Oxygen vacancy modulation in interfacial engineering Fe3O4 over carbon nanofiber boosting ambient electrocatalytic N2 reduction

Abstract

The oxygen vacancy modulation of interface-engineered Fe3O4 nanograins over carbon nanofiber (Fe@CNF) was achieved to improve electrocatalytic nitrogen reduction reaction (NRR) activity and stability via facile electrospinning and tuning thermal procedure. The optimal catalyst calcined at 800 ℃ (Fe@CNF-800) was endowed with abundant nanograin boundaries and optimized oxygen vacancy (Vo) concentration of iron oxides, thereby affording 37.1 μg h−1 mgcat.-1 (−0.2 V vs. reversible hydrogen electrode (RHE)) NH3 yield and rational Faraday efficiency (10.2%), with 13.6 times atomic activity enhancement compared to of that commercial Fe3O4. The interfacial effect of assembled nanograins in particles correlated with the formation of Vo and more intrinsic active sites, which is conducive to the trapping and activation of nitrogen (N2). The in-situ X-ray photoelectron spectroscopy (XPS) measurement revealed the real consumption of adsorbed oxygen when introducing N2 by the trapping effect of Vo. Density-Functional-Theory (DFT) calculation validates the promotive hydrogenation effect and elimination of hydrogen intermediate (H*) interacted with N2 transferring toward oxygen of the support. The optimal catalyst shows a lasting NRR activity at least 90 h, outperforming most reported Fe-based NRR catalysts.