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Fig. 17. (a) Schematic of a tandem electrocatalytic strategy enabled by coupling the PCET mediator Co(II,NH)⁺ with molecular NRR catalysts, allowing well-defined N₂ reduction at relatively mild applied potentials. (b) A series of molecular NRR catalysts was tested under electrocatalytic conditions in the presence of the Co(II,NH)⁺ PCET mediator. Reproduced with permission of Ref. [90]. Copyright 2022, Springer Nature.
Fig. 16. In the P₃^BFe⁺/Cp^*₂Co NRR system, anilinium acids tune the balance between NRR and HER by protonating Cp^*₂Co to form a PCET donor, which then drives N−H bond formation. Reproduced with permission of Ref. [89]. Copyright 2018, American Chemical Society.
Fig. 15. (a) Schematic of thermochemical Ti-mediated NRR. (b) Schematic of the sodium-mediated electrochemical cascade for NRR. Reproduced with permission of Ref. [85]. Copyright 2025, Elsevier.
Fig. 14. (a) CVs of the catholyte under standard PNPMoBr₃ electrocatalytic conditions after 0.1-1.3 C of charge has passed; inset: NH₃ production plotted as a function of charge. (b) CVs of SmI₃ (2 mmol·L^-1, blue), PNPMoBr₃ (0.5 mmol·L^-1, pink), and PNPMo(N)I (0.5 mmol·L^-1, red). (c) CVs of PNPMo(N)I (0.46 mmol·L^-1) with LutHNTf₂ (80 equiv., blue) under N₂, overlaid with the LutHNTf₂ background; inset: evolution of the Mo^V/IV couple upon sequential addition of LutHNTf₂ (blue) and Lut (4-160 equiv; light blue to red). (d) Proposed electron-delivery pathways for the 1 H⁺/1 e⁻ step converting PNPMo(N)I toward NH₃. Direct reduction of the Mo^V/IV couple requires E_app < −1.6 V vs. Fc^+/0, where competing LutH⁺ reduction lowers FE. With Sm, the Sm^III/II mediator delivers electrons to the Mo^V/IV couple around −1.45 V vs. Fc^+/0, accelerating a limiting ET step while suppressing background acid reduction. Reproduced with permission of Ref. [84]. Copyright 2025, American Chemical Society.
Fig. 13. (a) Mo-catalyzed NRR employing stoichiometric SmI₂ as the reductant. (b) Tandem Sm/ Mo-catalyzed electrochemical NRR. Reproduced with permission of Ref. [84]. Copyright 2025, American Chemical Society.
Fig. 12. (a) Schematic of NH₃ electrosynthesis from H₂O and N₂ using {SiFe^III₃W₉} with an alkali-metal cation. (b) Cyclic voltammograms of TBA{SiFe₃W₉} in the presence of ethanol under He and N₂. (c) In situ UV-vis spectra of {SiFe₃W₉} under N₂ with Li⁺ during electrolysis. Black: before electrolysis; red/blue/green/magenta: after 1/2/3/4 e⁻ per TBA{SiFe₃W₉}. Reproduced with permission of Ref. [73]. Copyright 2023, American Chemical Society.
Fig. 11. (a) Molecular structure of complex 10a, 10b. (b) Cyclic voltammograms of 10a in the presence of 0 (blue) and 5 (red) equiv. of HBArF₄ under 1 atm N₂. (c) Possible catalytic pathways for N₂-to-NH₃ conversion by 10a. Reproduced with permission of Ref. [70]. Copyright 2016, American Chemical Society.
Fig. 10. (a-c) Molecular structures of complex 8a, the nitride complex 8b, and [HIPTN₃N]Mo(N₂) (9a). (d) Cyclic voltammograms of 0.5 mmol·L^-1 8a (red trace), 50 mmol·L^-1 [ColH][OTf] (blue trace), and 0.5 mmol·L^-1 8a with 50 mmol·L^-1 [ColH][OTf] (purple trace) were recorded in THF containing 100 mmol·L^-1 [Li][NTf₂]. The Mo^III/II couple around −1.80 V (red) is enhanced upon adding [ColH][OTf], giving a catalytic current consistent with N₂R at potentials anodic to the background HER (blue). (e) Cyclic voltammograms of 8b recorded with and without [ColH][OTf] show a Mo^V/IV couple (−1.2 V vs. Fc^+/0) and a cathodic Mo^IV/III reduction (−2.5 V vs. Fc^+/0); addition of [ColH][OTf] generates an enhanced wave near −1.8 V vs. Fc^+/0. Reproduced with permission of Ref. [69] and [48]. Copyright 2023, American Chemical Society; Copyright 2003, The American Association for the Advancement of Science.
Fig. 9. A proposed pathway for N₂-to-NH₃ conversion by complex 7a. Reproduced with permission of Ref. [68]. Copyright 2017, The Chemical Society of Japan.
Fig. 8. Dinitrogen cleavage promoted by the Mo pincer complex 6a. Reproduced with permission of Ref. [67]. Copyright 2017, Wiley.
Fig. 7. (a) Electrochemical conversion of complex 5a to the Re(V) nitride. (b) Proposed “ECCEC” pathway for complex 5a under N₂atmosphere. Reproduced with permission of Ref. [66]. Copyright 2018, American Chemical Society.
Fig. 6. Two-pathway N₂-splitting mechanism for a complex 4a operating in the reaction-diffusion layer and in the bulk solution. Reproduced with permission of Ref. [65]. Copyright 2022, American Chemical Society.
Fig. 5. Proposed mechanism for the electrochemical reduction of N₂ by the complex 3a. Reproduced with permission of Ref. [64]. Copyright 2022, Wiley.
Fig. 4. Generation of a Mo^IV≡N via dinitrogen cleavage from one-electron oxidation of complex 2a. Reproduced with permission of Ref. [63]. Copyright 2019, Wiley.
Fig. 3. Molecular structure of complex 1a showing chemical protonation to give [W(NNH₂)]⁺ and subsequent controlled-potential electrolysis to release NH₃.
Fig. 2. Conceptual electron/proton delivery pathways for homogeneous N₂ reduction to NH₃. (a) Thermal N₂ reduction: a chemical reductant provides reducing equivalents (e⁻), while an external proton source supplies H⁺; both are coupled to the molecular catalyst cycle that converts N₂ to NH₃. (b) DET: the electrode directly transfers electrons to the molecular catalyst in solution, with H⁺ provided by the proton donor. (c) Mediated electron transfer with an ET mediator: the mediator cycles between reduced and oxidized forms (Red./Ox.). The electrode regenerates Red., which then shuttles electrons to the catalyst for N₂-to-NH₃ conversion without direct proton transfer by the mediator. (d) Mediated electron transfer with a PCET mediator: the mediator cycles between Med−H/Med, where Med−H delivers an H-atom (coupled e⁻/H⁺ transfer) to the catalytic cycle to facilitate N−H bond formation, and is regenerated electrochemically at the electrode”.
Scheme 1. Proposed pathways for the reduction of N₂ to NH₃ through metal complexes.
Fig. 1. Physicochemical origins of N₂ inertness and the orbital basis of transition-metal activation. (a) Representative molecular properties of N₂, which highlight its strong N≡N bond, stable electronic structure, and high molecular symmetry. (b) Simplified molecular orbital diagram of N₂. (c) Synergic σ-donation/π-back-donation for end-on M−N≡N binding.
Fig. 5. Electrochemical testing of Li-NRR under varied water content in flow cells. (a, b) Chronopotentiometry curves at the water content of 5-7 mmol·L^-1 (a) and 55-57 mmol·L^-1 (b) respectively, recorded at a current density of -6 mA·cm^-2 with an ethanol concentration of 43.0 mmol·L^-1. (c) Chronopotentiometry curves of the first two cycles at varying water content in a flow cell. All reported potentials are presented without ohmic drop correction. (d) Nyquist plots of SEIs formed under varied water content, measured at room temperature. (e, f) First-cycle (e) and second-cycle (f) CV curves under different water content. (g) Long-term ammonia synthesis performed at an initial water content of 5-7 mmol·L^-1. Insets show the Nyquist plot (left) and SEM image of the electrode after long-term operation (right). (h) Ammonia FE and electrolyte water content at cumulative charge passage during long-term experiments.
Fig. 4. Depth-profile XPS spectra of O 1s (a), Li 1s (b) and F 1s (c) for the SEIs formed under 5-7 mmol·L^-1 initial water content and 55-57 mmol·L^-1 initial water content. A consistent intensity scale on the y-axis is maintained across all spectra for each sputtering time. XPS analyses were conducted without air exposure. Binding energy scales are adjusted per element to highlight chemical shifts; absolute values are calibrated to adventitious carbon (C 1s at 284.8 eV).

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