fundamentals to full-scale water treatment applications. Applied Catalysis B: Environmental, 2018, 236: 546–568

[57] Li J, Li H, Fan K. . Electrocatalytic nitrate reduction to ammonia coupled with organic oxidation. Chem Catalysis, 2023, 3(6): 100638

[58] Ren T, Sheng Y, Wang M. . Recent advances of Cu-based materials for electrochemical nitrate reduction to ammonia. Chinese Journal of Structural Chemistry, 2022, 41(12): 2212089–2212106

[59] Theerthagiri J, Park J, Das H T. . Electrocatalytic conversion of nitrate waste into ammonia: A review. Environmental Chemistry Letters, 2022, 20(5): 2929–2949

[60] Chen G, Yuan Y, Jiang H. . Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst. Nature Energy, 2020, 5(8): 605–613

[61] Zheng Y, Wang J, Yu B. . A review of high temperature co-electrolysis of H₂O and CO₂ to produce sustainable fuels using solid oxide electrolysis cells (SOECs): Advanced materials and technology. Chemical Society Reviews, 2017, 11: 1427–1463

[62] Chen Q, Liang J, Liu Q. . Co nanoparticle-decorated pomelo-peel-derived carbon enabled high-efficiency electrocatalytic nitrate reduction to ammonia. Chemical Communications, 2022, 58(26): 4259–4262

[63] Li C, Liu S, Xu Y. . Controllable reconstruction of copper nanowires into nanotubes for efficient electrocatalytic nitrate conversion into ammonia. Nanoscale, 2022, 14(34): 12332–12338

[64] Xue Y, Yu Q, Ma Q. . Electrocatalytic hydrogenation boosts reduction of nitrate to ammonia over single-atom Cu with Cu(I)-N₃C₁ sites. Environmental Science & Technology, 2022, 56(20): 14797–14807

[65] Fang L, Wang S, Song C. . Boosting nitrate electroreduction to ammonia via in situ generated stacking faults in oxide-derived copper. Chemical Engineering Journal, 2022, 446: 137341

[66] Fang J, Fan J, Liu S. . Copper-based electrocatalysts for nitrate reduction to ammonia. Materials, 2023, 16(11): 4000

[67] Bai Z, Li X, Ding L. . Artificial Cu−Ni catalyst towards highly efficient nitrate-to-ammonia conversion. Science China Materials, 2023, 66(6): 2329–2338

[68] Zhang S, Wu J, Zheng M. . Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia. Nature Communications, 2023, 14(1): 3634

[69] Wang G, Zhang Y, Chen K. . PdP₂ nanoparticles on reduced graphene oxide: A catalyst for the electrocatalytic reduction of nitrate to ammonia. Inorganic Chemistry, 2023, 62(17): 6570–6575

[70] Huang P, Fan T, Ma X. . 3D flower-like zinc cobaltite for electrocatalytic reduction of nitrate to ammonia under ambient conditions. ChemSusChem, 2022, 15(4): e202102049

[71] Tao W, Wang P, Li H. . Engineering sulfur vacancies optimization in Ni₃Co₆S₈ nanospheres toward extraordinarily efficient nitrate electroreduction to ammonia. Applied Catalysis B: Environmental, 2023, 324: 122193

[72] Wu X, Liu Z, Gao T. . Boosting electrocatalytic reduction of nitrate to ammonia over Co₃O₄ nanosheets with oxygen vacancies. Metals, 2023, 13(4): 799

[73] Wang Y, Wang C, Li M. . Nitrate electroreduction: Mechanism insight, in situ characterization, performance evaluation, and challenges. Chemical Society Reviews, 2021, 50(12): 6720–6733

[74] Niu H, Zhang Z, Wang X. . Theoretical insights into the mechanism of selective nitrate-to-ammonia electroreduction on single-atom catalysts. Advanced Functional Materials, 2021, 31(11): 2008533

[75] Fichter F, Girard P, Erlenmeyer H. An electrolyte formed by compressed nitrogen at normal temperature. Helvetica Chimica Acta, 1930, 13(6): 1228–1236 (in German)

[76] Tsuneto A, Kudo A, Sakata T. Efficient electrochemical reduction of N₂ to NH₃ catalyzed by lithium. Chemistry Letters, 1993, 22(5): 851–854

[77] Tsuneto A, Kudo A, Sakata T. Lithium-mediated electrochemical reduction of high pressure N₂ to NH₃. Journal of Electroanalytical Chemistry, 1994, 367(1–2): 183–188

[78] Lazouski N, Schiffer Z J, Williams K. . Understanding continuous lithium-mediated electrochemical nitrogen reduction. Joule, 2019, 3(4): 1127–1139

[79] IqbalM SRuan YIftikharR, . Lithium-mediated electrochemical dinitrogen reduction reaction. Industrial Chemistry & Materials, 2023

[80] McEnaney J M, Singh A R, Schwalbe J A. . Ammonia synthesis from N₂ and H₂O using a lithium cycling electrification strategy at atmospheric pressure. Energy & Environmental Science, 2017, 10(7): 1621–1630

[81] Li S, Zhou Y, Li K. . Electrosynthesis of ammonia with high selectivity and high rates via engineering of the solid-electrolyte interphase. Joule, 2022, 6(9): 2083–2101

[82] Fu X, Pedersen J B, Zhou Y. . Continuous-flow electrosynthesis of ammonia by nitrogen reduction and hydrogen oxidation. Science, 2023, 379(6633): 707–712

[83] Suryanto B H, Matuszek K, Choi J. . Nitrogen reduction to ammonia at high efficiency and rates based on a phosphonium proton shuttle. Science, 2021, 372(6547): 1187–1191

[84] Cai X, Fu C, Iriawan H. . Lithium-mediated electrochemical nitrogen reduction: Mechanistic insights to enhance performance. iScience, 2021, 24(10): 103105

[85] Zheng Y, Wang J, Yu B. . A review of high temperature co-electrolysis of H₂O and CO₂ to produce sustainable fuels using solid oxide electrolysis cells (SOECs): Advanced materials and technology. Chemical Society Reviews, 2017, 46(5): 1427–1463

[86] Zheng Y, Chen Z, Zhang J. Solid oxide electrolysis of H₂O and CO₂ to produce hydrogen and low-carbon fuels. Electrochemical Energy Reviews, 2021, 4(3): 508–517

[87] Yoo C, Park J H, Kim K. . Role of protons in electrochemical ammonia synthesis using solid-state electrolytes. ACS Sustainable Chemistry & Engineering, 2017, 5(9): 7972–7978

[88] Zhang S, Duan G, Qiao L. . Electrochemical ammonia synthesis from N₂ and H₂O catalyzed by doped LaFeO₃ perovskite under mild conditions. Industrial & Engineering Chemistry Research, 2019, 58(20): 8935–8939

[89] Song Y, Chen J, Yang M. . Realizing simultaneous detrimental reactions suppression and multiple benefits generation from nickel doping toward improved protonic ceramic fuel cell performance. Small, 2022, 18(16): 2200450

[90] Amar I A, Lan R, Humphreys J. . Electrochemical synthesis of ammonia from wet nitrogen via a dual-chamber reactor using La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ-Ce_0.8Gd_0.18Ca_0.02O_2−δ composite cathode. Catalysis Today, 2017, 286: 51–56

[91] Klinsrisuk S, Irvine J T S. Electrocatalytic ammonia synthesis via a proton conducting oxide cell with BaCe_0.5Zr_0.3Y_0.16Zn_0.04O_3−δ electrolyte membrane. Catalysis Today, 2017, 286: 41–50

[92] Wang K, Chen H, Li S. . Sr_xTi_0.6Fe_0.4O_3−δ (x = 1.0, 0.9) catalysts for ammonia synthesis via proton-conducting solid oxide electrolysis cells (PCECs). Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2022, 10(46): 24813–24823

[93] Wang F, Wang Y, Li L. . Electrocatalytic ammonia synthesis on Fe@MXene catalyst as cathode of intermediate-temperature proton-conducting solid oxide cell. International Journal of Hydrogen Energy, 2023, 48(46): 17677–17688

[94] Ferree M, Gunduz S, Kim J. . Enhanced N₂ activation on a composite Co₃Mo₃N nitride and La_0.6Sr_0.4Co_0.2Fe_0.8O₃ perovskite cathode for high-temperature electrochemical ammonia synthesis. ACS Sustainable Chemistry & Engineering, 2023, 11(13): 5007–5013

[95] Ye L, Duan X, Xie K. Electrochemical oxidative dehydrogenation of ethane to ethylene in a solid oxide electrolyzer. Angewandte Chemie International Edition, 2021, 60(40): 21746–21750

[96] Song Y, Lin L, Feng W. . Interfacial enhancement by γ-Al₂O₃ of electrochemical oxidative dehydrogenation of ethane to ethylene in solid oxide electrolysis cells. Angewandte Chemie International Edition, 2019, 58(45): 16043–16046

[97] Chen W, Yang X, Chen Z. . Emerging applications, developments, prospects, and challenges of electrochemical nitrate-to-ammonia conversion. Advanced Functional Materials, 2023, 33(29): 2300512

[98] An L, Narouz M R, Smith P T. . Supramolecular enhancement of electrochemical nitrate reduction catalyzed by cobalt porphyrin organic cages for ammonia electrosynthesis in water. Angewandte Chemie International Edition, 2023, 135(35): e202305719

[99] Yin Q, Hu S, Liu J. . Electrochemical ammonia synthesis via nitrate reduction on perovskite La_xFeO_3−δ with enhanced efficiency by oxygen vacancy engineering. Sustainable Energy & Fuels, 2022, 6(20): 4716–4725

[100] Jia R, Wang Y, Wang C. . Boosting selective nitrate electroreduction to ammonium by constructing oxygen vacancies in TiO₂. ACS Catalysis, 2020, 10(6): 3533–3540

[101] Liu Q, Xie L, Liang J. . Ambient ammonia synthesis via electrochemical reduction of nitrate enabled by NiCo₂O₄ nanowire array. Small, 2022, 18(13): 2106961

[102] Fan X, Zhao D, Deng Z. . Constructing Co@TiO₂ nanoarray heterostructure with Schottky contact for selective electrocatalytic nitrate reduction to ammonia. Small, 2023, 19(17): 2208036

[103] Zhang S, Wu J, Zheng M. . Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia. Nature Communications, 2023, 14(1): 3634

[104] Blommaert M A, Aili D, Tufa R A. . Insights and challenges for applying bipolar membranes in advanced electrochemical energy systems. ACS Energy Letters, 2021, 6(7): 2539–2548

[105] Wan L, Xu Z, Xu Q. . Key components and design strategy of the membrane electrode assembly for alkaline water electrolysis. Energy & Environmental Science, 2023, 16(4): 1384–1430

[106] Xu Z, Liao Y, Pang M. . A chemically interlocked bipolar membrane achieving stable water dissociation for high output ammonia electrosynthesis. Energy & Environmental Science, 2023, 16(9): 3815–3824

[107] Giddey S, Badwal S P S, Kulkarni A. Review of electrochemical ammonia production technologies and materials. International Journal of Hydrogen Energy, 2013, 38(34): 14576–14594

RIGHTS & PERMISSIONS

Higher Education Press 2023