Citation: Longjian Li, Ping Zhang, Yongchong Yu, Reyila Tuerhong, Xiaoping Su, Lijuan Han, Enzhou Liu, Jizhou Jiang. Electron trap-induced charge accumulation and surface reaction kinetics synergistically enhance overall nitrogen photofixation[J]. Chinese Chemical Letters, ;2025, 36(8): 111118. doi: 10.1016/j.cclet.2025.111118 shu

Electron trap-induced charge accumulation and surface reaction kinetics synergistically enhance overall nitrogen photofixation

Longjian Li ^a ,
Ping Zhang ^{a, *,} ,
Yongchong Yu ^a ,
Reyila Tuerhong ^a ,
Xiaoping Su ^a ,
Lijuan Han ^b ,
Enzhou Liu ^c ,
Jizhou Jiang ^{d, *,}

a.
Key Laboratory of Environment-Friendly Composite Materials of the State Ethnic Affairs Commission, Gansu Province Engineering Research Center for Biomass Functional Composite Materials, Key Laboratory for the Utilization of Environment Friendly Composite Materials and Biomass in Universities of Gansu Province, Gansu Province Research Center for Basic Sciences of Surface and Interface Chemistry, College of Chemical Engineering, Northwest Minzu University, Lanzhou 730030, China
b.
Gansu Natural Energy Research Institute, Gansu Academy of Science, Lanzhou 730046, China
c.
School of Chemical Engineering, Xi'an Key Laboratory of Special Energy Materials, Northwest University, Xi'an 710069, China
d.
School of Materials Science and Engineering, Key Laboratory of Green Chemical Engineering Process of Ministry of Education, Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education, Wuhan Institute of Technology, Wuhan 430205, China

zhangping@xbmu.edu.cn

027wit@163.com

Received Date: 13 December 2024
Revised Date: 17 March 2025
Accepted Date: 19 March 2025
Available Online: 20 March 2025

Figures(8)

Available online Further oxidation of NH₃ produced via photocatalytic N₂ fixation represents a promising strategy to enhance the economic value of N₂ fixation. This work employs first-principles density functional theory (DFT) calculations to demonstrate that incorporating Co into NiO improves both N₂ adsorption and activation as well as M-N electron exchange intensity. Guided by these predictions, a novel Co single-atom photocatalyst supported by nanoconfined NiO@C nanosheets was synthesized using a direct metal atomization method, achieving high HNO₃ production (60.54%). NH₄⁺ and NO₃⁻ production rates during N₂ photofixation reached 67.97 µmol g_cat⁻¹ h⁻¹ and 104.28 µmol g_cat⁻¹ h⁻¹, respectively. The overall N₂ → NH₃ → HNO₃ photofixation pathway was validated through in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ¹⁵N isotopic labeling. Mechanistic studies reveal that Co single-atom introduction serves as an electron trap, enhancing photogenerated electron accumulation with a five-fold increase in carrier density compared to NiO@C, as observed via in-situ X-ray photoelectron spectroscopy (XPS). This synergistic effect between electron traps and N₂ adsorption/activation sites at Co single-atom centers supports rapid N₂ reduction kinetics. Additionally, nanoconfined ink-bottle pores in the carbon layer impede NH₃ desorption, further boosting NO₃⁻ production. This work offers a comprehensive approach to optimizing N₂ photofixation through electron regulation and surface reaction kinetics.
- N₂ photofixation,
- Co single-atom,
- Nanoconfined NiO@C,
- Electron trap,
- NO₃⁻ production
1. [1]
  K.A. Brown, D.F. Harris, M.B. Wilker, et al., Science 352 (2016) 448–450. doi: 10.1126/science.aaf2091
2. [2]
  K. Lakshmanamoorthy, S. Manivannan, Carbon Lett. 34 (2024) 141–151. doi: 10.1007/s42823-023-00627-8
3. [3]
  F. Li, G. Zhu, J. Jiang, et al., J. Mater. Sci. Technol. 177 (2024) 142–180.
4. [4]
  N. Song, J. Jiang, S. Hong, et al., Chin. J. Catal. 59 (2024) 38–81.
5. [5]
  B. Lin, H. Chen, Y. Zhou, et al., Chin. Chem. Lett. 32 (2021) 3128–3132.
6. [6]
  H. Ou, Y. Jin, B. Chong, et al., Adv. Mater. 36 (2024) 2404851.
7. [7]
  X. Gong, W. Teng, W. Liu, et al., Adv. Mater. 37 (2025) 2412924.
8. [8]
  M. Luo, B. Wang, J. Shao, et al., Carbon Lett. 34 (2024) 2291–2303. doi: 10.1007/s42823-024-00755-9
9. [9]
  A. Pashkova, B.O. Burek, J.Z. Bloh, Catal. Sci. Technol. 12 (2022) 2755–2760. doi: 10.1039/d2cy00350c
10. [10]
  J. Lim, C.A. Fernández, S.W. Lee, M.C. Hatzell, ACS Energy Lett. 6 (2021) 3676–3685. doi: 10.1021/acsenergylett.1c01614
11. [11]
  J. Yang, Y. Guo, R. Jiang, et al., J. Am. Chem. Soc. 140 (2018) 8497–8508. doi: 10.1021/jacs.8b03537
12. [12]
  X. Chen, N. Li, Z. Kong, W.J. Ong, X. Zhao, Mater. Horiz. 5 (2018) 9–27.
13. [13]
  C. Chen, R. Chen, L. Long, et al., Chin. Chem. Lett. 35 (2024) 108795.
14. [14]
  Y. Niu, C. Yue, S. Li, et al., Carbon Lett. 33 (2023) 957–9729. doi: 10.1007/s42823-023-00486-3
15. [15]
  C. Zhao, L. Yue, S. Yuan, et al., J. Ind. Eng. Chem. 132 (2024) 135–147.
16. [16]
  M. Lan, X. Dong, N. Zheng, et al., J. Mater. Sci. Technol. 167 (2023) 237–247.
17. [17]
  P. Xia, X. Pan, S. Jiang, et al., Adv. Mater. 34 (2022) 2200563.
18. [18]
  H. Li, M. Xia, B. Chong, et al., ACS Catal. 12 (2022) 10361–10372. doi: 10.1021/acscatal.2c02282
19. [19]
  K. Ba, D. Pu, X. Yang, et al., Appl. Catal. B: Environ. 317 (2022) 121755.
20. [20]
  J. Xiao, X. Pan, S. Guo, P. Ren, X. Bao, J. Am. Chem. Soc. 137 (2015) 477–482. doi: 10.1021/ja511498s
21. [21]
  X. Wang, S. Qiu, J. Feng, et al., Adv. Mater. 32 (2020) 2004382.
22. [22]
  P. Liu, Z. Huang, S. Yang, et al., ACS Catal. 12 (2022) 8139–8146. doi: 10.1021/acscatal.2c01704
23. [23]
  J. Luo, H. Han, X. Wang, et al., Appl. Catal. B: Environ. 328 (2023) 122495.
24. [24]
  W. Ding, Y. Yang, X. Li, et al., Langmuir 41 (2025) 340–349. doi: 10.1021/acs.langmuir.4c03624
25. [25]
  Z. Zhang, H. Sui, W. Shi, et al., Angew. Chem. Int. Ed. 64 (2024) e202416711.
26. [26]
  S. Xu, W. Shi, J. Huang, et al., Angew. Chem. Int. Ed. 63 (2024) e202406223.
27. [27]
  Q. Zhao, W. Shi, J. Zhang, et al., Nat. Synth. 3 (2024) 497–506. doi: 10.1038/s44160-024-00486-9
28. [28]
  T. Kandemir, M.E. Schuster, A. Senyshyn, M. Behrens, R. Schlögl, Angew. Chem. Int. Ed. 52 (2013) 12723–12726. doi: 10.1002/anie.201305812
29. [29]
  T. Cai, Q. Chang, C. Xue, et al., J. Colloid Interf. Sci. 630 (2023) 182–190.
30. [30]
  B. Huang, N. Li, W. Lin, H. Li, J. Hazard. Mater. 360 (2018) 578–586.
31. [31]
  F. Sastre, A. Corma, H. García, Angew. Chem. Int. Ed. 52 (2013) 12983–12987. doi: 10.1002/anie.201307851
32. [32]
  M. Yadav, A. Pophali, N. Verma, T. Kim, J. Ind. Eng. Chem. 105 (2022) 313–323.
33. [33]
  S. Wang, H. Maimaiti, B. Xu, et al., J. Phys. Chem. C 123 (2019) 31119–31129. doi: 10.1021/acs.jpcc.9b10189
34. [34]
  Z. Liu, X. Li, S. Su, et al., Appl. Surf. Sci. 611 (2023) 155627.
35. [35]
  P. Arod, S.A. Shivashankar, RSC Adv. 6 (2016) 65366–65372.
36. [36]
  Z. Lin, C. Du, B. Yan, C. Wang, G. Yang, Nat. Commun. 9 (2018) 4036.
37. [37]
  J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865–3868.
38. [38]
  P. Giannozzi, S. Baroni, N. Bonini, et al., J. Phys. Condens. Matter 21 (2009) 395502. doi: 10.1088/0953-8984/21/39/395502
39. [39]
  G. Kresse, D. Joubert, Phys. Rev. B 59 (1999) 1758–1775.
40. [40]
  L. Zhang, R. Li, L. Guo, et al., ACS Catal. 14 (2024) 5696–5709. doi: 10.1021/acscatal.3c05633
41. [41]
  T. Kamachi, T. Tatsumi, T. Toyao, et al., J. Phys. Chem. C 123 (2019) 20988–20997. doi: 10.1021/acs.jpcc.9b05707
42. [42]
  M.J. Hoffmann, A.J. Medford, T. Bligaard, J. Phys. Chem. C 120 (2016) 13087–13094. doi: 10.1021/acs.jpcc.6b03375
43. [43]
  Q. Wang, X. Kong, H. Han, et al., Phys. Chem. Chem. Phys. 21 (2019) 12597–12605. doi: 10.1039/c9cp02491c
44. [44]
  A. Shah, S. Senapati, H.C.A. Murthy, L.R. Singh, M. Mahato, ACS Omega 8 (2023) 33380–33391. doi: 10.1021/acsomega.3c03044
45. [45]
  Z. Yang, T. Huang, M. Li, et al., Adv. Mater. 36 (2024) 2313513.
46. [46]
  J. Shi, Y. Wei, D. Zhou, et al., ACS Catal. 12 (2022) 7760–7772. doi: 10.1021/acscatal.2c01873
47. [47]
  X. Chang, M. Fan, C. Gu, et al., Angew. Chem. Int. Ed. 61 (2022) e202202558.
48. [48]
  Z. Wu, T. Wang, J. Zou, Y. Li, C. Zhang, ACS Catal. 12 (2022) 5911–5920. doi: 10.1021/acscatal.2c01829
49. [49]
  J. Hou, C. Cao, F. Idrees, X. Ma, ACS Nano 9 (2015) 2556–2564. doi: 10.1021/nn506394r
50. [50]
  M. Kruk, M. Jaroniec, Chem. Mater. 13 (2001) 3169–3183.
51. [51]
  X. He, J. Liao, Z. Tang, et al., J. Power Sources 396 (2018) 533–541.
52. [52]
  K. Du, M. Hao, Z. Li, J. Fan, et al., Chin. J. Catal. 40 (2019) 1057–1062.
53. [53]
  J. Jiang, L. Ou-yang, L. Zhu, et al., Carbon 80 (2014) 213–221.
54. [54]
  Y. Li, H. Chen, L.Y. Voo, et al., J. Mater. Chem. 22 (2012) 15021–15024. doi: 10.1039/c2jm32307a
55. [55]
  J. Jiang, Z. Xiong, H. Wang, et al., J. Mater. Sci. Technol. 118 (2022) 15–24.
56. [56]
  J. Zheng, D. Meng, J. Guo, et al., Adv. Mater. 36 (2024) 2405129.
57. [57]
  F. Jafarzadeh, L.A. Castriotta, E. Calabrò, et al., Commun. Mater. 5 (2024) 186.
58. [58]
  R. Ge, Y. Wang, Z. Li, et al., Angew. Chem. Int. Ed. 134 (2022) e202200211.
59. [59]
  S. Li, R. Ma, J. Hu, et al., Nat. Commun. 13 (2022) 2916.
60. [60]
  T. Ma, C. Yang, L. Guo, R.A. Soomro, et al., Appl. Catal. B: Environ. 330 (2023) 122643.
61. [61]
  Y. Li, J. Fan, J. Peng, et al., Nano Res. 18 (2025) 94907054. doi: 10.26599/nr.2025.94907054
62. [62]
  J. Zou, S. Wu, Y. Liu, et al., Carbon 130 (2018) 652–663.
63. [63]
  D.P.H. Tran, M.T. Pham, Y. Wang, S. You, J. Ind. Eng. Chem. 127 (2023) 343–355.
64. [64]
  X. Chen, Y. Wu, Y. Tang, et al., Chin. Chem. Lett. 35 (2024) 109245.
65. [65]
  K. Wang, T. Sun, H. Ma, et al., Chem. Eng. J. 497 (2024) 154711.
66. [66]
  H. Ren, F. Qi, A. Labidi, et al., Appl. Catal. B: Environ. 330 (2023) 122587.
67. [67]
  F. Zhang, Y. Li, B. Ding, et al., Small 19 (2023) 2303867.
68. [68]
  P. Li, Z. Zhou, Q. Wang, et al., J. Am. Chem. Soc. 142 (2020) 12430–12439. doi: 10.1021/jacs.0c05097
69. [69]
  S. Wang, X. Hai, X. Ding, et al., Adv. Mater. 29 (2017) 1701774.
70. [70]
  K. Ding, A.W. Pierpont, W.W. Brennessel, et al., J. Am. Chem. Soc. 131 (2009) 9471–9472. doi: 10.1021/ja808783u
1. [1]
  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
2. [2]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
3. [3]
  Xiujuan Wang , Yijie Wang , Luyun Cui , Wenqiang Gao , Xiao Li , Hong Liu , Weijia Zhou , Jingang Wang . Coordination-based synthesis of Fe single-atom anchored nitrogen-doped carbon nanofibrous membrane for CO₂ electroreduction with nearly 100% CO selectivity. Chinese Chemical Letters, 2024, 35(12): 110031-. doi: 10.1016/j.cclet.2024.110031
4. [4]
  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
5. [5]
  Yiwen Xu , Chaozheng He , Chenxu Zhao , Ling Fu . Single-atom Ti doping on S-vacancy two-dimensional CrS₂ as a catalyst for ammonia synthesis: A DFT study. Chinese Chemical Letters, 2025, 36(4): 109797-. doi: 10.1016/j.cclet.2024.109797
6. [6]
  Xingyan Liu , Chaogang Jia , Guangmei Jiang , Chenghua Zhang , Mingzuo Chen , Xiaofei Zhao , Xiaocheng Zhang , Min Fu , Siqi Li , Jie Wu , Yiming Jia , Youzhou He . Single-atom Pd anchored in the porphyrin-center of ultrathin 2D-MOFs as the active center to enhance photocatalytic hydrogen-evolution and NO-removal. Chinese Chemical Letters, 2024, 35(9): 109455-. doi: 10.1016/j.cclet.2023.109455
7. [7]
  Jinshu Huang , Zhuochun Huang , Tengyu Liu , Yu Wen , Jili Yuan , Song Yang , Hu Li . Modulating single-atom Co and oxygen vacancy coupled motif for selective photodegradation of glyphosate wastewater to circumvent toxicant residue. Chinese Chemical Letters, 2025, 36(5): 110179-. doi: 10.1016/j.cclet.2024.110179
8. [8]
  Junqi Wang , Shuai Zhang , Jingjing Ma , Xiangjun Liu , Yayun Ma , Zhimin Fan , Jingfeng Wang . Augmenting levoglucosan production through catalytic pyrolysis of biomass exploiting Ti₃C₂T_x MXene. Chinese Chemical Letters, 2024, 35(12): 109725-. doi: 10.1016/j.cclet.2024.109725
9. [9]
  Hualin Jiang , Wenxi Ye , Huitao Zhen , Xubiao Luo , Vyacheslav Fominski , Long Ye , Pinghua Chen . Novel 3D-on-2D g-C₃N₄/AgI._x._y heterojunction photocatalyst for simultaneous and stoichiometric production of H₂ and H₂O₂ from water splitting under visible light. Chinese Chemical Letters, 2025, 36(2): 109984-. doi: 10.1016/j.cclet.2024.109984
10. [10]
  Jingtai Bi , Yupeng Cheng , Mengmeng Sun , Xiaofu Guo , Shizhao Wang , Yingying Zhao . Efficient and selective photocatalytic nitrite reduction to N₂ through CO₂ anion radical by eco-friendly tartaric acid activation. Chinese Chemical Letters, 2024, 35(11): 109639-. doi: 10.1016/j.cclet.2024.109639
11. [11]
  Hui Li , Yanxing Qi , Jia Chen , Juanjuan Wang , Min Yang , Hongdeng Qiu . Synthesis of amine-pillar[5]arene porous adsorbent for adsorption of CO₂ and selectivity over N₂ and CH₄. Chinese Chemical Letters, 2024, 35(11): 109659-. doi: 10.1016/j.cclet.2024.109659
12. [12]
  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
13. [13]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-0. doi: 10.3866/PKU.WHXB202408005
14. [14]
  Yi Liu , Zhe-Hao Wang , Guan-Hua Xue , Lin Chen , Li-Hua Yuan , Yi-Wen Li , Da-Gang Yu , Jian-Heng Ye . Photocatalytic dicarboxylation of strained C–C bonds with CO₂ via consecutive visible-light-induced electron transfer. Chinese Chemical Letters, 2024, 35(6): 109138-. doi: 10.1016/j.cclet.2023.109138
15. [15]
  Maomao Liu , Guizeng Liang , Ningce Zhang , Tao Li , Lipeng Diao , Ping Lu , Xiaoliang Zhao , Daohao Li , Dongjiang Yang . Electron-rich Ni2+ in Ni3S2 boosting electrocatalytic CO2 reduction to formate and syngas. Chinese Journal of Structural Chemistry, 2024, 43(8): 100359-100359. doi: 10.1016/j.cjsc.2024.100359
16. [16]
  Jijoe Samuel Prabagar , Kumbam Lingeshwar Reddy , Dong-Kwon Lim . Visible-light responsive gold nanoparticle and nano-sized Bi2O3-x sheet heterozygote structure for efficient photocatalytic conversion of N2 to NH3. Chinese Journal of Structural Chemistry, 2025, 44(4): 100564-100564. doi: 10.1016/j.cjsc.2025.100564
17. [17]
  Jingtao Bi , Yupeng Cheng , Mengmeng Sun , Xiaofu Guo , Shizhao Wang , Yingying Zhao . Corrigendum to “Efficient and selective photocatalytic nitrite reduction to N₂ through CO₂ anion radical by eco-friendly tartaric acid activation” [Chinese Chemical Letters 35 (2024) 109639]. Chinese Chemical Letters, 2025, 36(7): 110867-. doi: 10.1016/j.cclet.2025.110867
18. [18]
  Junchen Peng , Xue Yin , Dandan Dong , Zhongyuan Guo , Qinqin Wang , Minmin Liu , Fei He , Bin Dai , Chaofeng Huang . Promotion effect of epoxy group neighboring single-atom Cu site on acetylene hydrochlorination. Chinese Chemical Letters, 2024, 35(6): 109508-. doi: 10.1016/j.cclet.2024.109508
19. [19]
  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
20. [20]
  Zeyu Jiang , Yadi Wang , Changwei Chen , Chi He . Progress and challenge of functional single-atom catalysts for the catalytic oxidation of volatile organic compounds. Chinese Chemical Letters, 2024, 35(9): 109400-. doi: 10.1016/j.cclet.2023.109400

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(20)
HTML views(4)

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