Electrochemical nitrogen reduction reaction over gallium - a computational and experimental study

Vivek Sinha*, Fateme Rezai, Nihat Ege Sahin, Jacopo Catalano, Espen Drath Bøjesen, Farnaz Sotoodeh*, Emil Dražević*

*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review


Ga was identified earlier as one of the “overlooked” metals for catalyzing the electrochemical nitrogen reduction reaction (ENRR). We investigate here the electrocatalytic activity of Ga towards the nitrogen reduction reaction. We used a combination of molecular modelling and simulations using periodic density functional theory calculations (DFT), and experimental ENRR measurements. The ENRR was found to proceed via an associative mechanism where the first PCET to dinitrogen forming the surface adsorbed N2H* species is the overpotential limiting step. The bare Ga cathode has a high overpotential (>2 V (SHE)) for the ENRR. We also investigated the effect of a water-in-salt electrolyte (WISE) on the rate of ammonia formation. The addition of an Li salt lowers the overpotential to 1.88 V (SHE). DFT calculations revealed that the H-adatom was more favorably bound than the N-adatom, and the hydrogen evolution reaction (HER) is expected to dominate at high cathodic potentials. Experimental ENRR tests corroborate our results wherein no significant NH3 formation was detected. The low electrochemical activity of Ga is attributed to poor binding and activation of N2 which originates from an electropositive surface charge distribution.

Original languageEnglish
JournalFaraday Discussions
Pages (from-to)307-320
Number of pages14
Publication statusPublished - Jul 2023


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