Citation: Shijian Luo, Hao Chen, Yuran Yang, Yang Song, Yongduo Liu, Daojun Long, Siguo Chen, Zidong Wei. Plasma-calcium imide coupled pathway: A dual-mechanism strategy for ultra-efficient electro-driven nitrogen reduction[J]. Chinese Chemical Letters, ;2026, 37(12): 113084. doi: 10.1016/j.cclet.2026.113084 shu

Plasma-calcium imide coupled pathway: A dual-mechanism strategy for ultra-efficient electro-driven nitrogen reduction

State Key Laboratory of Advanced Chemical Power Sources (SKL–ACPS), School of Chemistry and Chemical Engineering, Center of Advanced Electrochemical Energy (CAEE), Institute of Advanced Interdisciplinary Studies, Chongqing University, Chongqing 401331, China

ldjsicau@163.com

csg810519@126.com

Received Date: 9 March 2026
Revised Date: 9 June 2026
Accepted Date: 15 June 2026
Available Online: 15 June 2026

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Plasma-catalytic ammonia (NH₃) synthesis has recently emerged as a promising complementary approach to the Haber–Bosch process for mild and electro-driven NH₃ production. However, its efficiency is severely limited by the incomplete utilization of plasma-generated reactive species and the lack of tailored catalysts capable of integrating both surface and gas-phase N₂ activation pathways within plasma-catalyst coupled systems. In this study, we present Ca₂NH, a metal imide catalyst that enables ultra-efficient NH₃ synthesis via a dual-mechanism strategy. Owing to its integrated nitride-hydride structure, Ca₂NH simultaneously facilitates a surface Mars–van Krevelen pathway for lattice-nitrogen hydrogenation and a gas-phase radical pathway driven by hydrogen radicals released from lattice hydrogen. This coupled mechanism ensures comprehensive N₂ activation throughout the reaction space and achieves a remarkable NH₃ synthesis rate of 371.8 mg h^–1 g^–1 under room temperature and atmospheric pressure, outperforming most reported electro–driven catalytic systems. These findings provide an effective strategy for integrating heterogeneous surface reactions with homogeneous radical–mediated pathways to achieve ultra-efficient activation of N₂ molecules.
- Ammonia synthesis,
- Nitrogen reduction,
- Plasma catalysis,
- Nonthermal plasma,
- Metal imide
1. [1]
  H.R. Li, X. Kang, R. Gao, et al., Chin. Chem. Lett. 36 (2025) 109958. doi: 10.1016/j.cclet.2024.109958
2. [2]
  X. Fu, J.B. Pedersen, Y. Zhou, et al., Science 379 (2023) 707–712. doi: 10.1126/science.adf4403
3. [3]
  X. Peng, X. Hu, R. Mao, et al., Chin. Chem. Lett. 37 (2026) 111820. doi: 10.1016/j.cclet.2025.111820
4. [4]
  C. Zhang, S. Shi, B. Fang, et al., Chin. Chem. Lett. 34 (2023) 107237. doi: 10.1016/j.cclet.2022.02.042
5. [5]
  Y. Wang, M. Batmunkh, H. Mao, et al., Chin. Chem. Lett. 33 (2022) 394–398. doi: 10.1016/j.cclet.2021.05.025
6. [6]
  K.H.R. Rouwenhorst, Y. Engelmann, K. Van ’T Veer, et al., Green Chem. 22 (2020) 6258–6287. doi: 10.1039/d0gc02058c
7. [7]
  P. Mehta, P. Barboun, F.A. Herrera, et al., Nat. Catal. 1 (2018) 269–275. doi: 10.1038/s41929-018-0045-1
8. [8]
  X. Zhang, Y. Liu, M. Zhang, et al., Chem 6 (2020) 3312–3328. doi: 10.1016/j.chempr.2020.09.016
9. [9]
  Z. Zhang, C. Kondratowicz, J. Smith, et al., ACS Energy Lett. 10 (2025) 3349–3358. doi: 10.1021/acsenergylett.5c01034
10. [10]
  Y. Wang, W. Yang, S. Xu, et al., J. Am. Chem. Soc. 144 (2022) 12020–12031. doi: 10.1021/jacs.2c01950
11. [11]
  S. Luo, Y. Liu, Y. Song, et al., Chem. Commun. 61 (2025) 16066–16069. doi: 10.1039/d5cc04331j
12. [12]
  S. Luo, Y. Liu, Y. Song, et al., Chem. Commun. 60 (2024) 3295–3298. doi: 10.1039/d4cc00042k
13. [13]
  Y. Wang, J. Yang, Y. Sun, et al., Chem 10 (2024) 2590–2606. doi: 10.1016/j.chempr.2024.06.022
14. [14]
  Y. Yang, L. Guo, S. Luo, et al., ACS Catal. 15 (2025) 14955–14965. doi: 10.1021/acscatal.5c01699
15. [15]
  S. Luo, Y. Liu, L. Guo, et al., J. Mater. Chem. A 13 (2025) 30546–30553. doi: 10.1039/d5ta04447b
16. [16]
  W. Gao, J. Guo, P. Wang, et al., Nat. Energy 3 (2018) 1067–1075. doi: 10.1038/s41560-018-0268-z
17. [17]
  P. Chen, Z. Xiong, J. Luo, J. Lin, K.L. Tan, Nature 420 (2002) 302–304. doi: 10.1038/nature01210
18. [18]
  H. Yu, X. Li, J. Zheng, ACS Catal. 14 (2024) 3139–3157. doi: 10.1021/acscatal.3c05696
19. [19]
  M. Kitano, K. Yamagata, H. Hosono, Res. Chem. Intermed. 47 (2021) 235–248. doi: 10.1007/s11164-020-04332-3
20. [20]
  H. Abe, Y. Niwa, M. Kitano, et al., Bull. Chem. Soc. Jpn. 90 (2017) 963–965. doi: 10.1246/bcsj.20170143
21. [21]
  C. Smith, A.K. Hill, L. Torrente-Murciano, Energy Environ. Sci. 13 (2020) 331–344. doi: 10.1039/c9ee02873k
22. [22]
  L. Hollevoet, F. Jardali, Y. Gorbanev, et al., Angew. Chem. Int. Ed. 59 (2020) 23825–23829. doi: 10.1002/anie.202011676
23. [23]
  W. Liu, M. Xia, C. Zhao, et al., Nat. Commun. 15 (2024) 3524. doi: 10.1038/s41467-024-47765-9
24. [24]
  L. Xu, Q. Wang, Q. Gu, et al., Angew. Chem. Int. Ed. 64 (2025) e202508091. doi: 10.1002/anie.202508091
25. [25]
  H.J. Niu, N. Ran, W. Zhou, et al., J. Am. Chem. Soc. 147 (2025) 2607–2615. doi: 10.1021/jacs.4c14675
26. [26]
  X.Y. Ran, T.J. Xiong, Y.P. Yang, et al., Chin. Chem. Lett. 37 (2026) 111864. doi: 10.1016/j.cclet.2025.111864
27. [27]
  C. Hu, J. Zhao, R. Chang, et al., J. Am. Chem. Soc. 147 (2025) 37428–37436. doi: 10.1021/jacs.5c11505
28. [28]
  J. Li, W. Yu, H. Yuan, et al., Nat. Commun. 15 (2024) 9499. doi: 10.24294/jipd9499
29. [29]
  Y. Bai, Y. Zhang, J. Hu, et al., ACS Catal. 15 (2025) 1455–1466. doi: 10.1021/acscatal.4c06966
30. [30]
  J. Lin, D. Liao, H. Zhang, H. Wan, K. Tsai, Chin. J. Catal. 31 (2010) 153–155. doi: 10.1016/S1872-2067(09)60040-1
31. [31]
  Z. Zhang, K. Miyashita, T. Wu, et al., Nat. Chem. 17 (2025) 679–687. doi: 10.1038/s41557-025-01737-8
32. [32]
  J. Li, G. Zhan, J. Yang, et al., J. Am. Chem. Soc. 142 (2020) 7036–7046. doi: 10.1021/jacs.0c00418
33. [33]
  Y. Xi, C. Zhang, W. Tu, et al., Angew. Chem. Int. Ed. 64 (2025) e202505046. doi: 10.1002/anie.202505046
34. [34]
  X. Feng, J. Liu, L. Chen, et al., J. Am. Chem. Soc. 145 (2023) 10259–10267. doi: 10.1021/jacs.3c01319
35. [35]
  C. Zhang, Z.H. Wang, H. Wang, et al., Natl. Sci. Rev. 11 (2024) nwae251. doi: 10.1093/nsr/nwae251
36. [36]
  H. Zhao, G. Song, Z. Chen, et al., ACS Energy Lett. 7 (2022) 53–58. doi: 10.1021/acsenergylett.1c02207
1. [1]
  Yating Yang , Ming Xu , Ze Gao , Ting Wang , Zhaoxing Li , Yuqi Wang , Daming Yang , Ming Feng . Oxygen vacancy engineering of Fe₂O₃ nanospindles via cobalt incorporation for enhanced electrocatalytic N₂ reduction towards NH₃ synthesis. Chinese Chemical Letters, 2026, 37(11): 112580-. doi: 10.1016/j.cclet.2026.112580
2. [2]
  Zhenfei Tang , Yunwu Zhang , Zhiyuan Yang , Haifeng Yuan , Tong Wu , Yue Li , Guixiang Zhang , Xingzhi Wang , Bin Chang , Dehui Sun , Hong Liu , Lili Zhao , Weijia Zhou . Iron-doping regulated light absorption and active sites in LiTaO₃ single crystal for photocatalytic nitrogen reduction. Chinese Chemical Letters, 2025, 36(3): 110107-. doi: 10.1016/j.cclet.2024.110107
3. [3]
  Chaozheng He , Jia Wang , Ling Fu , Wei Wei . Nitric oxide assists nitrogen reduction reaction on 2D MBene: A theoretical study. Chinese Chemical Letters, 2024, 35(5): 109037-. doi: 10.1016/j.cclet.2023.109037
4. [4]
  Yuwei Liu , Yihui Zhu , Weijian Duan , Yizhuo Yang , Haorui Tuo , Chunhua Feng . Electrocatalytic nitrate reduction on Fe, Fe₃O₄, and Fe@Fe₃O₄ cathodes: Elucidating structure-sensitive mechanisms of direct electron versus hydrogen atom transfer. Chinese Chemical Letters, 2025, 36(6): 110347-. doi: 10.1016/j.cclet.2024.110347
5. [5]
  Zunjie Zhang , Mengran Liu , Bingcheng Ge , Tianfang Yang , Shuaitong Wang , Yang Liu , Shuyan Gao . In-situ reconstructed Cu/NiO nanosheets synergistically boosting nitrate electroreduction to ammonia. Chinese Chemical Letters, 2025, 36(8): 110657-. doi: 10.1016/j.cclet.2024.110657
6. [6]
  Mingxing Chen , Xue Li , Nian Liu , Zihe Du , Zhitao Wang , Jing Qi . A zinc-nitrate battery for efficient ammonia electrosynthesis and energy output by a high entropy hydroxide catalyst. Chinese Chemical Letters, 2025, 36(10): 111294-. doi: 10.1016/j.cclet.2025.111294
7. [7]
  Chaozheng He , Menghui Xi , Chenxu Zhao , Ran Wang , Ling Fu , Jinrong Huo . Highly N₂ dissociation catalyst: Ir(100) and Ir(110) surfaces. Chinese Chemical Letters, 2025, 36(3): 109671-. doi: 10.1016/j.cclet.2024.109671
8. [8]
  Jieyu Liu , Junze Zhang , Haigang Deng , Shuoao Wang , Xingxing Jiang , Li Wang , Changhong Wang . Understanding the activity origin of Pd-anchored single-atom alloy catalysts for NO-to-NH₃ conversion by DFT studies and machine learning. Chinese Chemical Letters, 2025, 36(12): 110656-. doi: 10.1016/j.cclet.2024.110656
9. [9]
  Yaxin Zhao , Yaowei Xiang , Meijie Wang , Yuxing Lin , Zi-Zhong Zhu , Shunqing Wu , Xinrui Cao . Synergistic surface engineering of BCN catalysts: Boosting NO electroreduction to NH₃ via compositional tuning and electron-rich edge stabilization. Chinese Chemical Letters, 2026, 37(12): 112768-. doi: 10.1016/j.cclet.2026.112768
10. [10]
  Jie Hou , Bin Liu , Wenjing Zheng , Yaling Wang , Guangqun Cao , Shengliang Hu . Advancements in electrocatalytic nitrogen reduction to ammonia. Chinese Chemical Letters, 2026, 37(9): 112689-. doi: 10.1016/j.cclet.2026.112689
11. [11]
  Yihong Li , Zhong Qiu , Lei Huang , Shenghui Shen , Ping Liu , Haomiao Zhang , Feng Cao , Xinping He , Jun Zhang , Yang Xia , Xinqi Liang , Chen Wang , Wangjun Wan , Yongqi Zhang , Minghua Chen , Wenkui Zhang , Hui Huang , Yongping Gan , Xinhui Xia . Plasma enhanced reduction method for synthesis of reduced graphene oxide fiber/Si anode with improved performance. Chinese Chemical Letters, 2024, 35(11): 109510-. doi: 10.1016/j.cclet.2024.109510
12. [12]
  Sajid Mahmood , Haiyan Wang , Fang Chen , Yijun Zhong , Yong Hu . Recent progress and prospects of electrolytes for electrocatalytic nitrogen reduction toward ammonia. Chinese Chemical Letters, 2024, 35(4): 108550-. doi: 10.1016/j.cclet.2023.108550
13. [13]
  Qiaorui Wang , Dingyun Liang , Zhongwen Zhang , Yalan Yang , Yunran Zhang , Yirong Wang , Lei Liu , Wenfeng Jiang , Muneerah Alomar , Li-Long Zhang . Single-atom catalysts for electrocatalytic nitrogen reduction to ammonia: A review. Chinese Journal of Structural Chemistry, 2025, 44(6): 100599-100599. doi: 10.1016/j.cjsc.2025.100599
14. [14]
  Yuanjiang Dong , Shiqi Bi , Mengru Wang , Zongxian Yang , Xinnian Tian , Yurun Chen , Ziqi Sun , Renren Sun , Yuge Ouyang , Liuyang Bai , Jishi Wei , Fangli Yuan , Ming-Shui Yao . Plasma-driven material synthesis and structural chemical engineering of silicon-based anodes for lithium-ion batteries. Chinese Journal of Structural Chemistry, 2026, 45(6): 100907-100907. doi: 10.1016/j.cjsc.2026.100907
15. [15]
  Xueqi Du , Ge Gao , Guoxiang Pan , Zhong Qiu , Yongqi Zhang , Shenghui Shen , Tianqi Yang , Xinqi Liang , Ping Liu , Xinhui Xia . Utilizing BBr₃ plasma to create high-quality solid electrolyte interphases for enhanced lithium metal anodes. Chinese Chemical Letters, 2025, 36(11): 110753-. doi: 10.1016/j.cclet.2024.110753
16. [16]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-0. doi: 10.1016/j.actphy.2025.100054
17. [17]
  He Guo , Yongchun Wang , Junlei Wang , Shoufeng Tang , Tiecheng Wang . Review on application of non-thermal plasma for disinfection: Direct plasma and indirect plasma-activated water. Chinese Chemical Letters, 2026, 37(2): 111275-. doi: 10.1016/j.cclet.2025.111275
18. [18]
  Ting Xie , Xun He , Lang He , Kai Dong , Yongchao Yao , Zhengwei Cai , Xuwei Liu , Xiaoya Fan , Tengyue Li , Dongdong Zheng , Shengjun Sun , Luming Li , Wei Chu , Asmaa Farouk , Mohamed S. Hamdy , Chenggang Xu , Qingquan Kong , Xuping Sun . CoSe₂ nanowire array enabled highly efficient electrocatalytic reduction of nitrate for ammonia synthesis. Chinese Chemical Letters, 2024, 35(11): 110005-. doi: 10.1016/j.cclet.2024.110005
19. [19]
  Hong-Rui Li , Xia Kang , Rui Gao , Miao-Miao Shi , Bo Bi , Ze-Yu Chen , Jun-Min Yan . Interfacial interactions of Cu/MnOOH enhance ammonia synthesis from electrochemical nitrate reduction. Chinese Chemical Letters, 2025, 36(2): 109958-. doi: 10.1016/j.cclet.2024.109958
20. [20]
  Wenbi Wu , Yinchu Dong , Haofan Liu , Xuebing Jiang , Li Li , Yi Zhang , Maling Gou . Modification of plasma protein for bioprinting via photopolymerization. Chinese Chemical Letters, 2024, 35(8): 109260-. doi: 10.1016/j.cclet.2023.109260

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