Citation: Bin Chen, Chaoyang Zheng, Dehuan Shi, Yi Huang, Renxia Deng, Yang Wei, Zheyuan Liu, Yan Yu, Shenghong Zhong. p-d orbital hybridization induced by CuGa2 promotes selective N2 electroreduction[J]. Chinese Journal of Structural Chemistry, ;2025, 44(1): 100468. doi: 10.1016/j.cjsc.2024.100468 shu

p-d orbital hybridization induced by CuGa2 promotes selective N2 electroreduction

In the quest to align with industrial benchmarks, a noteworthy gap remains in the field of electrochemical nitrogen fixation, particularly in achieving high Faradaic efficiency (FE) and yield. The electrocatalytic nitrogen fixation process faces considerable hurdles due to the difficulty of cleaving the highly stable N≡N triple bond. Additionally, the electrochemical pathway for nitrogen fixation is often compromised by the concurrent hydrogen evolution reaction (HER), which competes aggressively for electrons and active sites on the catalyst surface, thereby reducing the FE of nitrogen reduction reactions (NRR). To surmount these challenges, this study introduces an innovative bimetallic catalyst, CuGa2, synthesized through p-d orbital hybridization to selectively facilitate N2 electroreduction. This catalyst has demonstrated a remarkable NH3 yield of 9.82 μg h-1 cm-2 and an associated Faradaic efficiency of 38.25%. Our findings elucidate that the distinctive p-d hybridization interaction between Ga and Cu enhances NH3 selectivity by reducing the reaction energy barrier for hydrogenation and suppressing hydrogen evolution. This insight highlights the significance of the p-d orbital hybridization in optimizing the electrocatalytic performance of CuGa2 for nitrogen fixation.
- Electrochemical nitrogen fixation,
- p-d orbital hybridization,
- Bimetallic catalyst,
- CuGa2 alloy,
- Liquid metals
1. [1]
  Yaoyin Lou , Xiaoyang Jerry Huang , Kuang-Min Zhao , Mark J. Douthwaite , Tingting Fan , Fa Lu , Ouardia Akdim , Na Tian , Shigang Sun , Graham J. Hutchings . Stable core-shell Janus BiAg bimetallic catalyst for CO₂ electrolysis into formate. Chinese Chemical Letters, 2025, 36(3): 110300-. doi: 10.1016/j.cclet.2024.110300
2. [2]
  Chao-Long Chen , Rong Chen , La-Sheng Long , Lan-Sun Zheng , Xiang-Jian Kong . Anchoring heterometallic cluster on P-doped carbon nitride for efficient photocatalytic nitrogen fixation in water and air ambient. Chinese Chemical Letters, 2024, 35(4): 108795-. doi: 10.1016/j.cclet.2023.108795
3. [3]
  Haodong Wang , Xiaoxu Lai , Chi Chen , Pei Shi , Houzhao Wan , Hao Wang , Xingguang Chen , Dan Sun . Novel 2D bifunctional layered rare-earth hydroxides@GO catalyst as a functional interlayer for improved liquid-solid conversion of polysulfides in lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(5): 108473-. doi: 10.1016/j.cclet.2023.108473
4. [4]
  Weilong Liu , Jipeng Dong , Luyao Zhang , Ning Li , Yangqin Gao , Lei Ge . Dynamic tuning of d-p orbital hybridization during sulfur vacancy evolution in Co9S8 toward efficient overall water splitting. Chinese Journal of Structural Chemistry, 2025, 44(9): 100661-100661. doi: 10.1016/j.cjsc.2025.100661
5. [5]
  Pengkun Li , Runjie Wu , Shuai Gao , Zeping Qin , Mingming Sun , Changzheng Wang , Wenming Sun , Qiang Wang . Bi-Bi₂Ti₂O₇ ohmic junction: Dual electron channels driving efficient photocatalytic nitrogen fixation. Chinese Chemical Letters, 2026, 37(1): 111116-. doi: 10.1016/j.cclet.2025.111116
6. [6]
  Yufei Jia , Fei Li , Ke Fan . Surface reconstruction of Cu-based bimetallic catalysts for electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100255-100255. doi: 10.1016/j.cjsc.2024.100255
7. [7]
  Xue Zhao , Rui Zhao , Qian Liu , Henghui Chen , Jing Wang , Yongfeng Hu , Yan Li , Qiuming Peng , John S Tse . A p-d block synergistic effect enables robust electrocatalytic oxygen evolution. Chinese Chemical Letters, 2024, 35(11): 109496-. doi: 10.1016/j.cclet.2024.109496
8. [8]
  Tan Zhang , Zhikai Che , Yuru Song , Jinping Li , Yuhan Sun , Guang Liu . Reinforced nitrogen fixation via synergistic Ru-Ni dual sites. Chinese Chemical Letters, 2025, 36(9): 111295-. doi: 10.1016/j.cclet.2025.111295
9. [9]
  Xiaoyu Du , Huan Wang . Tailoring mass transfer on electrochemical fixation of air-abundant molecules. Chinese Chemical Letters, 2025, 36(8): 110276-. doi: 10.1016/j.cclet.2024.110276
10. [10]
  Jundi Qin , Dezhong Hu , Dong Xiang , Xiongwu Kang . CuMoRuFeW high entropy alloy surfaced nanorods: Superior electrochemical CO2 reduction to ethylene. Chinese Journal of Structural Chemistry, 2025, 44(5): 100571-100571. doi: 10.1016/j.cjsc.2025.100571
11. [11]
  Linfeng Li , Bao Wang , Tiantong Zhang , Xinyuan Wang , Dingqiang Feng , Wei Li , Jiangjiexing Wu , Jinli Zhang . Identifying the catalytic active site of durable Ru-based liquid-phase catalyst for acetylene hydrochlorination. Chinese Chemical Letters, 2025, 36(10): 111303-. doi: 10.1016/j.cclet.2025.111303
12. [12]
  Xiaochun Liu , Gaoyan Chen , Xiaodong Yue , Chaoyue Wang , Xue-Xin Zhang , Xuecheng Ran , Yingxiao Zong , Junke Wang , Xicun Wang . A novel N-stable Co₂P nano-catalyst for the synthesis of quinoxalines by annulation of alkynes and 1,2-diaminobenzenes. Chinese Chemical Letters, 2025, 36(8): 110707-. doi: 10.1016/j.cclet.2024.110707
13. [13]
  Yuqing Ding , Zhiying Yi , Zhihui Wang , Hongyu Chen , Yan Zhao . Liquid nitrogen post-treatment for improved aggregation and electrical properties in organic semiconductors. Chinese Chemical Letters, 2024, 35(12): 109918-. doi: 10.1016/j.cclet.2024.109918
14. [14]
  Jincheng Zhang , Mengjie Sun , Jiali Ren , Rui Zhang , Min Ma , Qingzhong Xue , Jian Tian . Oxygen vacancies-rich molybdenum tungsten oxide nanowires as a highly active nitrogen fixation electrocatalyst. Chinese Chemical Letters, 2025, 36(1): 110491-. doi: 10.1016/j.cclet.2024.110491
15. [15]
  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
16. [16]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
17. [17]
  Yanling Yang , Zhenfa Ding , Huimin Wang , Jianhui Li , Yanping Zheng , Hongquan Guo , Li Zhang , Bing Yang , Qingqing Gu , Haifeng Xiong , Yifei Sun . Dynamic tracking of exsolved PdPt alloy/perovskite catalyst for efficient lean methane oxidation. Chinese Chemical Letters, 2024, 35(4): 108585-. doi: 10.1016/j.cclet.2023.108585
18. [18]
  Sixiao Liu , Tianyi Wang , Lei Zhang , Chengyin Wang , Huan Pang . Cerium-based metal-organic framework-modified natural mineral vermiculite for photocatalytic nitrogen fixation under visible-light irradiation. Chinese Chemical Letters, 2025, 36(3): 110058-. doi: 10.1016/j.cclet.2024.110058
19. [19]
  Lanxin Wang , Kaiwei Liang , Xuelian Yu , Guocheng Lv , Libing Liao . Facile method for creating frustrated Lewis pairs in g-C₃N₄ to enhance photocatalytic nitrogen fixation performance. Chinese Chemical Letters, 2026, 37(1): 110572-. doi: 10.1016/j.cclet.2024.110572
20. [20]
  Ji Chen , Yifan Zhao , Shuwen Zhao , Hua Zhang , Youyu Long , Lingfeng Yang , Min Xi , Zitao Ni , Yao Zhou , Anran Chen . Heterogeneous bimetallic oxides/phosphides nanorod with upshifted d band center for efficient overall water splitting. Chinese Chemical Letters, 2024, 35(9): 109268-. doi: 10.1016/j.cclet.2023.109268

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