Electrochemical dinitrogen to ammonia reduction at a nickel(ii) site: an easy access to an air-stable catalyst†
Abstract
The electrochemical nitrogen reduction reaction (NRR) for producing NH3 (ammonia) is a suitable alternative to the Haber–Bosch process due to its eco-friendly and non-polluting nature. Herein, we report a homogeneous Ni-based tetranuclear solvated oligomer [(L-Me)4Ni4(EtOH)4] as a precatalyst for the NRR to NH3 in THF (tetrahydrofuran) medium. The monomeric tri-coordinated Ni(II) ion chelated by a spencer type O2N hard-donor dianionic ligand (Me-L2−) is the first of its type for electrochemical N2 (dinitrogen) fixation. The factors that control the facile N2 binding at the Ni atom of the catalyst have not been much studied before by energy decomposition analysis-natural orbital for chemical valence (EDA-NOCV) analysis. Coordinating solvents energetically prefer to bind at the single Ni(II) site of the monomeric active catalyst (L-Me)Ni(II), and due to the σ-donation (Ni(II) ← N2) ability of N2, while under electrochemical conditions, the Ni(II) centre of (L-Me)Ni(II) prefers to strongly bind N2via desired π-backdonation (Ni(II) → N2). The Ni(II) state of this molecule was studied by EPR (electron paramagnetic resonance). The proposed solution dynamics involving oligomers binding with the N2 molecule and electrochemical N2-bonded intermediates have been characterised by electrospray ionisation mass spectrometry (ESI-MS). Due to the favourable electron affinity of (L-Me)Ni(II)(N2), it is suitable to undergo protonation at the terminal N atom of the bonded N2. The lone pair of electrons of O atoms of the L-Me ligand stabilises the N–H unit via intramolecular H-bond formation. Our detailed density functional theory (DFT) calculations showed that all the steps leading to the reduction of N2 to NH3via the addition of electrons and protons are favourable.
- This article is part of the themed collection: Journal of Materials Chemistry A HOT Papers