Citation: 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[J]. Chinese Chemical Letters, ;2025, 36(8): 110657. doi: 10.1016/j.cclet.2024.110657 shu

In-situ reconstructed Cu/NiO nanosheets synergistically boosting nitrate electroreduction to ammonia

a.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China
b.
School of Materials Science and Engineering, Henan Normal University, Xinxiang 453007, China

shuyangao@htu.cn

Received Date: 14 June 2024
Revised Date: 30 October 2024
Accepted Date: 19 November 2024
Available Online: 21 November 2024

Figures(4)

Electrochemical reduction of nitrate (NO₃⁻) serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia (NH₃) synthesis process. The Cu electrocatalyst is widely recognized for its strong adsorption capacity towards nitrate, but its limited H adsorption and slow hydrogenation of oxynitride intermediates hinder the efficiency of converting NO₃⁻ into NH₃. Herein, a series of nanocomposite catalysts composed of CuO nanostructure with low NiO content that grow in-situ on carbon paper (CuO/NiO_x-CP) were synthesized via hydrothermal method and calcination for enhanced nitrate electroreduction utilizing the strong nitrate adsorption capacity of copper and excellent water dissociation ability of NiO to supply hydrogen free radicals (^•H). In-situ Raman spectroscopy reveals dynamic reconstruction of Cu/NiO_x during the electrochemical nitrate reduction process from CuO/NiO_x. Due to the synergistic effect of Cu and NiO, a high Faradaic efficiency (FE, ~97.9%) and yield rate (YR, 391.5 µmol h⁻¹ cm⁻²) of ammonia are achieved on CuO/NiO_2.3%-CP. Electron paramagnetic resonance (EPR) proves that the presence of NiO enhances the generation of ^•H, which can be rapidly consumed during nitrate reduction process. Density functional theory (DFT) calculations indicate that the activation energy of NiO (0.57 eV) is much lower than Cu (0.84 eV) for water splitting to generate ^•H, thus facilitating ^*NO hydrogenations. This drives us to create more effective catalysts for nitrate reduction under neutral conditions by promoting H₂O dissociation.
- Nitrate reduction,
- Ammonia synthesis,
- Synergistic effect,
- Hydrogenation,
- Water dissociation
1. [1]
  S. Luo, H. Guo, T. Li, et al., Appl. Catal. B: Environ. 351 (2024) 123967.
2. [2]
  T.N. Ye, S.W. Park, Y. Lu, et al., Nature 583 (2020) 391–395. doi: 10.1038/s41586-020-2464-9
3. [3]
  F. Ni, Y. Ma, J. Chen, W. Luo, J. Yang, Chin. Chem. Lett. 32 (2021) 2073–2078.
4. [4]
  Y. Gong, J. Wu, M. Kitano, et al., Nat. Catal. 1 (2018) 178–185. doi: 10.1038/s41929-017-0022-0
5. [5]
  M. Lim, Z. Ma, G. O'Connell, et al., Small 20 (2024) 2401333.
6. [6]
  W. Liao, J. Wang, G. Ni, et al., Nat. Commun. 15 (2024) 1264.
7. [7]
  M. Fu, Y. Mao, H. Wang, et al., Chin. Chem. Lett. 35 (2024) 108341.
8. [8]
  K. Liu, H. Li, M. Xie, et al., J. Am. Chem. Soc. 146 (2024) 7779–7790. doi: 10.1021/jacs.4c00429
9. [9]
  N. Zhou, Z. Wang, N. Zhang, et al., ACS Catal. 13 (2023) 7529–7537. doi: 10.1021/acscatal.3c01315
10. [10]
  Y. Wang, F. Hao, M. Sun, et al., Adv. Mater. 36 (2024) 2313548.
11. [11]
  M. Tang, Q. Tong, Y. Li, et al., Chinese Chem. Lett. 34 (2023) 108410.
12. [12]
  H. Luo, S. Li, Z. Wu, et al., Adv. Funct. Mater. 34 (2024) 2403838.
13. [13]
  J. John, D.R. MacFarlane, A.N. Simonov, Nat. Catal. 6 (2023) 1125–1130. doi: 10.1038/s41929-023-01060-w
14. [14]
  P. Li, R. Li, Y. Liu, et al., J. Am. Chem. Soc. 145 (2023) 6471–6479. doi: 10.1021/jacs.3c00334
15. [15]
  Q. Peng, D. Xing, L. Dong, et al., J. Mater. Chem. A 12 (2024) 8689–8693. doi: 10.1039/d3ta07506k
16. [16]
  L. Sun, B. Liu, Adv. Mater. 35 (2023) 1–8.
17. [17]
  B. Zhang, Z. Dai, Y. Chen, et al., Nat. Commun. 15 (2024) 2816.
18. [18]
  Y. Shi, M. Hou, J. Li, L. Li, Z. Zhang, Acta Phys. Chim. Sin. 38 (2022) 2206020. doi: 10.3866/pku.whxb202206020
19. [19]
  G. Jiang, M. Peng, L. Hu, et al., Chem. Eng. J. 435 (2022) 134853.
20. [20]
  X. Fan, D. Zhao, Z. Deng, et al., Small 19 (2023) 2208036.
21. [21]
  K. Fan, W. Xie, J. Li, et al., Nat. Commun. 13 (2022) 7958.
22. [22]
  R. Jia, Y. Wang, C. Wang, et al., ACS Catal. 10 (2020) 3533–3540. doi: 10.1021/acscatal.9b05260
23. [23]
  Z. Deng, C. Ma, X. Fan, et al., Mater. Today Phys. 28 (2022) 100854.
24. [24]
  X. Cheng, J. He, H. Ji, et al., Adv. Mater. 34 (2022) 2205767.
25. [25]
  H. Chen, C. Zhang, L. Sheng, et al., J. Hazard. Mater. 434 (2022) 128892.
26. [26]
  Y. Zhou, R. Duan, H. Li, et al., ACS Catal. 13 (2023) 10846–10854. doi: 10.1021/acscatal.3c02951
27. [27]
  W. Luo, Z. Guo, L. Ye, et al., Small 20 (2024) 2311336.
28. [28]
  Y. Bu, C. Wang, W. Zhang, et al., Angew. Chem. Int. Ed. 62 (2023) e202217337.
29. [29]
  Y. Fu, S. Wang, Y. Wang, et al., Angew. Chem. Int. Ed. 62 (2023) e202303327.
30. [30]
  H. Liu, X. Lang, C. Zhu, et al., Angew. Chem. Int. Ed. 61 (2022) e202202556.
31. [31]
  F.Y. Chen, Z.Y. Wu, S. Gupta, et al., Nat. Nanotechnol. 17 (2022) 759–767. doi: 10.1038/s41565-022-01121-4
32. [32]
  Y. Zheng, M.X. Qin, X. Yu, et al., Small 19 (2023) 2302266.
33. [33]
  Y. Huang, C. He, C. Cheng, et al., Nat. Commun. 14 (2023) 7368.
34. [34]
  J. Li, G. Zhan, J. Yang, et al., J. Am. Chem. Soc. 142 (2020) 7036–7046. doi: 10.1021/jacs.0c00418
35. [35]
  Z. Ge, T. Wang, Y. Ding, et al., Adv. Energy Mater. 12 (2022) 2103916.
36. [36]
  Y. Zhang, X. Chen, W. Wang, L. Yin, J.C. Crittenden, Appl. Catal. B: Environ. 310 (2022) 121346.
37. [37]
  Y. Wang, Z. Ji, Y. Pei, J. Hazard. Mater. 463 (2024) 132813.
38. [38]
  Q. Gao, H.S. Pillai, Y. Huang, et al., Nat. Commun. 13 (2022) 2338.
39. [39]
  H. Xu, J. Wu, W. Luo, et al., Small 16 (2020) 2001775.
40. [40]
  J. Lim, C.Y. Liu, J. Park, et al., ACS Catal. 11 (2021) 7568–7577. doi: 10.1021/acscatal.1c01413
41. [41]
  C. Li, J.Y. Xue, W. Zhang, et al., Nano Res. 16 (2023) 4742–4750. doi: 10.1007/s12274-022-5194-5
42. [42]
  F. Guo, Z. Zhang, R. Chen, et al., Mater. Horiz. 10 (2023) 2913–2920. doi: 10.1039/d3mh00416c
43. [43]
  P. Wang, H. Yang, C. Tang, Y. Wu, et al., Nat. Commun. 13 (2022) 3754.
44. [44]
  J. Wang, Y. Wang, C. Cai, et al., Nano Lett. 23 (2023) 1897–1903. doi: 10.1021/acs.nanolett.2c04949
45. [45]
  Y. Wang, W. Zhou, R. Jia, Y. Yu, B. Zhang, Angew. Chem. Int. Ed. 59 (2020) 5350–5354. doi: 10.1002/anie.201915992
46. [46]
  Y. Deng, A.D. Handoko, Y. Du, S. Xi, B.S. Yeo, ACS Catal. 6 (2016) 2473–2481. doi: 10.1021/acscatal.6b00205
47. [47]
  W.J. Duan, S.H. Lu, Z.L. Wu, Y.S. Wang, J. Phys. Chem. C 116 (2012) 26043–26051. doi: 10.1021/jp308073c
48. [48]
  R. Daiyan, T. Tran-Phu, P. Kumar, et al., Energy Environ. Sci. 14 (2021) 3588–3598. doi: 10.1039/d1ee00594d
49. [49]
  K. Huang, K. Tang, M. Wang, et al., Adv. Funct. Mater. 34 (2024) 2315324.
50. [50]
  S. He, V. Somayaji, M. Wang, et al., Nano Res. 15 (2022) 4785–4791. doi: 10.1007/s12274-021-3665-8
51. [51]
  X. Huang, Y. Ma, L. Zhi, Acta Phys. Chim. Sin. 38 (2021) 2011050.
52. [52]
  B. Deng, M. Huang, K. Li, et al., Angew. Chem. Int. Ed. 61 (2022) e202114080.
53. [53]
  W. He, J. Zhang, S. Dieckhöfer, et al., Nat. Commun. 13 (2022) 1129.
54. [54]
  L.H. Zhang, Y. Jia, J. Zhan, et al., Angew. Chem. Int. Ed. 62 (2023) e202303483.
55. [55]
  W. Liu, P. Zhai, A. Li, et al., Nat. Commun. 13 (2022) 1877.
56. [56]
  X. Yang, R. Wang, S. Wang, et al., Appl. Catal. B: Environ. 325 (2023) 122360.
57. [57]
  Y. Shi, Y. Li, R. Li, et al., Chem. Eng. J. 479 (2024) 147574.
58. [58]
  Z. Chang, G. Meng, Y. Chen, et al., Adv. Mater. 35 (2023) 2304508.
59. [59]
  Z. Huang, B. Yang, Y. Zhou, et al., ACS Nano 17 (2023) 25091–25100. doi: 10.1021/acsnano.3c07734
60. [60]
  Y. Hu, J. Liu, C. Lee, et al., ACS Nano 17 (2023) 23637–23648. doi: 10.1021/acsnano.3c06798
1. [1]
  Lingyun Shen , Shenxiang Yin , Qingshu Zheng , Zheming Sun , Wei Wang , Tao Tu . A rechargeable and portable hydrogen storage system grounded on soda water. Chinese Chemical Letters, 2025, 36(3): 110580-. doi: 10.1016/j.cclet.2024.110580
2. [2]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  Linping Li , Junhui Su , Yanping Qiu , Yangqin Gao , Ning Li , Lei Ge . Design and fabrication of ternary Au/Co3O4/ZnCdS spherical composite photocatalyst for facilitating efficient photocatalytic hydrogen production. Chinese Journal of Structural Chemistry, 2024, 43(12): 100472-100472. doi: 10.1016/j.cjsc.2024.100472
6. [6]
  Zimo Peng , Quan Zhang , Gaocan Qi , Hao Zhang , Qian Liu , Guangzhi Hu , Jun Luo , Xijun Liu . Nanostructured Pt@RuOx catalyst for boosting overall acidic seawater splitting. Chinese Journal of Structural Chemistry, 2024, 43(1): 100191-100191. doi: 10.1016/j.cjsc.2023.100191
7. [7]
  Hua Liu , Jian Zhao , Qi Li , Xiang-Yu Zhang , Zhi-Wei Zheng , Kun Huang , Da-Bin Qin , Bin Zhao . Indium-captured zirconium-porphyrin frameworks displaying rare multi-selectivity for catalytic transfer hydrogenation of aldehydes and ketones. Chinese Chemical Letters, 2025, 36(6): 110593-. doi: 10.1016/j.cclet.2024.110593
8. [8]
  Rui Liu , Yue Yu , Lu Deng , Maoxia Xu , Haorong Ren , Wenjie Luo , Xudong Cai , Zhenyu Li , Jingyu Chen , Hua Yu . The synergistic effect of A-site cation engineering and phase regulation enables efficient and stable Ruddlesden-Popper perovskite solar cells. Chinese Chemical Letters, 2024, 35(12): 109545-. doi: 10.1016/j.cclet.2024.109545
9. [9]
  Fengrui Yang , Debing Wang , Xinying Zhang , Jie Zhang , Zhichao Wu , Qiaoying Wang . Synergistic effects of peroxydisulfate on UV/O₃ process for tetracycline degradation: Mechanism and pathways. Chinese Chemical Letters, 2024, 35(10): 109599-. doi: 10.1016/j.cclet.2024.109599
10. [10]
  Yuxin Zeng , Yan Luo , Yao He , Kaihang Zhang , Binbin Zhu , Yuanzheng Zhang , Junfeng Niu . Photo-assisted electrocatalysis with bimetallic PdCu/TiO_x catalysts: Enhancing denitrification and economic viability. Chinese Chemical Letters, 2025, 36(6): 110514-. doi: 10.1016/j.cclet.2024.110514
11. [11]
  Ke Gong , Jinghan Liao , Jiangtao Lin , Quan Wang , Zhihua Wu , Liting Wang , Jiali Zhang , Yi Dong , Yourong Duan , Jianhua Chen . Mitochondria-targeted nanoparticles overcome chemoresistance via downregulating BACH1/CD47 axis in ovarian carcinoma. Chinese Chemical Letters, 2024, 35(5): 108888-. doi: 10.1016/j.cclet.2023.108888
12. [12]
  Liping Zhao , Xixi Guo , Zhimeng Zhang , Xi Lu , Qingxuan Zeng , Tianyun Fan , Xintong Zhang , Fenbei Chen , Mengyi Xu , Min Yuan , Zhenjun Li , Jiandong Jiang , Jing Pang , Xuefu You , Yanxiang Wang , Danqing Song . Novel berberine derivatives as adjuvants in the battle against Acinetobacter baumannii: A promising strategy for combating multi-drug resistance. Chinese Chemical Letters, 2024, 35(10): 109506-. doi: 10.1016/j.cclet.2024.109506
13. [13]
  Xuejie Gao , Xinyang Chen , Ming Jiang , Hanyan Wu , Wenfeng Ren , Xiaofei Yang , Runcang Sun . Long-lifespan thin Li anode achieved by dead Li rejuvenation and Li dendrite suppression for all-solid-state lithium batteries. Chinese Chemical Letters, 2024, 35(10): 109448-. doi: 10.1016/j.cclet.2023.109448
14. [14]
  Wenhao Feng , Chunli Liu , Zheng Liu , Huan Pang . In-situ growth of N-doped graphene-like carbon/MOF nanocomposites for high-performance supercapacitor. Chinese Chemical Letters, 2024, 35(12): 109552-. doi: 10.1016/j.cclet.2024.109552
15. [15]
  Tong Zhang , Xiaojing Liang , Licheng Wang , Shuai Wang , Xiaoxiao Liu , Yong Guo . An ionic liquid assisted hydrogel functionalized silica stationary phase for mixed-mode liquid chromatography. Chinese Chemical Letters, 2025, 36(1): 109889-. doi: 10.1016/j.cclet.2024.109889
16. [16]
  Shuai Li , Liuting Zhang , Fuying Wu , Yiqun Jiang , Xuebin Yu . Efficient catalysis of FeNiCu-based multi-site alloys on magnesium-hydride for solid-state hydrogen storage. Chinese Chemical Letters, 2025, 36(1): 109566-. doi: 10.1016/j.cclet.2024.109566
17. [17]
  Shimei Wu , Yining Li , Lantao Chen , Yufei Zhang , Lingxing Zeng , Haosen Fan . Hexapod cobalt phosphosulfide nanorods encapsulating into multiple hetero-atom doped carbon frameworks for advanced sodium/potassium ion battery anodes. Chinese Chemical Letters, 2025, 36(4): 109796-. doi: 10.1016/j.cclet.2024.109796
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]
  Ying Chen , Xingyuan Xia , Lei Tian , Mengying Yin , Ling-Ling Zheng , Qian Fu , Daishe Wu , Jian-Ping Zou . Constructing built-in electric field via CuO/NiO heterojunction for electrocatalytic reduction of nitrate at low concentrations to ammonia. Chinese Chemical Letters, 2024, 35(12): 109789-. doi: 10.1016/j.cclet.2024.109789

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(18)
HTML views(1)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142