The feasibility of electrochemical ammonia synthesis in molten LiCl-KCl eutectics

Journal article

Molten LiCl and related eutectic electrolytes are known to permit direct electrochemical reduction of N2 to N3- with high efficiency. It had been proposed that this could be coupled with H2 oxidation in an electrolytic cell to produce NH3 at ambient pressure. Here, this proposal is tested in a LiCl-KCl-Li3 N cell and is found not to be the case, as the previous assumption of the direct electrochemical oxidation of N3- to NH3 is grossly over-simplified. We find that Li3 N added to the molten electrolyte promotes the spontaneous and simultaneous chemical disproportionation of H2 (H oxidation state 0) into H- (H oxidation state -1) and H+ in the form of NH2- /NH2 - /NH3 (H oxidation state +1) in the absence of applied current, resulting in non-Faradaic release of NH3 . It is further observed that NH2- and NH2 - possess their own redox chemistry. However, these spontaneous reactions allow us to propose an alternative, truly catalytic cycle. By adding LiH, rather than Li3 N, N2 can be reduced to N3- while stoichiometric amounts of H- are oxidised to H2 . The H2 can then react spontaneously with N3- to form NH3 , regenerating H- and closing the catalytic cycle. Initial tests show a peak NH3 synthesis rate of 2.4×10-8  mol cm-2  s-1 at a maximum current efficiency of 4.2 %. Isotopic labelling with 15 N2 confirms the resulting NH3 is from catalytic N2 reduction.

Authors: McPherson, I; Sudmeier, T; Fellowes, J; Wilkinson, I; Hughes, T

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Wiley
• Journal: Angewandte Chemie
• Volume: 58
• Issue: 48
• Pages: 17433-17441
• Publication date: 2019-10-15
• Acceptance date: 2019-09-16
• DOI: 10.1002/anie.201909831
• EISSN: 1521-3773
• ISSN: 1433-7851
• Pmid: 31535776
• Language: English
• Keywords: renewable resources; electrochemistry; ammonia; nitrogen; heterogeneous catalysis