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Low‐Coordinate Step Atoms via Plasma‐Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia
Author(s) -
Yang Xiaohui,
Ling Faling,
Zi Xiangrong,
Wang Yanwei,
Zhang Han,
Zhang Huijuan,
Zhou Miao,
Guo Zaiping,
Wang Yu
Publication year - 2020
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202000421
Subject(s) - faraday efficiency , electrochemistry , nanocrystal , ammonia production , materials science , nanotechnology , ammonia , catalysis , chemical engineering , chemistry , electrode , organic chemistry , engineering
Abstract The electrochemical N 2 reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber–Bosch process for distributed and modular production of NH 3 . Nevertheless, developing high‐efficiency catalysts to simultaneously realize both high activity and selectivity for the development of a sustainable NRR is very critical but extremely challenging. Here, a unique plasma‐assisted strategy is developed to synthesize iridium diphosphide nanocrystals with abundant surface step atoms anchored in P,N‐codoped porous carbon nanofilms (IrP 2 @PNPC‐NF), where the edges of the IrP 2 nanocrystals are extremely irregular, and the ultrathin PNPC‐NF possesses a honeycomb‐like macroporous structure. These characteristics ensure that IrP 2 @PNPC‐NF delivers superior NRR performance with an NH 3 yield rate of 94.0 µg h −1 mg −1 cat. and a faradaic efficiency (FE) of 17.8%. Density functional theory calculations reveal that the unique NRR performance originates from the low‐coordinate step atoms on the edges of IrP 2 nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH 3 formation. More importantly, such a plasma‐assisted strategy is general and can be extended to the synthesis of other high‐melting‐point noble‐metal phosphides (OsP 2 @PNPC‐NF, Re 3 P 4 @PNPC‐NF, etc.) with abundant step atoms at lower temperatures.