
Ammonia (NH₃) is a crucial raw material for fertilizer production and a potential renewable, carbon-free energy storage solution. It is produced in the Haber-Bosch process using natural gas (CH4). During this process, natural gas is converted into hydrogen (H₂) and CO₂ by steam reforming. The Haber-Bosch process accounts for approximately 1-3% of global CO₂ emissions. This method requires stable energy supply and CAPEX intensive facilities, leading to highly centralized ammonia production. In contrast, alternative electrochemical pathways for ammonia production represent sustainable and decentralized solutions.
Electrochemical ammonia production is not a new process and is based on hydrogen electrolysis. In a subsequent step, hydrogen is used for catalytic nitrogen reduction. Experimentally, lithium and calcium have been used as electrocatalysts. Ammonia has been produced in continuous flow cells with efficiencies of up to 76%, as well as in other electrochemical cells. However, stable ammonia production in flow cells requires dry and purified hydrogen.
The primary issue with moist hydrogen is the excessive formation of lithium hydroxide (LiOH):
2 Li + 2 H₂O → 2 LiOH + H₂
However, water electrolysis could be completely eliminated if the protons (H+) generated from water oxidation were directly supplied to the lithium-coated cathode. This would further simplify systems and lower investment costs.
Researchers at Imperial College London followed exactly that approach. They coupled continuous water oxidation directly to lithium-mediated nitrogen reduction under non-aqueous conditions in a two-chamber flow cell. They recently published their results in the journal ACS Energy Letters.
The coupling was achieved through an electrically isolated, hydrogen-permeable palladium membrane between the chambers. On the anodic side (aqueous), water was oxidized at an iridium oxide-coated titanium anode to produce protons, meaning adsorbed H. This form of hydrogen permeated the palladium membrane. It then entered the dry, non-aqueous cathodic chamber, where N₂ was reduced on lithium.

The palladium membrane was not integrated into the external circuit during nitrogen reduction. It simultaneously served as both a proton source and sink, made possible by its electrical conductivity and hydrogen permeability.
The scientists first validated proton transport through the palladium membrane while preventing water crossover through symmetric cell tests and ¹H-NMR isotopic exchange using water (H₂O) and deuterium oxide (D₂O, heavy water).
Real-time mass spectrometry of D₂O at the anode confirmed that deuterons supplied through the palladium membrane were incorporated into ammonia (ND₂H). This demonstrates that the protons in NH₃ originated from water oxidation and not solely from the ethanol used as well. It was evidence for linear charge transfer while maintaining negligible water transport.
As a control, an experiment was conducted using a Nafion™ membrane to demonstrate that membranes allowing water crossover prevented lithium-mediated ammonia synthesis. Nafion™ permits proton transfer while being permeable to water.
The researchers showed that the electrical conductivity of the palladium membrane enabled it to operate simultaneously as both an anode and a cathode. This allowed for continuous conversion of nitrogen and water into ammonia without producing molecular hydrogen as an intermediate. The Nafion™ control proved that the transport of protons while preventing water crossover allowed for lithium-mediated ammonia synthesis.
The necessity for pre-hydration of the membrane and the gradual increase in membrane potential during pulsed operation indicated that the kinetics of hydrogen transfer and membrane stability were key factors for performance. This was because the system was optimized for the neutral aqueous electrolyte with isotopic labeling. The researchers proposed ways to improve efficiency in their article, including the exploration of alternative hydrogen-permeable metals and alloys.
The presented membrane could find applications beyond ammonia synthesis, in other electrochemical transformations where anhydrous conditions and controlled proton release are required. These include CO₂ reduction and non-aqueous redox flow batteries.
For further research, the authors suggested:
- Increase proton flow and reduce membrane transition resistance,
- Test alternative hydrogen-permeable metals or alloys to reduce costs, and
- Conduct pulse and idle protocols to monitor lithium loss.
At Frontis Energy, we are eager to see how individual monolithic palladium membranes will enter in the market. Continuous ammonia electrosynthesis represents a conceptual advancement towards simpler, more robust green fertilizer production and energy storage.
Ye et al. 2026, Continuous ammonia electrosynthesis from nitrogen and water in a monolithic Pd membrane-based flow cell, ACS Energy Letters, DOI: 10.1021/acsenergylett.5c03617
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