Low-Coordinate Step Atoms via Plasma-Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Xiaohui Yang; Faling Ling; Xiangrong Zi; Yanwei Wang; Han Zhang; Huijuan Zhang; Miao Zhou; Zaiping Guo; Yu Wang

doi:10.1002/smll.202000421

Low-Coordinate Step Atoms via Plasma-Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Xiaohui Yang
, Faling Ling
, Xiangrong Zi
, Yanwei Wang
, Han Zhang
, Huijuan Zhang
, Miao Zhou^*
, Zaiping Guo^*
, Yu Wang^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

47 Citations (Scopus)

Abstract

The electrochemical N₂ reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber–Bosch process for distributed and modular production of NH₃. 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 (IrP₂@PNPC-NF), where the edges of the IrP₂ nanocrystals are extremely irregular, and the ultrathin PNPC-NF possesses a honeycomb-like macroporous structure. These characteristics ensure that IrP₂@PNPC-NF delivers superior NRR performance with an NH3 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 IrP₂ nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH₃ 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 (OsP₂@PNPC-NF, Re₃P₄@PNPC-NF, etc.) with abundant step atoms at lower temperatures.

© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Original language	English
Article number	2000421
Journal	Small
Volume	16
Issue number	17
Online published	29 Mar 2020
DOIs	https://doi.org/10.1002/smll.202000421
Publication status	Published - 28 Apr 2020
Externally published	Yes

Funding

This work was financially supported by the Fundamental Research Funds for the Central Universities (0301005202017, 2018CDQYFXCS0017, and 106112017CDJXSYY0001), the Thousand Young Talents Program of the Chinese Central Government (Grant No. 0220002102003), the National Natural Science Foundation of China (NSFC, Grant Nos. U19A20100, 21971027, 21373280, and 21403019), Beijing National Laboratory for Molecular Sciences (BNLMS) and Hundred Talents Program at Chongqing University (Grant No. 0903005203205), and the State Key Laboratory of Mechanical Transmissions Project (SKLMT-ZZKT-2017M11).

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy
SDG 9 Industry, Innovation, and Infrastructure

Research Keywords

iridium diphosphide
nanocrystals
nitrogen reduction
plasma-assisted calcinations
step atoms

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title = "Low-Coordinate Step Atoms via Plasma-Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia",

abstract = "The electrochemical N2 reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber–Bosch process for distributed and modular production of NH3. 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 (IrP2@PNPC-NF), where the edges of the IrP2 nanocrystals are extremely irregular, and the ultrathin PNPC-NF possesses a honeycomb-like macroporous structure. These characteristics ensure that IrP2@PNPC-NF delivers superior NRR performance with an NH3 yield rate of 94.0 µg h−1 mg−1cat. 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 IrP2 nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH3 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 (OsP2@PNPC-NF, Re3P4@PNPC-NF, etc.) with abundant step atoms at lower temperatures. {\textcopyright} 2020 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim",

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author = "Xiaohui Yang and Faling Ling and Xiangrong Zi and Yanwei Wang and Han Zhang and Huijuan Zhang and Miao Zhou and Zaiping Guo and Yu Wang",

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AU - Yang, Xiaohui

AU - Ling, Faling

AU - Zi, Xiangrong

AU - Wang, Yanwei

AU - Zhang, Han

AU - Zhang, Huijuan

AU - Zhou, Miao

AU - Guo, Zaiping

AU - Wang, Yu

PY - 2020/4/28

Y1 - 2020/4/28

N2 - The electrochemical N2 reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber–Bosch process for distributed and modular production of NH3. 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 (IrP2@PNPC-NF), where the edges of the IrP2 nanocrystals are extremely irregular, and the ultrathin PNPC-NF possesses a honeycomb-like macroporous structure. These characteristics ensure that IrP2@PNPC-NF delivers superior NRR performance with an NH3 yield rate of 94.0 µg h−1 mg−1cat. 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 IrP2 nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH3 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 (OsP2@PNPC-NF, Re3P4@PNPC-NF, etc.) with abundant step atoms at lower temperatures. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

AB - The electrochemical N2 reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber–Bosch process for distributed and modular production of NH3. 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 (IrP2@PNPC-NF), where the edges of the IrP2 nanocrystals are extremely irregular, and the ultrathin PNPC-NF possesses a honeycomb-like macroporous structure. These characteristics ensure that IrP2@PNPC-NF delivers superior NRR performance with an NH3 yield rate of 94.0 µg h−1 mg−1cat. 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 IrP2 nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH3 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 (OsP2@PNPC-NF, Re3P4@PNPC-NF, etc.) with abundant step atoms at lower temperatures. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

KW - iridium diphosphide

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VL - 16

JO - Small

JF - Small

IS - 17

M1 - 2000421

ER -

Low-Coordinate Step Atoms via Plasma-Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Abstract

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UN SDGs

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