Fabrication of an Au₂₅‐Cys‐Mo Electrocatalyst for Efficient Nitrogen Reduction to Ammonia under Ambient Conditions

Abstract

Ammonia (NH 3 ) is an essential nitrogen feedstock for fertilizer and efficient energy carrier. [1,2] The traditional process for synthesizing NH 3 is mostly produced via the Haber-Bosch process. [3] Up to now, the well-established Haber-Bosch process Electrocatalysts for efficient production of ammonia from nitrogen reduction reaction (NRR) under ambient conditions are attracted growing interest in recent years, which demonstrate a great potential to replace the Haber-Bosch method which suffers the problems of the huge energy consumption and massive CO 2 production. In this work, a novel electrocatalyst of Au 25 -Cys-M is fabricated for NRR under ambient conditions, with transition metal ions (e.g., Mo 6+ , Fe 3+ , Co 2+ , Ni 2+ ) atomically decorated on Au 25 nanoclusters via thiol bridging. The Au 25 -Cys-Mo catalyst exhibits the highest Faradaic efficiency (26.5%) and NH 3 yield (34.5 µg h −1 mg cat −1 ) in 0.1 m HCl solution. X-ray photoelectron spectroscopy analysis and high angle annular dark field imagescanning transmission electron microscopy characterization reveal that the electronic structure of Mo is optimized by forming the structure of Au-S-Mo and Mo acts as active sites for activating the nitrogen to promote the electrochemical production of ammonia. This work provides a new insight into the precise fabrication of efficient NRR electrocatalysts.

Interface coupling induced built-in electric fields boost electrochemical nitrate reduction to ammonia over CuO@MnO2 core–shell hierarchical nanoarrays

“…[10][11][12][13][14][15][16] Nowadays, ammonia is mainly produced by the energy-intensive and highly polluting Haber-Bosch process. [17][18][19][20] Alternatively, electrocatalytic nitrate reduction to ammonia, due to its high efficiency and environmental characteristics, raises a storm of discussions and has a great impact on media and public imaginations. [21][22][23][24] The past decade has witnessed signicant progress in the study of electrocatalytic nitrate reduction to ammonia.…”

Delicate Tuning of the Ni/Co Ratio in Bimetal Layered Double Hydroxides for Efficient N2 Electroreduction

“…+ in the acidic solution, contrasting to the triplet pattern with a coupling constant of 52 Hz for 14 NH 4 + . [66,67] This result unambiguously revealed that the NH 3 indeed originates from N 2 fixation. To further confirm the reliability, the quantitative analysis of isotope 1 H NMR spectra were carried out.…”

Gold Nanoclusters as Electrocatalysts: Atomic Level Understanding from Fundamentals to Applications

“…The application of Au NCs as electrocatalysts to explore the transformation of dinitrogen (N 2 ) to ammonia (NH 3 ) through the electrocatalytic process is another interesting research topic. However, so far very few reports have demonstrated the NRR using mono- or bimetallic Au NCs. − Nevertheless, in most cases, the yields of NH 3 and FEs were much less due to the competing HER. Therefore, the key strategies to improve the yield of NH 3 would be constraining the competing HER and introducing more active sites by modulating the electronic structure of active sites.…”