PdFe Single‐Atom Alloy Metallene for N2 Electroreduction

• Published in: Angewandte Chemie International Edition 2022-07, Vol.61 (28), p.e202205923-n/a
• Main Authors: Li, Xingchuan, Shen, Peng, Luo, Yaojing, Li, Yunhe, Guo, Yali, Zhang, Hu, Chu, Ke
• Format: Article
• Language: English
• Subjects: Ammonia; Chemical reduction; Density Functional Calculations; Electrocatalysts; Electrocatalytic Nitrogen Reduction; Electrolysis; Hydrogen evolution; Molecular Dynamics Simulations; Operando Spectroscopy; Protonation; Raman spectroscopy; Selectivity; Single-Atom Alloys; Stability
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202205923

Single‐atom alloys hold great promise for electrocatalytic nitrogen reduction reaction (NRR), while the comprehensive experimental/theoretical investigations of SAAs for the NRR are still missing. Herein, PdFe1 single‐atom alloy metallene, in which the Fe single atoms are confined on a Pd metallene support, is first developed as an effective and robust NRR electrocatalyst, delivering exceptional NRR performance with an NH3 yield of 111.9 μg h−1 mg−1, a Faradaic efficiency of 37.8 % at −0.2 V (RHE), as well as a long‐term stability for 100 h electrolysis. In‐depth mechanistic investigations by theoretical computations and operando X‐ray absorption/Raman spectroscopy indentify Pd‐coordinated Fe single atoms as active centers to enable efficient N2 activation via N2‐to‐Fe σ‐donation, reduced protonation energy barriers, suppressed hydrogen evolution and excellent thermodynamic stability, thus accounting for the high activity, selectivity and stability of PdFe1 for the NRR. PdFe1 single‐atom alloy metallene is demonstrated as an effective and robust catalyst for the nitrogen reduction reaction (NRR), delivering an NH3 yield of 111.9 μg h−1 mg−1 and a Faradaic efficiency of 37.8 % at −0.2 V (RHE). Combined theoretical computations and operando XAS/Raman spectroscopy identify Pd‐coordinated Fe single atoms as active centers to enable efficient N2 activation, reduced protonation energy barriers, suppressed hydrogen evolution and high electrocatalytic stability.