Citation: Shibo Zhang, Xiang Chu, Meng Zhao, Baokang Geng, Xiao Wang, Shuyan Song, Hongjie Zhang. Ba-doping to modulate surface electronic states in Eu_0.9Ba_0.1O_x catalysts for oxidation coupling of methane[J]. Chinese Chemical Letters, ;2026, 37(7): 111126. doi: 10.1016/j.cclet.2025.111126 shu

Ba-doping to modulate surface electronic states in Eu_0.9Ba_0.1O_x catalysts for oxidation coupling of methane

Shibo Zhang ^{a, b} ,
Xiang Chu ^{a, b} ,
Meng Zhao ^{a, *,} ,
Baokang Geng ^{a, b} ,
Xiao Wang ^{a, b, *,} ,
Shuyan Song ^{a, b, *,} ,
Hongjie Zhang ^{a, b, c, *,}

a.
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
c.
Department of Chemistry, Tsinghua University, Beijing 100084, China

Received Date: 11 January 2025
Revised Date: 14 March 2025
Accepted Date: 20 March 2025
Available Online: 20 March 2025

Figures(4)

The oxidative coupling reaction of methane (OCM) process offers a promising pathway for the direct conversion of methane into high value C₂ hydrocarbons (C₂H₆ and C₂H₄), albeit facing the challenges of harsh reaction conditions and competing overoxidation reaction. Herein, Ba-doped Eu₂O₃ synthesized via the spray pyrolysis method was employed as highly active dopant catalyst for the methane oxidative coupling reaction. The prepared Eu_0.9Ba_0.1O_x catalyst showed satisfactory reactivity and stability, with a C₂₊ product selectivity of 52.4%, a C₂₊ yield of 16.2%, and a stabilization time of at least 100 h. The incorporation of Ba atoms into Eu₂O₃ lattice leads to an increased molar ratio of Eu²⁺/Eu³⁺ and a higher oxygen vacancies (O_v) concentration. Such modulation of surface electronic state significantly improves the adsorption and activation behavior of oxygen, thereby accelerating the production of reactive oxygen species (O₂⁻). Meanwhile, the acid-base properties of Eu₂O₃ substrate also undergo obvious alteration with more basic site generation after Ba doping, which is conducive to the stabilization activated oxygen. O₂⁻ substances can promote the activation of methane into methyl radicals, and also facilitate the dehydrogenation of ethane into ethylene, thus improving the catalytic activity.
- Oxidative coupling of methane,
- Spray pyrolysis,
- Ba-doping,
- Oxygen vacancies,
- Europium oxide
1. [1]
  X. Sun, G. Liu, T. Shen, et al., Small 20 (2024) e2310857. doi: 10.1002/smll.202310857
2. [2]
  M. Li, A.C. van Veen, Appl. Catal. B: Environ. 237 (2018) 641–648. doi: 10.1016/j.apcatb.2018.06.032
3. [3]
  S.R. Patlolla, K. Katsu, A. Sharafian, et al., Renew. Sust. Energ. Rev. 181 (2023) 113323. doi: 10.1016/j.rser.2023.113323
4. [4]
  J. Kim, M. Ferree, S. Gunduz, et al., ChemCatChem 15 (2023) 122026.
5. [5]
  P. Wang, R. Shi, Y. Zhao, et al., Angew. Chem. Int. Ed. 62 (2023) e202304301. doi: 10.1002/anie.202304301
6. [6]
  Y. Wang, G. Hong, Y. Zhang, et al., Angew. Chem. Int. Ed. 62 (2023) e202310525. doi: 10.1002/anie.202310525
7. [7]
  A.L.A. Marinho, F.S. Toniolo, F.B. Noronha, et al., Appl. Catal. B: Environ. 281 (2021) 119459. doi: 10.1016/j.apcatb.2020.119459
8. [8]
  A.L.A. Marinho, R.C. Rabelo-Neto, F. Epron, et al., Appl. Catal. B: Environ. 268 (2020) 118387. doi: 10.1016/j.apcatb.2019.118387
9. [9]
  N. Sun, J. Zhang, L. Ling, et al., Fuel 354 (2023) 129398. doi: 10.1016/j.fuel.2023.129398
10. [10]
  J. Kim, Y.J. Kim, M. Ferree, et al., Appl. Catal. B: Environ. 321 (2023) 122026. doi: 10.1016/j.apcatb.2022.122026
11. [11]
  A. Zanina, V.A. Kondratenko, H. Lund, et al., ACS Catal. 12 (2022) 15361–15372. doi: 10.1021/acscatal.2c04916
12. [12]
  C. Karakaya, R.J. Kee, Prog. Energy Combust. Sci. 55 (2016) 60–97. doi: 10.1016/j.pecs.2016.04.003
13. [13]
  Y. Jiang, H. Fu, Z. Liang, et al., Chem. Soc. Rev. 53 (2024) 714–763. doi: 10.1039/d3cs00708a
14. [14]
  X. Wu, X. Wang, L. Zhang, et al., Angew. Chem. Int. Ed. 63 (2024) e202317594. doi: 10.1002/anie.202317594
15. [15]
  K. Zhao, Y. Gao, X. Wang, et al., Nat. Commun. 14 (2023) 7749. doi: 10.1038/s41467-023-43682-5
16. [16]
  J. Xu, Y. Zhang, X. Xu, et al., ACS Catal. 9 (2019) 4030–4045. doi: 10.1021/acscatal.9b00022
17. [17]
  K. Wang, M. Lv, T. Si, et al., J. Hazard. Mater. 461 (2024) 132479. doi: 10.1016/j.jhazmat.2023.132479
18. [18]
  Y. Gambo, A.A. Jalil, S. Triwahyono, et al., J. Ind. Eng. Chem. 59 (2018) 218–229. doi: 10.1016/j.jiec.2017.10.027
19. [19]
  Y. Ivanova, R. Petrov, S. Reshetnikov, et al., Mater. Today Chem. 26 (2022) 101124. doi: 10.1016/j.mtchem.2022.101124
20. [20]
  Y. Sim, J. Yoo, J.M. Ha, et al., J. Energy Chem. 35 (2019) 1–8.
21. [21]
  Z. Zhang, Y. Gong, J. Xu, et al., Catal. Today 400-401 (2022) 73–81. doi: 10.1016/j.cattod.2021.11.012
22. [22]
  H. Du, K. Huang, M. Li, et al., Nano Res. 11 (2018) 1490–1499. doi: 10.1007/s12274-017-1766-1
23. [23]
  J. Leng, Z. Wang, J. Wang, et al., Chem. Soc. Rev. 48 (2019) 3015–3072. doi: 10.1039/c8cs00904j
24. [24]
  K. Yuan, Y.W. Zhang, Inorg. Chem. Front. 7 (2020) 4256–4280. doi: 10.1039/d0qi00750a
25. [25]
  M. Luo, M. Wang, W. Niu, et al., Chem. Eng. J. 412 (2021) 128471. doi: 10.1016/j.cej.2021.128471
26. [26]
  M.V. Abrashev, N.D. Todorov, J. Appl. Phys. 116 (2014) 103508. doi: 10.1063/1.4894775
27. [27]
  J. Ibáñez, O. Blázquez, S. Hernández, et al., J. Raman Spectrosc. 49 (2018) 2021–2027. doi: 10.1002/jrs.5488
28. [28]
  S.M. Wu, X.L. Liu, X.L. Lian, et al., Adv. Mater. 30 (2018) e1802173. doi: 10.1002/adma.201802173
29. [29]
  R. Feng, P. Niu, B. Hou, et al., J. Energy Chem. 67 (2022) 342–353. doi: 10.1016/j.jechem.2021.10.018
30. [30]
  C. Zheng, J. Feng, Z. Wei, et al., Chem. Eng. J. 467 (2023) 143390. doi: 10.1016/j.cej.2023.143390
31. [31]
  M. Wang, P. Guo, Y. Zhang, et al., J. Hazard. Mater. 349 (2018) 224–233. doi: 10.1016/j.jhazmat.2018.01.058
32. [32]
  Y. Zhu, X. Wu, Z. Wu, et al., Adv. Funct. Mater. 34 (2024) 2409324. doi: 10.1002/adfm.202409324
33. [33]
  T. Wu, Y. Wei, J. Xiong, et al., J. Energy Chem. 91 (2024) 331–344. doi: 10.1016/j.jechem.2023.12.025
34. [34]
  T. Wu, P. Zhang, Y. Wei, et al., ACS Catal. 14 (2024) 1882–1902. doi: 10.1021/acscatal.3c05094
35. [35]
  R.S. Pal, S. Rana, S.K. Sharma, et al., Chem. Eng. J. 458 (2023) 141379. doi: 10.1016/j.cej.2023.141379
1. [1]
  Jincheng Zhang , Mengjie Sun , Jiali Ren , Rui Zhang , Min Ma , Qingzhong Xue , Jian Tian . Oxygen vacancies-rich molybdenum tungsten oxide nanowires as a highly active nitrogen fixation electrocatalyst. Chinese Chemical Letters, 2025, 36(1): 110491-. doi: 10.1016/j.cclet.2024.110491
2. [2]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
3. [3]
  Junhao Dai , Zhu He , Xinhai Li , Guochun Yan , Hui Duan , Guangchao Li , Zhixing Wang , Huajun Guo , Wenjie Peng , Jiexi Wang . Ultrafast spray pyrolysis for synthesizing uniform Mg-doped LiNi_0.9Co_0.05Mn_0.05O₂. Chinese Chemical Letters, 2025, 36(6): 110063-. doi: 10.1016/j.cclet.2024.110063
4. [4]
  Jinli Chen , Shouquan Feng , Tianqi Yu , Yongjin Zou , Huan Wen , Shibin Yin . Modulating Metal-Support Interaction Between Pt3Ni and Unsaturated WOx to Selectively Regulate the ORR Performance. Chinese Journal of Structural Chemistry, 2023, 42(10): 100168-100168. doi: 10.1016/j.cjsc.2023.100168
5. [5]
  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. Chinese Chemical Letters, 2025, 36(6): 110309-. doi: 10.1016/j.cclet.2024.110309
6. [6]
  Fengchen Wang , Yujia Xiang , Yuqi Zhang , Xin Zhou , Jing Zhang , Chuanshu He , Heng Zhang , Zhaokun Xiong , Peng Zhou , Hongyu Zhou , Yang Liu , Bo Lai . A comprehensive review on oxygen vacancies modified catalysts: Synthesis, characterization, and crucial role in catalytic ozonation. Chinese Chemical Letters, 2026, 37(2): 111315-. doi: 10.1016/j.cclet.2025.111315
7. [7]
  Zihou Zhang , Haozhe Xu , Yuxiang Wang , Pin Fang , Olga Demidenko , Yujing Li . Dynamically stabilized PtCuNi/C catalyst enabled by oxygen vacancies in WO_3-x. Chinese Chemical Letters, 2026, 37(5): 110889-. doi: 10.1016/j.cclet.2025.110889
8. [8]
  Mengxiang Zhu , Tao Ding , Yunzhang Li , Yuanjie Peng , Ruiping Liu , Quan Zou , Leilei Yang , Shenglei Sun , Pin Zhou , Guosheng Shi , Dongting Yue . Graphene controlled solid-state growth of oxygen vacancies riched V₂O₅ catalyst to highly activate Fenton-like reaction. Chinese Chemical Letters, 2024, 35(12): 109833-. doi: 10.1016/j.cclet.2024.109833
9. [9]
  Huizhong Wu , Ruiheng Liang , Ge Song , Zhongzheng Hu , Xuyang Zhang , Minghua Zhou . Enhanced interfacial charge transfer on Bi metal@defective Bi₂Sn₂O₇ quantum dots towards improved full-spectrum photocatalysis: A combined experimental and theoretical investigation. Chinese Chemical Letters, 2024, 35(6): 109131-. doi: 10.1016/j.cclet.2023.109131
10. [10]
  Jianing He , Xiao Wang , Zijian Wang , Ruize Jiang , Ke Wang , Rui Zhang , Huilin Wang , Baokang Geng , Hongyi Gao , Shuyan Song , Hongjie Zhang . Investigation on Cu promotion effect on Ce-based solid solution-anchored Rh single atoms for three-way catalysis. Chinese Chemical Letters, 2025, 36(2): 109640-. doi: 10.1016/j.cclet.2024.109640
11. [11]
  Longsheng Zhan , Yuchao Wang , Mengjie Liu , Xin Zhao , Danni Deng , Xinran Zheng , Jiabi Jiang , Xiang Xiong , Yongpeng Lei . BiVO₄ as a precatalyst for CO₂ electroreduction to formate at large current density. Chinese Chemical Letters, 2025, 36(3): 109695-. doi: 10.1016/j.cclet.2024.109695
12. [12]
  Ruiheng Liang , Huizhong Wu , Zhongzheng Hu , Ge Song , Xuyang Zhang , Omotayo A. Arotiba , Minghua Zhou . Hierarchical Fe-Bi/Bi₇O₉I₃/OVs microspheres coupled with natural air diffusion electrode to achieve efficient heterogeneous visible-light-driven photoelectro-Fenton degradation of tetracycline without aeration. Chinese Chemical Letters, 2025, 36(4): 110136-. doi: 10.1016/j.cclet.2024.110136
13. [13]
  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
14. [14]
  Qijun Tang , Wenguang Tu , Yong Zhou , Zhigang Zou . High efficiency and selectivity catalyst for photocatalytic oxidative coupling of methane. Chinese Journal of Structural Chemistry, 2023, 42(12): 100170-100170. doi: 10.1016/j.cjsc.2023.100170
15. [15]
  Zhuwei Yang , Linsen Li , Yijie Lin , Xinyuan Tao , Xiao Liu , Lei Chen , Ming Ma , Li Lin , Riguang Zhang , Jiayuan Li , Zhao Jiang . Regulating the Oxygen Vacancies in Ni-CexZr1-xO2/ZSM-5 to Improve the Long-term Stability for Methane Dry Reforming. Chinese Journal of Structural Chemistry, 2025, 44(8): 100632-100632. doi: 10.1016/j.cjsc.2025.100632
16. [16]
  Deyun Ma , Fenglan Liang , Qingquan Xue , Yanping Liu , Chunqiang Zhuang , Shijie Li . Interfacial engineering of Cd_0.5Zn_0.5S/BiOBr S-scheme heterojunction with oxygen vacancies for effective photocatalytic antibiotic removal. Acta Physico-Chimica Sinica, 2025, 41(12): 100190-0. doi: 10.1016/j.actphy.2025.100190
17. [17]
  Bei Li , Zhaoke Zheng . In situ monitoring of the spatial distribution of oxygen vacancies at the single-particle level. Chinese Journal of Structural Chemistry, 2024, 43(10): 100331-100331. doi: 10.1016/j.cjsc.2024.100331
18. [18]
  Yi Herng Chan , Zhe Phak Chan , Serene Sow Mun Lock , Chung Loong Yiin , Shin Ying Foong , Mee Kee Wong , Muhammad Anwar Ishak , Ven Chian Quek , Shengbo Ge , Su Shiung Lam . Thermal pyrolysis conversion of methane to hydrogen (H₂): A review on process parameters, reaction kinetics and techno-economic analysis. Chinese Chemical Letters, 2024, 35(8): 109329-. doi: 10.1016/j.cclet.2023.109329
19. [19]
  Siyang Xue , Chen Cheng , Jieqiong Kang , Kaixuan Zheng , Adela Jing Li , Renli Yin . Oxygen vacancies-rich BiOBr bridged direct electron transfer with peroxymonosulfate for integrating superoxide radical and singlet oxygen on selective pollutants degradation. Chinese Chemical Letters, 2025, 36(10): 110776-. doi: 10.1016/j.cclet.2024.110776
20. [20]
  Zhiling Du , Zhiqi Zhou , Nan Sun , Cailiang Yue , Fuqiang Liu . Pyromellitic diimide induced TiO₂ mesocrystals with oxygen vacancies for synergistic photocatalytic H₂O₂ production and antibiotics degradation. Chinese Chemical Letters, 2026, 37(3): 111341-. doi: 10.1016/j.cclet.2025.111341

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(15)
HTML views(0)

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

Ba-doping to modulate surface electronic states in Eu0.9Ba0.1Ox catalysts for oxidation coupling of methane

Metrics

通讯作者: 陈斌, bchen63@163.com

Ba-doping to modulate surface electronic states in Eu_0.9Ba_0.1O_x catalysts for oxidation coupling of methane