A General Strategy to Glassy M-Te (M = Ru, Rh, Ir) Porous Nanorods for Efficient Electrochemical N₂ Fixation

Electrochemical conversion of nitrogen (N₂) into value-added ammonia (NH₃) is highly desirable yet formidably challenging due to the extreme inertness of the N₂ molecule, which makes the development of a robust electrocatalyst prerequisite. Herein, a new class of bullet-like M-Te (M = Ru, Rh, Ir) glassy porous nanorods (PNRs) is reported as excellent electrocatalysts for N₂ reduction reaction (NRR). The optimized IrTe₄ PNRs present superior activity with the highest NH₃ yield rate (51.1 µg h⁻¹ mg⁻¹_cat.) and Faraday efficiency (15.3%), as well as long-term stability of up to 20 consecutive cycles, making them among the most active NRR electrocatalysts reported to date. Both the N₂ temperature-programmed desorption and valence band X-ray photoelectron spectroscopy data show that the strong chemical adsorption of N₂ is the key for enhancing the NRR and suppressing the hydrogen evolution reaction of IrTe₄ PNRs. Density functional theory calculations comprehensively identify that the superior adsorption strength of IrTe₄ adsorptions originates from the synergistic collaboration between electron-rich Ir and the highly electroactive surrounding Te atoms. The optimal adsorption of both N₂ and H₂O in alkaline media guarantees the superior consecutive NRR process. This work opens a new avenue for designing high-performance NRR electrocatalysts based on glassy materials. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim