Ambient Electrochemical Ammonia Synthesis With High Selectivity On Fe/Fe Oxide Catalyst

Electrochemical reduction of N2 to NH3 under ambient conditions can provide an alternative to the Haber-Bosch process for distributed NH3 production that can be powered by renewable electricity. The major challenge for realizing such a process is to develop efficient electrocatalysts for the N2 reduction reaction (N2RR), as typical catalysts show a low activity and selectivity due to the barrier for N2 activation and the competing hydrogen evolution reaction (HER). Here we report an Fe/Fe3O4 catalyst for ambient electrochemical NH3 synthesis, which was prepared by oxidizing an Fe foil at 300 °C followed by in situ electrochemical reduction. The Fe/Fe3O4 catalyst exhibits a Faradaic efficiency of 8.29% for NH3 production at -0.3 V vs the reversible hydrogen electrode in phosphate buffer solution, which is around 120 times higher than that of the original Fe foil. The high selectivity is enabled by an enhancement of the intrinsic (surface-area-normalized) N2RR activity by up to 9-fold as well as an effective suppression of the HER activity. The N2RR selectivity of the Fe/Fe3O4 catalyst is also higher than that of Fe, Fe3O4, and Fe2O3 nanoparticles, suggesting Fe/Fe oxide composite to be an efficient catalyst for ambient electrochemical NH3 synthesis

Hydrogen Evolution from Metal–Surface Hydroxyl Interaction

The redox interaction between hydroxyl groups on oxide surfaces and metal atoms and clusters deposited thereon, according to which metals get oxidized and hydrogen released, is an effective route to tune both the morphological (particle size and shape) and electronic (oxidation state) properties of oxide-supported metals. While the oxidation state of the metals can straightforwardly be probed by X-ray based methods (e.g., XPS), hydrogen is much more difficult to capture, in particular in highly reactive systems where the redox interaction takes place directly during the nucleation of the metals at room temperature. In the present study, the interaction of Pd with a hydroxylated MgO(001) surface was studied using a combination of vibrational spectroscopy, electronic structure studies including Auger parameter analysis, and thermal desorption experiments. The results provide clear experimental evidence for the redox nature of the interaction by showing a direct correlation between metal oxidation and hydrogen evolution at slightly elevated temperature (390 K). Moreover, a second hydrogen evolution pathway opens up at 500 K, which involves hydroxyl groups on the MgO support and carbon monoxide adsorbed on the Pd particles (water–gas shift reaction)