Citation: Xiaoyu Zhao, Kai Gao, Sen Xue, Wei Ran, Rui Liu. Synergistic effects of oxygen vacancies and Pd single atoms on Pd@TiO_2−x for efficient HER catalysis[J]. Chinese Chemical Letters, ;2025, 36(6): 110309. doi: 10.1016/j.cclet.2024.110309 shu

Synergistic effects of oxygen vacancies and Pd single atoms on Pd@TiO_2−x for efficient HER catalysis

Xiaoyu Zhao ^a ,
Kai Gao ^a ,
Sen Xue ^a ,
Wei Ran ^b ,
Rui Liu ^{b, c, *,}

a.
Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-utilization, College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin 300457, China
b.
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
c.
School of Environment, Hangzhou Institute for Advanced Study, UCAS, Hangzhou 310024, China

ruiliu@rcees.ac.cn

Received Date: 19 February 2024
Revised Date: 25 June 2024
Accepted Date: 30 July 2024
Available Online: 31 July 2024

Figures(3)

Electrocatalytic water splitting for hydrogen production is a key approach to tackling the current energy crisis. Among the catalysts, the traditional Pd@C catalysts are remarkable for their efficiency in hydrogen evolution. However, the high cost and scarcity of Pd catalysts, as well as the instability caused by the corrosiveness of carbon-based substrates, hinder their large-scale application. To overcome this challenge, an effective strategy is to construct highly dispersed Pd single atoms to improve palladium utilization and choose more stable materials as supports. In this study, TiO_2−x carriers with abundant oxygen vacancies were prepared and loaded with Pd by photoreduction deposition. Adjusting the palladium content resulted in three forms of Pd-loaded TiO_2−x: nanoparticles (Pd@TiO_2−x(6%, 10%)), nanoclusters (Pd@TiO_2−x(3%)) and single atoms (Pd@TiO_2−x(1.5%)). The oxygen vacancies improved the stability of the titanium dioxide materials by providing more active hydrogen adsorption sites and increasing the affinity of Pd for active hydrogen. Single atom loading increased the frequency of oxygen holes in the support and the high activity of monatomic Pd promoted the adsorption of active hydrogen and facilitated the formation of active hydrogen intermediates. The synergistic effect of single atoms and oxygen vacancies improved the stability and catalytic activity of the composite material. Pd@TiO_2−x(1.5%) showed outstanding performance in hydrogen evolution in an acidic medium with an overpotential of only 24 mV at a current density of 10 mA/cm² and a low Tafel rise of 41.9 mV/dec. This study provides an effective strategy for the development of high-performance hydrogen evolution (HER) catalysts.
- Electrocatalytic water splitting,
- Single-atom Pd catalysts,
- Oxygen vacancies,
- Synergistic effects,
- HER catalysis
1. [1]
  Q. Gao, W. Zhang, Z. Shi, et al., Adv. Mater. 31 (2019) 1802880. doi: 10.1002/adma.201802880
2. [2]
  Z. He, X. Huang, Q. Chen, M. Zhu, J. Colloid Interface Sci. 616 (2022) 279–286. doi: 10.1016/j.jcis.2022.02.073
3. [3]
  K. Pramoda, C.N.R. Rao, J. Mater, Chem. A 11 (2023) 16933–16962. doi: 10.1039/d3ta01629c
4. [4]
  M. Muhyuddin, G. Tseberlidis, M. Acciarri, et al., J. Energy Chem. 87 (2023) 256–285. doi: 10.1016/j.jechem.2023.08.011
5. [5]
  L.N. Shi, L.T. Cui, Y.R. Ji, et al., Coord. Chem. Rev. 469 (2022) 214668. doi: 10.1016/j.ccr.2022.214668
6. [6]
  X. Zhao, X. Lu, W. Chen, et al., J. Colloid Interface Sci. 659 (2024) 11–20. doi: 10.1117/12.3047938
7. [7]
  J. Li, Z. Jing, H. Bai, et al., Environ. Chem. Lett. 21 (2023) 2583–2617. doi: 10.1007/s10311-023-01616-z
8. [8]
  P. Aggarwal, D. Sarkar, K. Awasthi, P.W. Menezes, Coord. Chem. Rev. 452 (2022) 214289. doi: 10.1016/j.ccr.2021.214289
9. [9]
  C. Lei, W. Zhou, Q. Feng, et al., Nano-Micro Lett. 11 (2019) 1–10. doi: 10.11648/j.sr.20190701.11
10. [10]
  X. Shi, C. Dai, X. Wang, et al., Nat. Commun. 13 (2022) 1287. doi: 10.1038/s41467-022-28995-1
11. [11]
  X. Liu, Z. Hao, H. Wang, et al., Proc. Natl. Acad. Sci. U. S. A. 119 (2022) e2119723119. doi: 10.1073/pnas.2119723119
12. [12]
  H. Zhao, X. Yang, Y. Duan, Z. Shen, ChemCatChem 16 (2024) e202301295. doi: 10.1002/cctc.202301295
13. [13]
  C.Z. Yuan, K.S. Hui, H. Yin, et al., ACS Mater. Lett. 3 (2021) 752–780. doi: 10.1021/acsmaterialslett.0c00549
14. [14]
  J. Li, J. Hu, M. Zhang, et al., Nat. Commun. 12 (2021) 3502. doi: 10.1039/d1qo00111f
15. [15]
  E. Heydari-Bafrooei, S. Askari, Int. J. Hydrog, Energy. 42 (2017) 2961–2969. doi: 10.1016/j.ijhydene.2016.11.101
16. [16]
  Z. Pu, I.S. Amiinu, R. Cheng, et al., Nano-Micro Lett. 12 (2020) 1–29. doi: 10.1080/14786419.2020.1830398
17. [17]
  X. Liu, S. Gao, P. Yang, et al., Appl. Mater. Today 13 (2018) 158–165. doi: 10.3390/catal8040158
18. [18]
  X. Wu, H. Zhang, S. Zuo, et al., Nano-Micro Lett. 13 (2021) 136. doi: 10.1007/s40820-021-00668-6
19. [19]
  F. Zheng, C. Zhang, X. Gao, et al., Electrochim. Acta 306 (2019) 627–634. doi: 10.1016/j.electacta.2019.03.175
20. [20]
  N.W.J. Scott, N. Jeddi M.J. Ford, A. Eyles, et al., J. Am. Chem. Soc. 143 (2021) 9682–9693. doi: 10.1021/jacs.1c05294
21. [21]
  X. Gao, G. Yu, L. Zheng, et al., ACS Appl. Energy Mater. 2 (2019) 966–973. doi: 10.1021/acsaem.8b01783
22. [22]
  J. Chen, Y. Ha, R. Wang, et al., Nano-Micro Lett. 14 (2022) 186. doi: 10.1007/s40820-022-00933-2
23. [23]
  Z. Chen, S. Yun, L. Wu, et al., Nano-Micro Lett. 15 (2023) 4. doi: 10.1007/s40820-022-00974-7
24. [24]
  B. Geng, X. Chu, L. Liu, et al., Chin. Chem. Lett. 35 (2024) 108924. doi: 10.1016/j.cclet.2023.108924
25. [25]
  H. Yu, Y. Xue, B. Huang, et al., iScience 11 (2019) 31–41. doi: 10.1016/j.isci.2018.12.006
26. [26]
  J. Zhu, L. An, X. Li, et al., Appl. Surf. Sci. 644 (2024) 158809. doi: 10.1016/j.apsusc.2023.158809
27. [27]
  B. Guo, Y. Ding, H. Huo, et al., Nano-Micro Lett. 15 (2023) 57. doi: 10.1007/s40820-023-01038-0
28. [28]
  A.S.B. Mohd-Najib, M. Iqbal, M.B. Zakaria, et al., J. Mater. Chem. A 8 (2020) 19788–19792. doi: 10.1039/d0ta04223d
29. [29]
  X. Chen, S. Guan, J. Zhou, et al., Catalysts 62 (2023) e202312734.
30. [30]
  C. Zhai, Y. Chen, X. Huang, et al., Environ. Funct. Mater. 1 (2022) 219–229. doi: 10.1177/0308518x211055181
31. [31]
  Q. Qiao, Y. Chen, Y. Wang, et al., Chin. Chem. Lett. 34 (2023) 107394. doi: 10.1016/j.cclet.2022.03.117
32. [32]
  H. Zhang, Q. Liu, Z. Shen, Chin. Chem. Lett. 35 (2024) 108607. doi: 10.1016/j.cclet.2023.108607
33. [33]
  S.H. Wang, L.N. Chen, P.Y. Zhang, et al., Nano Energy 88 (2021) 106211. doi: 10.1016/j.nanoen.2021.106211
34. [34]
  X. Zeng, Y. Bai, S.M. Choi, et al., Mater. Today Nano 6 (2019) 100038. doi: 10.1016/j.mtnano.2019.100038
35. [35]
  C. Li, N.C.S. Selvam, J. Fang, Nano-Micro Lett. 15 (2023) 83. doi: 10.1007/s40820-023-01060-2
36. [36]
  X. You, D. Zhang, X.G. Zhang, et al., Nano-Micro Lett. 16 (2024) 53. doi: 10.1007/s40820-023-01285-1
37. [37]
  J. Yang, M. Zhang, M. Chen, et al., Adv. Mater. 35 (2023) 2209885. doi: 10.1002/adma.202209885
38. [38]
  T. Zhang, T. Yang, G. Qu, et al., J. Energy Chem. 68 (2022) 71–77. doi: 10.1016/j.jechem.2021.10.031
39. [39]
  T. Zhang, T. Yang, B. Li, S. Wei, W. Gao, J. Alloys Compd. 905 (2022) 164165. doi: 10.1016/j.jallcom.2022.164165
40. [40]
  Z. Wu, P. Yang, Q. Li, et al., Angew. Chem. Int. Ed. 135 (2023) e202300406. doi: 10.1002/ange.202300406
41. [41]
  M. Zhou, X. Jiang, W. Kong, et al., Nano-Micro Lett. 15 (2023) 166. doi: 10.1007/s40820-023-01135-0
42. [42]
  M. Song, Q. Zhang, T. Shen, et al., Chin. Chem. Lett. 35 (2024) 109083. doi: 10.1016/j.cclet.2023.109083
43. [43]
  A. Zhao, J. Masa, W. Xia, J. Energy Chem. 23 (2014) 701–707. doi: 10.1016/S2095-4956(14)60202-3
44. [44]
  C. Wang, Q. Zhang, B. Yan, et al., Nano-Micro Lett. 15 (2023) 52. doi: 10.1007/s40820-023-01024-6
45. [45]
  K. He, Z. Huang, C. Chen, et al., Nano-Micro Lett. 16 (2023) 23.
46. [46]
  Z. Zeng, S. Küspert, S.E. Balaghi, et al., Small 19 (2023) 2205885. doi: 10.1002/smll.202205885
47. [47]
  J. Zhang, M. Zhang, W. Li, et al., J. Phys. Chem. C 112 (2008) 19506–19515. doi: 10.1021/jp8036523
48. [48]
  W. He, X. Zhang, K. Zheng, et al., Angew. Chem. Int. Ed. 62 (2023) e202213365. doi: 10.1002/anie.202213365
49. [49]
  N. Xu, K. Wang, Y. Zhu, Y. Zhang, Adv. Mater. 35 (2023) e2303173. doi: 10.1002/adma.202303173
50. [50]
  W. Wu, S. Bu, L. Bai, et al., Nanoscale 15 (2023) 5909–5918. doi: 10.1039/d2nr04952j
51. [51]
  T. Luo, J. Huang, Y. Hu, et al., Adv. Funct. Mater. 33 (2023) 2213058. doi: 10.1002/adfm.202213058
52. [52]
  L. Chen, S.I. Allec, M.T. Nguyen, et al., J. Am. Chem. Soc. 145 (2023) 10847–10860. doi: 10.1021/jacs.3c02326
53. [53]
  C. Wang, X. Liu, J. Wang, et al., Chin. Chem. Lett. 35 (2024) 108739. doi: 10.1016/j.cclet.2023.108739
54. [54]
  Y. Zhao, L. Tao, Chin. Chem. Lett. 35 (2024) 108571. doi: 10.1016/j.cclet.2023.108571
55. [55]
  S. Wu, X. Liu, X. Lian, et al., Adv. Mater. 30 (2018) 1802173. doi: 10.1002/adma.201802173
56. [56]
  S. Wang, T. Ding, T. Liu, et al., Angew. Chem. Int. Ed. 62 (2023) e202218630. doi: 10.1002/anie.202218630
57. [57]
  E.D. Corro, M. Taravillo, V.G. Baonza, Phys. Rev. B 85 (2012) 033407.
58. [58]
  S. Wan, Y. Chen, S. Fang, et al., Nat. Mater. 20 (2021) 624–631. doi: 10.1038/s41563-020-00892-2
59. [59]
  K.M. Naik, E. Higuchi, H. Inoue, Nanoscale 12 (2020) 11055–11062. doi: 10.1039/d0nr02092c
60. [60]
  M. Zhang, W. Guo, Y. Chen, et al., Chin. Chem. Lett. 34 (2023) 108229. doi: 10.1016/j.cclet.2023.108229
61. [61]
  H. Wei, X. Li, B. Deng, et al., Chin. J. Catal. 43 (2022) 1058–1065. doi: 10.1016/S1872-2067(21)63968-2
62. [62]
  J.Y. Yue, X.L. Ding, L.P. Song, et al., Micropor. Mesopor. Mat. 5 (2021) 3859–3866. doi: 10.1039/d1qm00314c
63. [63]
  F. Meng, X. Qin, L. Yang, et al., Small 18 (2022) 2203283. doi: 10.1002/smll.202203283
64. [64]
  Z. Wei, H. Wang, C. Zhang, et al., Angew. Chem. Int. Ed. 60 (2021) 16622–16627. doi: 10.1002/anie.202104856
65. [65]
  Y. Chen, L. Soler, M. Armengol-Profitós, et al., Appl. Catal. B 309 (2022) 121275. doi: 10.1016/j.apcatb.2022.121275
66. [66]
  W. He, X. Zhang, K. Zheng, et al., Angew. Chem. Int. Ed. 62 (2023) e202213365. doi: 10.1002/anie.202213365
67. [67]
  J. Cui, Z. Hao, Y. Wang, et al., Chem. Eng. J. 446 (2022) 136989. doi: 10.1016/j.cej.2022.136989
68. [68]
  O.A. Qamar, F. Jamil, M. Hussain, et al., Chem. Eng. J. 460 (2023) 141734. doi: 10.1016/j.cej.2023.141734
69. [69]
  X. Chen, M. Peng, X. Cai, et al., Nat. Commun. 12 (2021) 2664. doi: 10.1158/1078-0432.ccr-21-0936
70. [70]
  S. Ji, Y. Chen, G. Zhao, et al., Appl. Catal. B 304 (2022) 120922. doi: 10.1016/j.apcatb.2021.120922
71. [71]
  S. Weon, M. J Suh, C. Chu, et al., Environ. Sci. Technol. 1 (2021) 512–522. doi: 10.1021/acsestengg.0c00210
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Synergistic effects of oxygen vacancies and Pd single atoms on Pd@TiO2−x for efficient HER catalysis

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通讯作者: 陈斌, bchen63@163.com

Synergistic effects of oxygen vacancies and Pd single atoms on Pd@TiO_2−x for efficient HER catalysis