Single Mo1(Cr1) Atom on Nitrogen-Doped Graphene Enables Highly Selective Electroreduction of Nitrogen into Ammonia

Wanghui Zhao; Lifu Zhang; Qiquan Luo; Zhenpeng Hu; Wenhua Zhang; Sean Smith; Jinlong Yang

doi:10.1021/acscatal.8b05061

Single Mo₁(Cr₁) Atom on Nitrogen-Doped Graphene Enables Highly Selective Electroreduction of Nitrogen into Ammonia

Wanghui Zhao, Lifu Zhang, Qiquan Luo, Zhenpeng Hu, Wenhua Zhang^*, Sean Smith, Jinlong Yang

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

285 Citations (Scopus)

Abstract

Searching for new types of electrocatalysts with high stability, activity, and selectivity is essential for the production of ammonia via electroreduction of nitrogen. Using density functional theory (DFT) calculations, we explore the stability of single metal atoms (M₁) supported on nitrogen-doped graphene (N₃-G); the competitive adsorption of dinitrogen and hydrogen; and the potential competition of first dinitrogen protonation and hydrogen adsorption on metal sites. Consequently, we identify Mo₁/N₃-G and Cr₁/N₃-G as candidate electrocatalysts for nitrogen reduction reaction (NRR). The theoretically predicted selectivities (overpotentials) are 40% (0.34 V) and 100% (0.59 V) on Mo₁/N₃-G and Cr₁/N₃-G, respectively. The electroreduction of nitrogen proceeds via distal-to-alternating hybrid mechanism with two spectator dinitrogen molecules. The high stability, high selectivity to ammonia, and relatively low overpotentials for NRR suggest Mo₁(Cr₁)/N₃-G as the most promising electrocatalyst among those studied for electroreduction of nitrogen.

Original language	English
Pages (from-to)	3419-3425
Number of pages	7
Journal	ACS Catalysis
Volume	9
Issue number	4
DOIs	https://doi.org/10.1021/acscatal.8b05061
Publication status	Published - 5 Apr 2019

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title = "Single Mo1(Cr1) Atom on Nitrogen-Doped Graphene Enables Highly Selective Electroreduction of Nitrogen into Ammonia",

abstract = "Searching for new types of electrocatalysts with high stability, activity, and selectivity is essential for the production of ammonia via electroreduction of nitrogen. Using density functional theory (DFT) calculations, we explore the stability of single metal atoms (M1) supported on nitrogen-doped graphene (N3-G); the competitive adsorption of dinitrogen and hydrogen; and the potential competition of first dinitrogen protonation and hydrogen adsorption on metal sites. Consequently, we identify Mo1/N3-G and Cr1/N3-G as candidate electrocatalysts for nitrogen reduction reaction (NRR). The theoretically predicted selectivities (overpotentials) are 40% (0.34 V) and 100% (0.59 V) on Mo1/N3-G and Cr1/N3-G, respectively. The electroreduction of nitrogen proceeds via distal-to-alternating hybrid mechanism with two spectator dinitrogen molecules. The high stability, high selectivity to ammonia, and relatively low overpotentials for NRR suggest Mo1(Cr1)/N3-G as the most promising electrocatalyst among those studied for electroreduction of nitrogen.",

keywords = "ammonia selectivity, density functional theory, electroreduction of nitrogen, graphene, single atom catalysts",

author = "Wanghui Zhao and Lifu Zhang and Qiquan Luo and Zhenpeng Hu and Wenhua Zhang and Sean Smith and Jinlong Yang",

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doi = "10.1021/acscatal.8b05061",

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AU - Zhao, Wanghui

AU - Zhang, Lifu

AU - Luo, Qiquan

AU - Hu, Zhenpeng

AU - Zhang, Wenhua

AU - Smith, Sean

AU - Yang, Jinlong

PY - 2019/4/5

Y1 - 2019/4/5

N2 - Searching for new types of electrocatalysts with high stability, activity, and selectivity is essential for the production of ammonia via electroreduction of nitrogen. Using density functional theory (DFT) calculations, we explore the stability of single metal atoms (M1) supported on nitrogen-doped graphene (N3-G); the competitive adsorption of dinitrogen and hydrogen; and the potential competition of first dinitrogen protonation and hydrogen adsorption on metal sites. Consequently, we identify Mo1/N3-G and Cr1/N3-G as candidate electrocatalysts for nitrogen reduction reaction (NRR). The theoretically predicted selectivities (overpotentials) are 40% (0.34 V) and 100% (0.59 V) on Mo1/N3-G and Cr1/N3-G, respectively. The electroreduction of nitrogen proceeds via distal-to-alternating hybrid mechanism with two spectator dinitrogen molecules. The high stability, high selectivity to ammonia, and relatively low overpotentials for NRR suggest Mo1(Cr1)/N3-G as the most promising electrocatalyst among those studied for electroreduction of nitrogen.

AB - Searching for new types of electrocatalysts with high stability, activity, and selectivity is essential for the production of ammonia via electroreduction of nitrogen. Using density functional theory (DFT) calculations, we explore the stability of single metal atoms (M1) supported on nitrogen-doped graphene (N3-G); the competitive adsorption of dinitrogen and hydrogen; and the potential competition of first dinitrogen protonation and hydrogen adsorption on metal sites. Consequently, we identify Mo1/N3-G and Cr1/N3-G as candidate electrocatalysts for nitrogen reduction reaction (NRR). The theoretically predicted selectivities (overpotentials) are 40% (0.34 V) and 100% (0.59 V) on Mo1/N3-G and Cr1/N3-G, respectively. The electroreduction of nitrogen proceeds via distal-to-alternating hybrid mechanism with two spectator dinitrogen molecules. The high stability, high selectivity to ammonia, and relatively low overpotentials for NRR suggest Mo1(Cr1)/N3-G as the most promising electrocatalyst among those studied for electroreduction of nitrogen.

KW - ammonia selectivity

KW - density functional theory

KW - electroreduction of nitrogen

KW - graphene

KW - single atom catalysts

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DO - 10.1021/acscatal.8b05061

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ER -

Single Mo₁(Cr₁) Atom on Nitrogen-Doped Graphene Enables Highly Selective Electroreduction of Nitrogen into Ammonia

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