Citation: 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[J]. Chinese Chemical Letters, ;2025, 36(4): 109797. doi: 10.1016/j.cclet.2024.109797 shu

Single-atom Ti doping on S-vacancy two-dimensional CrS₂ as a catalyst for ammonia synthesis: A DFT study

Yiwen Xu ^a ,
Chaozheng He ^{a, *,} ,
Chenxu Zhao ^{a, *,} ,
Ling Fu ^{b, *,}

a.
Institute of Environment and Energy Catalysis, Shanxi Key Laboratory of Optoelectronic Functional Materials and Devices, School of Materials Science and Chemical Engineering, Xi’an Technological University, Xi’an 710021, China
b.
College of Resources and Environmental Engineering, Tianshui Normal University, Tianshui 741001, China

hecz2019@xatu.edu.cn

zhaochenxu@xatu.edu.cn

ful263@nenu.edu.cn

Received Date: 24 January 2024
Revised Date: 15 March 2024
Accepted Date: 19 March 2024
Available Online: 20 March 2024

Figures(7)

Electrocatalytic reduction of NO (NORR) is an effective method for NH₃ synthesis, due to low bonding energy of NO bond. In this work, we have investigated many CrS₂ based catalysts, including pristine CrS₂, CrS₂ with one S vacancy (v-CrS₂), and Ti doped CrS₂ (Ti@CrS₂). The results have shown that the pristine CrS₂ exhibits inert character for NO activation. However, v-CrS₂ and Ti@CrS₂ can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates (0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts (-0.96~-1.64 eV), compared to the situation of CrS₂ (0.065 e/-0.30 eV). From the free energy profiles of NO electro-reduction to NH₃, we can see that the v-CrS₂ and Ti@CrS₂ all exhibit ultralow limiting potentials of -0.03~-0.47 V, following both *NOH and *NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.
- CrS₂,
- NO electrocatalytic reduction,
- First principles calculation,
- Introducing vacancy doping
1. [1]
  A. Liu, Y. Yang, D. Kong, et al., Appl. Surf. Sci. 536 (2021) 147851. doi: 10.1016/j.apsusc.2020.147851
2. [2]
  X. Liu, Y. Zhang, T. Liu, et al., Appl. Surf. Sci. 605 (2022) 154831. doi: 10.1016/j.apsusc.2022.154831
3. [3]
  B. Ma, Y. Peng, D. Ma, Z. Deng, Z. Lu, Appl. Surf. Sci. 495 (2019) 143463. doi: 10.1016/j.apsusc.2019.07.205
4. [4]
  X.G. Ma, J.S. Hu, M.K. Zheng, et al., Appl. Surf. Sci. 489 (2019) 684–692. doi: 10.1016/j.apsusc.2019.05.022
5. [5]
  B. Castellano-Varona, M. Harb, J. Arana, L. Cavallo, L.M. Azofra, Chem. Commun. 56 (2020) 13343–13346. doi: 10.1039/d0cc05921h
6. [6]
  S.Y. Lv, C.X. Huang, G. Li, L.M. Yang, ACS Appl. Mater. Interfaces 13 (2021) 29641–29653. doi: 10.1021/acsami.1c06368
7. [7]
  L. Xu, L.M. Yang, E. Ganz, ACS Appl. Mater. Interfaces 13 (2021) 14091–14101. doi: 10.1021/acsami.0c20553
8. [8]
  Z. Wei, J. He, Y. Yang, et al., J. Energy Chem. 53 (2021) 303–308. doi: 10.1016/j.jechem.2020.04.014
9. [9]
  Z. Xue, X. Zhang, J. Qin, R. Liu, J. Energy Chem. 57 (2021) 443–450. doi: 10.1016/j.jechem.2020.09.002
10. [10]
  Y. Abghoui, A.L. Garden, J.G. Howalt, T. Vegge, E. Skúlason, ACS Catal. 6 (2016) 635–646. doi: 10.1021/acscatal.5b01918
11. [11]
  P. Liu, J. Liang, J. Wang, et al., Chem. Commun. 57 (2021) 13562–13565. doi: 10.1039/d1cc06113e
12. [12]
  Z. Lang, J. Miao, H. Tan, et al., Inorg. Chem. Front. 7 (2020) 4507–4516. doi: 10.1039/d0qi01014f
13. [13]
  T. Mou, J. Liang, Z. Ma, et al., J. Mater. Chem. A 9 (2021) 24268–24275. doi: 10.1039/d1ta07455e
14. [14]
  Y. Bai, M. Mavrikakis, J. Phys. Chem. B 122 (2018) 432–443. doi: 10.1021/acs.jpcb.7b01115
15. [15]
  L. Ling, Z. Zhao, X. Feng, et al., J. Phys. Chem. C 121 (2017) 16399–16414. doi: 10.1021/acs.jpcc.7b05024
16. [16]
  X.Y. Xie, Q. Wang, W.H. Fang, G. Cui, J. Phys. Chem. C 121 (2017) 16373–16380. doi: 10.1021/acs.jpcc.7b04811
17. [17]
  Z. Li, Z. Ma, J. Liang, et al, Mater. Today Phys. 22 (2021) 100586.
18. [18]
  S. Ji, J. Zhao, New J. Chem. 48 (2018) 16346–16353. doi: 10.1039/c8nj03279c
19. [19]
  M. Tursun, C. Wu, Phys. Chem. Chem. Phys. 23 (2021) 19872–19883. doi: 10.1039/d1cp02764f
20. [20]
  Y. Xiao, C. Shen, Small 17 (2021) 2100776. doi: 10.1002/smll.202100776
21. [21]
  Z. Wang, J. Zhao, J. Wang, C.R. Cabrera, Z. Chen, J. Mater. Chem. A 6 (2018) 7547–7556. doi: 10.1039/c8ta00875b
22. [22]
  C. He, R. Sun, L. Fu, et al., Chin. Chem. Lett. 33 (2021) 527–532.
23. [23]
  K. Chu, Y.P. Liu, Y.B. Li, Y.L. Guo, Y. Tian, ACS Appl. Mater. Interfaces 12 (2020) 7081–7090. doi: 10.1021/acsami.9b18263
24. [24]
  X. Zhang, T. Wu, H. Wang, et al., ACS Catal. 9 (2019) 4609–4615. doi: 10.1021/acscatal.8b05134
25. [25]
  Y. Li, C. Cheng, S. Han, et al., ACS Energy Lett. 7 (2022) 1187–1194. doi: 10.1021/acsenergylett.2c00207
26. [26]
  H. Wan, A. Bagger, J. Rossmeisl, Angew. Chem. Int. Ed. 60 (2021) 21966–21972. doi: 10.1002/anie.202108575
27. [27]
  S. Lu, F. Luo, Z. Yu, Catalysts 12 (2022) 228. doi: 10.3390/catal12020228
28. [28]
  C. Martín, K. Kostarelos, M. Prato, A. Bianco, Chem. Commun. 55 (2019) 5540–5546. doi: 10.1039/c9cc01205b
29. [29]
  X. Sun, L. Shi, H. Huang, X. Song, T. Ma, Chem. Commun. 56 (2020) 11000–11013. doi: 10.1039/d0cc04790b
30. [30]
  H. Bergeron, D. Lebedev, M.C. Hersam, Chem. Rev. 121 (2021) 2713–2775. doi: 10.1021/acs.chemrev.0c00933
31. [31]
  Y. Wang, Z. Zhang, Y. Mao, X. Wang, Energy Environ. Sci. 13 (2020) 3993–4016. doi: 10.1039/d0ee01714k
32. [32]
  Y. Zhang, P. Liu, X. Zhu, Z. Liu, Int. J. Hydrog. Energy 46 (2021) 32936–32948. doi: 10.1016/j.ijhydene.2021.07.144
33. [33]
  X. Hu, S. Guo, S. Zhang, et al., J. Mater. Chem. A 7 (2019) 25887–25893. doi: 10.1039/c9ta08820b
34. [34]
  T. Sun, G. Zhang, D. Xu, et al., Mater. Today Energy 12 (2019) 215–238. doi: 10.1016/j.mtener.2019.01.004
35. [35]
  B. Luo, G. Liu, L. Wang, Nanoscale 8 (2016) 6904–6920. doi: 10.1039/C6NR00546B
36. [36]
  Y. Wang, Y. Du, Y. Meng, et al., Appl. Surf. Sci. 563 (2021) 150277. doi: 10.1016/j.apsusc.2021.150277
37. [37]
  D. Zhou, C. Li, F. Yin, et al., Chin. Chem. Lett. 31 (2020) 2325–2329. doi: 10.1016/j.cclet.2020.04.045
38. [38]
  C. He, J. Wang, L. Fu, W. Wei, Chin. Chem. Lett. 35 (2023) 109037.
39. [39]
  F. Li, L. Chen, H. Liu, et al., J. Phys. Chem. C 123 (2019) 22221–22227. doi: 10.1021/acs.jpcc.9b04730
40. [40]
  K. Chen, J. Deng, Y. Yan, et al., NPJ Comput. Mater. 7 (2021) 79. doi: 10.1038/s41524-021-00547-z
41. [41]
  G.B.M. Stan, K. Dhaka, M.C. Toroker, Israel J. Chem. 60 (2019) 888–896.
42. [42]
  Z. Qin, Z. Wang, X. Li, et al., Nanomaterials 12 (2022) 3012. doi: 10.3390/nano12173012
43. [43]
  Q. Wang, Q. Feng, Y. Lei, et al., Nat. Commun. 13 (2022) 3689. doi: 10.1038/s41467-022-31383-4
44. [44]
  Q. Wang, S. Tang, Z. Wang, et al, Adv. Funct. Mater. 33 (2023) 2307390. doi: 10.1002/adfm.202307390
45. [45]
  H. Zheng, S. Wang, S. Liu, et al, Adv. Funct. Mater. 33 (2023) 2300815. doi: 10.1002/adfm.202300815
46. [46]
  B.A. Kalwar, W. Zong, I. Ahmed, M.H. Saeed, J. Chin. Chem. Soc. 68 (2021) 2243–2253. doi: 10.1002/jccs.202100369
47. [47]
  S. Liu, G. Xing, J. Liu, Appl. Surf. Sci. 611 (2022) 155764.
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沈阳化工大学材料科学与工程学院沈阳 110142

Single-atom Ti doping on S-vacancy two-dimensional CrS2 as a catalyst for ammonia synthesis: A DFT study

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通讯作者: 陈斌, bchen63@163.com

Single-atom Ti doping on S-vacancy two-dimensional CrS₂ as a catalyst for ammonia synthesis: A DFT study