Activation of N≡N bonds by CN<sub>4</sub> tetrahedron leading to energetic carbon polynitrides under high pressure

Zhang Guanghui; Yi Wencai; Cao Yiqing; Zhang Shengli; Liu Xiaobing

doi:10.1063/5.0282879

Volume 10 Issue 5

Sep. 2025

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Zhang Guanghui, Yi Wencai, Cao Yiqing, Zhang Shengli, Liu Xiaobing. Activation of N≡N bonds by CN4 tetrahedron leading to energetic carbon polynitrides under high pressure[J]. Matter and Radiation at Extremes, 2025, 10(5): 057801. doi: 10.1063/5.0282879

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Zhang Guanghui, Yi Wencai, Cao Yiqing, Zhang Shengli, Liu Xiaobing. Activation of N≡N bonds by CN₄ tetrahedron leading to energetic carbon polynitrides under high pressure[J]. Matter and Radiation at Extremes, 2025, 10(5): 057801. doi: 10.1063/5.0282879

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Activation of N≡N bonds by CN₄ tetrahedron leading to energetic carbon polynitrides under high pressure

doi: 10.1063/5.0282879

Zhang Guanghui^1
,,
Yi Wencai^{1, 2
,
,
,},
Cao Yiqing^1
,,
Zhang Shengli^{3
,
,
,},
Liu Xiaobing^{1, 2
,
,
,}

1.
Key Laboratory of Quantum Materials under Extreme Conditions in Shandong Province, School of Physics and Physical Engineering, Qufu Normal University, Qufu 273165, China
2.
Laboratory of High Pressure Physics and Material Science (HPPMS), Advanced Research Institute of Multidisciplinary Sciences, Qufu Normal University, Qufu 273165, China
3.
Department of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, China

More Information

Corresponding author: a)Authors to whom correspondence should be addressed: yiwc@qfnu.edu.cn; zhangslvip@njust.edu.cn; and xiaobing.phy@qfnu.edu.cn
Received Date: 2025-05-28
Accepted Date: 2025-08-03

Available Online: 2025-11-28

Publish Date: 2025-09-01

Abstract

Abstract

The activation of the N≡N triple bond in N₂ is a fascinating topic in nitrogen chemistry. The transition metals have been demonstrated to effectively modulate the reactivity of N₂ molecules under high pressure, leading to nitrogen-rich compounds. However, their use often results in a significant reduction in energy density. In this work, we propose a series of low-enthalpy nitrogen-rich phases in CN_x (x = 3, …, 7) compounds using a first-principles crystal structure search method. The results of calculations reveal that all these CN compounds are assembled from both CN₄ tetrahedra and N_x (x = 1, 2, or 5) species. Strikingly, we find that the CN₄ tetrahedron can effectively activate the N≡N bond through weakening of the π orbital of N₂ under a pressure of 40 GPa, leading to stable CN polynitrides. The robust structural framework of CN polynitrides containing C–N and N–N bonds plays a crucial role in enhancing their structural stability, energy density, and hardness. Among these polynitrides, CN₆ possesses not only a very high mass density of 3.19 g/cm³, but also an ultrahigh energy density of 28.94 kJ/cm³, which represents a significant advance in the development of energetic materials using high-pressure methods. This work provides new insights into the mechanism of N₂ activation under high pressure, and offers a promising pathway to realize high-performance energetic materials.

Conflict of Interest
The authors have no conflicts to disclose.
Guanghui Zhang: Data curation (equal); Investigation (equal); Writing – original draft (equal). Wencai Yi: Conceptualization (equal); Funding acquisition (equal); Methodology (equal); Supervision (equal); Writing – original draft (equal); Writing – review & editing (equal). Yiqing Cao: Investigation (equal); Validation (equal). Shengli Zhang: Methodology (equal); Supervision (equal). Xiaobing Liu: Conceptualization (equal); Supervision (equal); Writing – review & editing (equal).
Author Contributions
The data that support the findings of this study are available within the article and its supplementary material.

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References(52)

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