Citation: Yunqing Zhu, Kaiyue Wen, Xuequan Wan, Gaigai Dong, Junfeng Niu. High efficiency conversion of low concentration nitrate boosted with amorphous Cu⁰ nanorods prepared via in-situ reconstruction[J]. Chinese Chemical Letters, ;2025, 36(6): 110399. doi: 10.1016/j.cclet.2024.110399 shu

High efficiency conversion of low concentration nitrate boosted with amorphous Cu⁰ nanorods prepared via in-situ reconstruction

Yunqing Zhu ^{a, *,} ,
Kaiyue Wen ^a ,
Xuequan Wan ^a ,
Gaigai Dong ^a ,
Junfeng Niu ^b

a.
School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China
b.
College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, China

zhuyunqing@sust.edu.cn

Received Date: 23 May 2024
Revised Date: 23 July 2024
Accepted Date: 31 August 2024
Available Online: 1 September 2024

Figures(6)

Electrocatalytic nitrate reduction reaction (NO₃⁻RR) is a green and competitive method for removing nitrate from water, requiring highly active and long-term stable electrocatalysts. In this work, we report a Cu⁰ nanorod catalyst with disordered structure (re-Cu NRs), prepared by electrochemical in situ reconfiguration of copper-based nitrides (Cu₃N NRs). The amorphous structure allows the exposure of abundant active sites to enhance the electrocatalytic activity because of the disordered atomic arrangement. At a potential of −1.2 V vs. Ag/AgCl, the re-Cu NRs catalyst achieved nearly 100% nitrate conversion within 120 min at a low nitrate concentration (50 mg/L), without the accumulation of nitrite. In-situ DEMS detection reveals that the NO₃⁻RR on re-Cu NRs followed the pathway of *NO₃⁻→ *NO₂⁻→ *NO → *N → *NH → *NH₂ → *NH₃. Furthermore, combining this proposed pathway with electrochlorination could efficiently transform ammonia into harmless N₂ (~99.41%). Theoretical calculations confirm that the amorphous structure on the surface of re-Cu NRs catalysts can facilitate strongly adsorbed nitrate, weaken the rate-determining step of *NH₃ → NH₃, and suppress hydrogen evolution reaction (HER). This study provides a new approach for designing efficient and stable amorphous catalysts for electrocatalytic nitrate reduction.
- Cu₃N,
- Electrochemical reconstruction,
- Cu⁰ nanorods,
- Amorphous structure,
- Electrochemical nitrate reduction
1. [1]
  X. Zhang, Y. Zhang, P. Shi, et al., Sci. Total Environ. 770 (2021) 144674. doi: 10.1016/j.scitotenv.2020.144674
2. [2]
  S. Singh, A.G. Anil, V. Kumar, et al., Chemosphere 187 (2022) 131996.
3. [3]
  X. Zou, C. Chen, C. Wang, et al., Sci. Total Environ. 800 (2021) 149645. doi: 10.1016/j.scitotenv.2021.149645
4. [4]
  X. Zhang, Y. Wang, C. Liu, et al., Chem. Eng. J. 403 (2021) 126269. doi: 10.1016/j.cej.2020.126269
5. [5]
  J. Chen, M. Gu, Y. Zhou, et al., Chem. Eng. J. 430 (2022) 132952. doi: 10.1016/j.cej.2021.132952
6. [6]
  M. Kalaruban, P. Loganathan, W.G. Shim, et al., Sep. Purif. Technol. 158 (2016) 62–70. doi: 10.1016/j.seppur.2015.12.022
7. [7]
  W. Li, S. Patton, J.M. Gleason, et al., Environ. Sci. Technol. 52 (2018) 6417–6425. doi: 10.1021/acs.est.7b06042
8. [8]
  L. Gao, F. Han, X. Zhang, et al., Bioresour. Technol. 314 (2020) 123714. doi: 10.1016/j.biortech.2020.123714
9. [9]
  R. Chauhan, V.C. Srivastava, Chem. Eng. J. 386 (2020) 122065. doi: 10.1016/j.cej.2019.122065
10. [10]
  S. Meng, Y. Ling, M. Yang, et al., J. Environ. Chem. Eng. 11 (2023) 109418. doi: 10.1016/j.jece.2023.109418
11. [11]
  F. Pan, J. Zhou, T. Wang, et al., J. Colloid Interf. Sci. 638 (2023) 26–38. doi: 10.1016/j.jcis.2023.01.121
12. [12]
  Y. Wang, C. Wang, M. Li, et al., Chem. Soc. Rev. 50 (2021) 6720–6733. doi: 10.1039/d1cs00116g
13. [13]
  F.Y. Chen, Z.Y. Wu, S. Gupta, et al., Nat. Nanotechnol. 17 (2022) 759–767. doi: 10.1038/s41565-022-01121-4
14. [14]
  Y. Xue, Q. Yu, J. Fang, et al., Small (2024) 2400505. doi: 10.1002/smll.202400505
15. [15]
  F. Ni, Y. Ma, J. Chen, et al., Chin. Chem. Lett. 32 (2021) 2073–2078. doi: 10.1016/j.cclet.2021.03.042
16. [16]
  W. Zheng, L. Zhu, Z. Yan, et al., Environ. Sci. Technol. 55 (2021) 13231–13243.
17. [17]
  G. Tokazhanov, E. Ramazanova, S. Hamid, et al., Chem. Eng. J. 384 (2020) 12352.
18. [18]
  Y. Wang, W. Zhou, R. Jia, et al., Angew. Chem. Int. Ed. 59 (2020) 5350–5354. doi: 10.1002/anie.201915992
19. [19]
  J. Zhou, F. Pan, Q. Yao, et al., Appl. Catal. B: Environ. 317 (2022) 121811. doi: 10.1016/j.apcatb.2022.121811
20. [20]
  Y. Wang, A. Xu, Z. Wang, et al., J. Am. Chem. Soc. 142 (2020) 5702–5708. doi: 10.1021/jacs.9b13347
21. [21]
  J. Cai, Y. Wei, A. Cao, et al., Appl. Catal. B: Environ. 316 (2022) 121683. doi: 10.1016/j.apcatb.2022.121683
22. [22]
  Q. Song, S. Zhang, X. Hou, et al., J. Hazard. Mater. 438 (2022) 129455. doi: 10.1016/j.jhazmat.2022.129455
23. [23]
  H. Yu, K. Deng, Z. Wang, et al., Appl. Catal. B: Environ. 318 (2022) 121805. doi: 10.1016/j.apcatb.2022.121805
24. [24]
  P.L. Gai-Boyes, Catal. Rev. 34 (1992) 1–54. doi: 10.1080/01614949208021918
25. [25]
  S. Sun, T. Zhai, C. Liang, et al., Nano Energy 45 (2018) 390–397. doi: 10.1016/j.nanoen.2018.01.015
26. [26]
  L. Zhang, H. Jang, H. Liu, et al., Angew. Chem. Int. Ed. 60 (2021) 18821–18829. doi: 10.1002/anie.202106631
27. [27]
  S. Deng, Z. Yuan, Z. Tie, et al., Angew. Chem. Int. Ed. 59 (2020) 22002–22006. doi: 10.1002/anie.202010287
28. [28]
  N. Liu, V. Häublein, X. Zhou, et al., Nano Lett. 15 (2015) 6815–6820. doi: 10.1021/acs.nanolett.5b02663
29. [29]
  L. Li, Z. Hu, L. Tao, et al., ACS Appl. Energy Mater. 3 (2020) 3071–3081. doi: 10.1021/acsaem.0c00190
30. [30]
  P.A. Shinde, S. Park, N.R. Chodankar, et al., Appl. Mater. Today 22 (2021) 100951. doi: 10.1016/j.apmt.2021.100951
31. [31]
  Q. Liang, L. Zhong, C. Du, et al., Adv. Funct. Mater. 2 (2018) 1805075.
32. [32]
  X. Wang, X. Yu, S. Wu, et al., ACS Appl. Mater. Interfaces 15 (2023) 15533–15544. doi: 10.1021/acsami.3c00547
33. [33]
  Y. Mi, S. Shen, X. Peng, et al., ChemElectroChem 6 (2019) 2393–2397. doi: 10.1002/celc.201801826
34. [34]
  C. Li, S. Liu, Y. Xu, et al., Nanoscale 14 (2022) 12332. doi: 10.1039/d2nr03767j
35. [35]
  T. Feng, J. Wang, Y. Wang, et al., Chem. Eng. J. 433 (2022) 133495. doi: 10.1016/j.cej.2021.133495
36. [36]
  Z. Wang, L. Xu, F. Huang, et al., Adv. Energy Mater. 9 (2019) 1900390. doi: 10.1002/aenm.201900390
37. [37]
  Y. Sun, S. Gao, F. Lei, et al., Chem. Soc. Rev. 44 (2015) 623–636. doi: 10.1039/C4CS00236A
38. [38]
  H. Xu, J. Wu, W. Luo, et al., Small 16 (2020) 2001775. doi: 10.1002/smll.202001775
39. [39]
  M. Fu, Y. Mao, H. Wang, et al., Chin. Chem. Lett. 35 (2024) 108341. doi: 10.1016/j.cclet.2023.108341
40. [40]
  Q. Song, M. Li, X. Hou, et al., Appl. Catal. B: Environ. 317 (2022) 121721. doi: 10.1016/j.apcatb.2022.121721
41. [41]
  M. Tang, Q. Tong, Y. Li, et al., Chin. Chem. Lett. 34 (2023) 108410. doi: 10.1016/j.cclet.2023.108410
42. [42]
  J. Zhao, Z. Shen, J. Yu, et al., J. Hazard. Mater. 439 (2022) 129653. doi: 10.1016/j.jhazmat.2022.129653
43. [43]
  R. Qi, Z. Wang, M. Zhong, et al. Small 10 (2023) 2308311. doi: 10.1002/smll.202308311
44. [44]
  M. Li, C. Feng, Z. Zhang, et al., J. Hazard. Mater. 171 (2009) 724–730. doi: 10.1016/j.jhazmat.2009.06.066
45. [45]
  X. Zhang, W. Li, E.R. Blatchley, et al., Water Res. 68 (2015) 804–811. doi: 10.1016/j.watres.2014.10.044
1. [1]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  Junchen Peng , Zhongyuan Guo , Dandan Dong , Yusheng Lu , Bao Wang , Fangjie Lu , Chaofeng Huang , Bin Dai . Cu⁰/Cu^δ⁺ site construction and its catalytic role in acetylene hydrochlorination. Chinese Chemical Letters, 2025, 36(8): 111208-. doi: 10.1016/j.cclet.2025.111208
5. [5]
  Zekun Zhang , Shiji Li , Qian Zhang , Shanshan Li , Liu Yang , Wei Yan , Hao Xu . Further study of CO₂ electrochemical reduction to gas products on Cu: Influence of the electrolyte. Chinese Chemical Letters, 2025, 36(9): 110742-. doi: 10.1016/j.cclet.2024.110742
6. [6]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
7. [7]
  Doudou Liu , Weiwei Guo , Guoliang Mei , Youpeng Dan , Rong Yang , Chao Huang , Yanling Zhai , Xiaoquan Lu . Application of catalyst Cu-t-ZrO₂ based on the electronic metal-support interaction in electrocatalytic nitrate reduction. Chinese Chemical Letters, 2025, 36(8): 110578-. doi: 10.1016/j.cclet.2024.110578
8. [8]
  Muhammad Humayun , Mohamed Bououdina , Abbas Khan , Sajjad Ali , Chundong Wang . Designing single atom catalysts for exceptional electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100193-100193. doi: 10.1016/j.cjsc.2023.100193
9. [9]
  Xin Han , Zhihao Cheng , Jinfeng Zhang , Jie Liu , Cheng Zhong , Wenbin Hu . Design of Amorphous High-Entropy FeCoCrMnBS (Oxy) Hydroxides for Boosting Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2025, 41(4): 100033-0. doi: 10.3866/PKU.WHXB202404023
10. [10]
  Tong Li , Leping Pan , Yan Zhang , Jihu Su , Kai Li , Kuiliang Li , Hu Chen , Qi Sun , Zhiyong Wang . Electrochemical construction of 2,5-diaryloxazoles via N–H and C(sp³)-H functionalization. Chinese Chemical Letters, 2024, 35(4): 108897-. doi: 10.1016/j.cclet.2023.108897
11. [11]
  Yuan ZHU , Xiaoda ZHANG , Shasha WANG , Peng WEI , Tao YI . Conditionally restricted fluorescent probe for Fe³⁺ and Cu²⁺ based on the naphthalimide structure. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 183-192. doi: 10.11862/CJIC.20240232
12. [12]
  Zhengzheng LIU , Pengyun ZHANG , Chengri WANG , Shengli HUANG , Guoyu YANG . Synthesis, structure, and electrochemical properties of a sandwich-type {Co₆}-cluster-added germanotungstate. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1173-1179. doi: 10.11862/CJIC.20240039
13. [13]
  Xue Zhao , Mengshan Chen , Dan Wang , Haoran Zhang , Guangzhi Hu , Yingtang Zhou . Ultrafine nano-copper derived from dopamine polymerization & synchronous adsorption achieve electrochemical purification of nitrate to ammonia in complex water environments. Chinese Chemical Letters, 2024, 35(8): 109327-. doi: 10.1016/j.cclet.2023.109327
14. [14]
  Liang Ma , Zhou Li , Zhiqiang Jiang , Xiaofeng Wu , Shixin Chang , Sónia A. C. Carabineiro , Kangle Lv . Effect of precursors on the structure and photocatalytic performance of g-C3N4 for NO oxidation and CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100416-100416. doi: 10.1016/j.cjsc.2024.100416
15. [15]
  Tianbo Jia , Lili Wang , Zhouhao Zhu , Baikang Zhu , Yingtang Zhou , Guoxing Zhu , Mingshan Zhu , Hengcong Tao . Modulating the degree of O vacancy defects to achieve selective control of electrochemical CO₂ reduction products. Chinese Chemical Letters, 2024, 35(5): 108692-. doi: 10.1016/j.cclet.2023.108692
16. [16]
  Xueyang Zhao , Bangwei Deng , Hongtao Xie , Yizhao Li , Qingqing Ye , Fan Dong . Recent process in developing advanced heterogeneous diatomic-site metal catalysts for electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(7): 109139-. doi: 10.1016/j.cclet.2023.109139
17. [17]
  Qian-Qian Tang , Li-Fang Feng , Zhi-Peng Li , Shi-Hao Wu , Long-Shuai Zhang , Qing Sun , Mei-Feng Wu , Jian-Ping Zou . Single-atom sites regulation by the second-shell doping for efficient electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(9): 109454-. doi: 10.1016/j.cclet.2023.109454
18. [18]
  Tinghui Yang , Min Kuang , Jianping Yang . Mesoporous CuCe dual-metal catalysts for efficient electrochemical reduction of CO2 to methane. Chinese Journal of Structural Chemistry, 2024, 43(8): 100350-100350. doi: 10.1016/j.cjsc.2024.100350
19. [19]
  Xiaoxi Zhao , Qingyun Dou , Pei Tang , Bingjun Yang , Qunji Xue , Xingbin Yan . In-situ construction of solid electrolyte interphase for stable zinc anode via synergy of electrochemical reduction and chemical precipitation. Chinese Chemical Letters, 2025, 36(11): 110422-. doi: 10.1016/j.cclet.2024.110422
20. [20]
  Qinyu Zhao , Yunchao Zhao , Songjing Zhong , Zhaoyang Yue , Zhuoheng Jiang , Shaobo Wang , Quanhong Hu , Shuncheng Yao , Kaikai Wen , Linlin Li . Urchin-like piezoelectric ZnSnO₃/Cu₃P p-n heterojunction for enhanced cancer sonodynamic therapy. Chinese Chemical Letters, 2024, 35(12): 109644-. doi: 10.1016/j.cclet.2024.109644

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(846)
HTML views(19)

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

High efficiency conversion of low concentration nitrate boosted with amorphous Cu0 nanorods prepared via in-situ reconstruction

Metrics

通讯作者: 陈斌, bchen63@163.com

High efficiency conversion of low concentration nitrate boosted with amorphous Cu⁰ nanorods prepared via in-situ reconstruction