Strategic design of VO2 encased in N-doped carbon as an efficient electrocatalyst for the nitrogen reduction reaction in neutral and acidic media.

Abstract

Electrocatalytic nitrogen fixation to ammonia (NH3), a precursor for fertilizer production and a promising energy carrier, has garnered widespread interest as an environment-friendly and sustainable alternative to the energy-intensive fossil-feedstock-dependent Haber-Bosch process. The large-scale deployment of this process is contingent on the identification of inexpensive, Earth-abundant systems that can operate efficiently, irrespective of the electrolyte pH for the selective production of NH3. In this regard, we discuss the scalable synthesis of VO2 anchored on N-doped carbon (VO2@CN), and its applicability as a robust electrocatalyst for the nitrogen reduction reaction (NRR). Benefitting from the presence of exposed VO2, which presumably acts as the active site for nitrogen reduction, and its activity over a broad pH range (from acidic to neutral), VO2@CN exhibits a high NH3 yield of 0.31 and 0.52 μmol h-1 mgcat-1 and a maximum Faradaic efficiency (FE) of 67.9% and 61.9% at -0.1 V vs. RHE, under neutral and acidic conditions, respectively. The obscured reaction intermediates of the NRR were identified from in situ ATR-IR studies under both electrolyte conditions. Additionally, the high selectivity of the catalyst was ascertained from the absence of hydrazine production and the competing hydrogen evolution reaction (HER). However, ammonia production underwent a reduction over 12 h of continuous operation presumably owing to the leaching of catalyst under these electrolysis conditions, which was more pronounced in electrolytes with acidic pH. Overall, the present report unveils the performance of an earth-abundant vanadium oxide-based system as an efficient electrocatalyst for the NRR under acidic and neutral pH conditions.