Citation: Dawei Han, Jing Xiong, Yitao Yang, Zhenpeng Wang, Qifeng Sun, Zhen Zhao, Yuechang Wei. Binary Ni-Ce active sites embedded on 3D ordered macro-mesoporous ZrO₂ for boosting coke-resistance dry reforming of methane[J]. Chinese Chemical Letters, ;2026, 37(11): 113210. doi: 10.1016/j.cclet.2026.113210 shu

Binary Ni-Ce active sites embedded on 3D ordered macro-mesoporous ZrO₂ for boosting coke-resistance dry reforming of methane

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State Key Laboratory of Heavy Oil Processing, Key Laboratory of Optical Detection Technology for Oil and Gas, China University of Petroleum, Beijing 102249, China

weiyc@cup.edu.cn

Received Date: 10 March 2026
Revised Date: 16 June 2026
Accepted Date: 13 July 2026
Available Online: 14 July 2026

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The coke-resistance property of industrial catalysts for dry reforming of methane (DRM) reaction is still a challenge. Herein, the multifunctional nanocatalysts of binary Ni-Ce active sites embedded on 3D ordered macro-mesoporous ZrO₂ (NiCeO_x/3DOMM-ZrO₂) were successfully fabricated by the carboxy-modified colloidal crystal templating (CMCCT)-impregnation method. 3DOMM structure can improve the mass transfer and diffusion of reactants (CH₄ and CO₂) in the pore channel, which can increase the contact efficiency between reactants and binary Ni-Ce active sites. The Ni-sites in binary Ni-Ce active components can activate the C—H bond dissociation of CH₄, while the oxygen vacancy of CeO_x-component can trap the oxygen atom in CO₂ reactant. NiCeO_x/3DOMM-ZrO₂ catalyst exhibits the highest catalytic activity and stability during DRM reaction in comparison with single Ni- or Ce-based catalysts, and its coke-resistance property is dependent on 3DOMM nanostructure of ZrO₂, i.e., its conversion rates of CH₄ and CO₂ remain above 91% at 750 °C for 50 h, and its apparent activation energy (E_a) decreases to 70.2 kJ/mol. Based on the results of the in situ DRIFTS and DFT, the catalytic mechanism of NiCeO_x/3DOMM-ZrO₂ catalyst for DRM was proposed: the synergy effect of binary Ni-Ce active sites can promote the rate key steps of C—H and C—O bond dissociation, and the formed coke in the macropores during DRM can accessibly react with the surface oxygen on the binary Ni-Ce active sites to CO, which effectively inhibits the formation of carbon deposits. It provides an effective strategy to develop high-efficient coke-resistance catalysts during DRM reaction.
- Ordered macro-mesoporous catalysts,
- Binary active sites,
- Dry reforming of methane,
- Synergy effect,
- Coke resistance
1. [1]
  Y. Tang, Y. Wei, Z. Wang, et al., J. Am. Chem. Soc. 141 (2019) 7283–7293. doi: 10.1021/jacs.8b10910
2. [2]
  L. Yao, M.E. Galvez, C. Hu, et al., Ind. Eng. Chem. Res. 57 (2018) 16645–16656. doi: 10.1021/acs.iecr.8b04183
3. [3]
  C. Palmer, D. Upham, S. Smart, et al., Nat. Catal. 3 (2020) 83–89. doi: 10.1038/s41929-019-0416-2
4. [4]
  S. Chen, J. Zaffram, B. Yang, ACS Catal. 10 (2020) 3074–3083. doi: 10.1021/acscatal.9b04429
5. [5]
  J. Deng, K. Bu, Y. Shen, et al., Appl. Catal. B 302 (2022) 120859. doi: 10.1016/j.apcatb.2021.120859
6. [6]
  Y. Wang, L. Yao, Y. Wang, et al., ACS Catal. 8 (2018) 6495–6506. doi: 10.1021/acscatal.8b00584
7. [7]
  I. Yentekakis, P. Panagiotopoulou, G. Artemakis, Appl. Catal. B 296 (2021) 120210. doi: 10.1016/j.apcatb.2021.120210
8. [8]
  L. Foppa, M. Silaghi, K. Larmier, et al., J. Catal. 343 (2016) 196–207. doi: 10.1016/j.jcat.2016.02.030
9. [9]
  D. Liu, X. Quek, W. Cheo, et al., J. Catal. 266 (2009) 380–390. doi: 10.1016/j.jcat.2009.07.004
10. [10]
  P. Wu, Y. Tao, H. Ling, et al., ACS Catal. 9 (2019) 10060–10069. doi: 10.1021/acscatal.9b02286
11. [11]
  W. Cai, L. Qian, B. Yue, et al., Chin. Chem. Lett. 25 (2014) 1411–1415. doi: 10.1016/j.cclet.2014.06.016
12. [12]
  Q. Zhu, H. Zhou, L. Wang, et al., Nat. Catal. 5 (2022) 1030–1037. doi: 10.1038/s41929-022-00870-8
13. [13]
  P. Djinović, A. Pintar, Appl. Catal. B 206 (2017) 675–682. doi: 10.1016/j.apcatb.2017.01.064
14. [14]
  Y. Lu, D. Guo, Y. Zhao, et al., J. Catal. 396 (2021) 65–80. doi: 10.3390/foods11010065
15. [15]
  L. Buelens, V. Galvita, H. Poelman, et al., Science 354 (2016) 449–452. doi: 10.1126/science.aah7161
16. [16]
  W. Cai, L. Qian, B. Yue, et al., Chin. Chem. Lett. 24 (2013) 777–779. doi: 10.1016/j.cclet.2013.05.034
17. [17]
  J. Xiong, Z. Li, P. Zhang, et al., Chin. Chem. Lett. 32 (2021) 1447–1450. doi: 10.1016/j.cclet.2020.10.014
18. [18]
  S. Lin, J. Wang, Y. Mi, et al., Chin. J. Catal. 42 (2021) 1808–1820. doi: 10.1016/S1872-2067(21)63789-0
19. [19]
  J. Zhang, X. Liu, Y. Pan, et al., Energy Fuels 39 (2025) 24320–24332. doi: 10.1021/acs.energyfuels.5c04173
20. [20]
  M. Hosseinpour, T. Moser, B. Klötzer, et al., ACS Catal. 15 (2025) 3314–3327. doi: 10.1021/acscatal.4c06230
21. [21]
  H. Jiao, G. Wang, ACS Catal. 15 (2025) 3846–3859. doi: 10.1021/acscatal.4c05758
22. [22]
  L. Teh, H. Setiabudi, S. Timmiati, et al., Chem. Eng. Sci. 242 (2021) 116606. doi: 10.1016/j.ces.2021.116606
23. [23]
  H. Ay, D. Üner, Appl. Catal. B 179 (2015) 128–138. doi: 10.1016/j.apcatb.2015.05.013
24. [24]
  X. Zhang, J. Deng, M. Pupucevski, et al., ACS Catal. 11 (2021) 12087–12095. doi: 10.1021/acscatal.1c02124
25. [25]
  Z. Ni, X. Djitcheu, X. Gao, et al., Sci. Rep. 12 (2022) 5344. doi: 10.1038/s41598-022-09291-w
26. [26]
  D. Kim, K. Stowe, F. Muller, et al. J. Catal. 247 (2007) 101–111. doi: 10.1016/j.jcat.2007.01.011
27. [27]
  J. Gao, J. Yang, T. Ma, et al., Chin. Chem. Lett. 34 (2023) 108395. doi: 10.1016/j.cclet.2023.108395
28. [28]
  P. Lustemberg, Z. Mao, A. Salcedo, et al., ACS Catal. 11 (2021) 10604–10613. doi: 10.1021/acscatal.1c02154
29. [29]
  P. Zhang, X. Mei, X. Zhao, et al., Environ. Sci. Technol. 55 (2021) 11245–11254. doi: 10.1021/acs.est.1c01781
30. [30]
  D. Guo, M. Li, Y. Lu, et al., ACS Catal. 12 (2022) 316–330. doi: 10.1021/acscatal.1c04004
31. [31]
  M. Li, Z. Sun, Y. Hu, et al., J. Mater. Chem. A 9 (2021) 12495–12520. doi: 10.1039/d1ta00440a
32. [32]
  D. Pakhare, J. Spivey, Chem. Soc. Rev. 43 (2014) 7813–7837. doi: 10.1039/C3CS60395D
33. [33]
  W. Chen, G. Zhao, Q. Xue, et al., Appl. Catal. B 136-137 (2013) 260–268. doi: 10.1016/j.apcatb.2013.01.044
34. [34]
  M. Grabchenko, G. Pantaleo, F. Puleo, et al., Catal. Today 382 (2021) 71–81. doi: 10.1016/j.cattod.2021.07.012
35. [35]
  M. Yusuf, M. Beg, M. Ubaidullah, et al., Int. J. Hydrog. Energy 47 (2022) 42150–42159. doi: 10.1016/j.ijhydene.2021.08.021
36. [36]
  K. Bu, J. Deng, X. Zhang, et al., Appl. Catal. B 267 (2020) 118692. doi: 10.1016/j.apcatb.2020.118692
37. [37]
  S. Zhao, S. Wang, Y. Zhao, et al., Chin. Chem. Lett. 28 (2017) 65–69. doi: 10.1016/j.cclet.2016.06.003
38. [38]
  Y. Wang, L. Li, G. Li, et al., ACS Catal. 13 (2023) 6486–6496. doi: 10.1021/acscatal.2c06412
39. [39]
  D. He, J. Yan, K. Chen, et al., ACS Catal. 13 (2023) 12114–12124. doi: 10.1021/acscatal.3c00752
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2. [2]
  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
3. [3]
  Junchuan Sun , Lu Wang . Carbon exchange enabled supra-photothermal methane dry reforming. Chinese Journal of Structural Chemistry, 2024, 43(10): 100330-100330. doi: 10.1016/j.cjsc.2024.100330
4. [4]
  Fanxin Kong , Hongzhi Wang , Huimei Duan . Inhibition effect of sulfation on Pt/TiO2 catalysts in methane combustion. Chinese Journal of Structural Chemistry, 2024, 43(5): 100287-100287. doi: 10.1016/j.cjsc.2024.100287
5. [5]
  Xu He , Wenjie Gao , Jinglei Xu , Zhanjun Cheng , Wenchao Peng , Beibei Yan , Guanyi Chen , Ning Li . Machine learning-assisted construction of C=O and pyridinic N active sites in sludge-based catalysts. Chinese Chemical Letters, 2025, 36(12): 111019-. doi: 10.1016/j.cclet.2025.111019
6. [6]
  Shaoqing Du , Xinyong Liu , Xueping Hu , Peng Zhan . Targeting novel sites represents an effective strategy for combating drug resistance. Chinese Chemical Letters, 2025, 36(1): 110378-. doi: 10.1016/j.cclet.2024.110378
7. [7]
  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
8. [8]
  Tao Ban , Xi-Yang Yu , Hai-Kuo Tian , Zheng-Qing Huang , Chun-Ran Chang . One-step conversion of methane and formaldehyde to ethanol over SA-FLP dual-active-site catalysts: A DFT study. Chinese Chemical Letters, 2024, 35(4): 108549-. doi: 10.1016/j.cclet.2023.108549
9. [9]
  Mengli Xu , Zhenmin Xu , Zhenfeng Bian . Achieving Ullmann coupling reaction via photothermal synergy with ultrafine Pd nanoclusters supported on mesoporous TiO2. Chinese Journal of Structural Chemistry, 2024, 43(7): 100305-100305. doi: 10.1016/j.cjsc.2024.100305
10. [10]
  Xuan Liu , Qing Li . Tailoring interatomic active sites for highly selective electrocatalytic biomass conversion reaction. Chinese Chemical Letters, 2025, 36(4): 110670-. doi: 10.1016/j.cclet.2024.110670
11. [11]
  Zhili Yang , Liqun Liu , Xuebi Rao , Zeyu Jin , Jialin Sun , Yongkang Zhu , Shiming Zhang . Deprotonation effect doubles active site density in Fe-N₄-C catalyst for oxygen reduction electrocatalysis. Chinese Chemical Letters, 2025, 36(11): 111440-. doi: 10.1016/j.cclet.2025.111440
12. [12]
  Lan Tang , Ji Chen , Yucheng Wu , Linxin Qi , Xingyi Tian , Ming Li , Wenbin Wang , Rongxing He . Interface effect induced electron-deficient Ni sites for efficient glycerol electrooxidation. Chinese Chemical Letters, 2026, 37(6): 111001-. doi: 10.1016/j.cclet.2025.111001
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  Heng Gao , Zhaocong Cheng , Guangshui Tu , Zonglin Qiu , Xieyi Xiao , Haotian Zhou , Handou Zheng , Haiyang Gao . Thermally robust bis(imino)pyridyl iron catalysts for ethylene polymerization: Synergy effects of weak π-π interaction, steric bulk, and electronic tuning. Chinese Chemical Letters, 2025, 36(5): 110762-. doi: 10.1016/j.cclet.2024.110762
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  Weiping Xiao , Yuhang Chen , Qin Zhao , Danil Bukhvalov , Caiqin Wang , Xiaofei Yang . Constructing the synergistic active sites of nickel bicarbonate supported Pt hierarchical nanostructure for efficient hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(12): 110176-. doi: 10.1016/j.cclet.2024.110176
17. [17]
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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

Binary Ni-Ce active sites embedded on 3D ordered macro-mesoporous ZrO2 for boosting coke-resistance dry reforming of methane

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通讯作者: 陈斌, bchen63@163.com

Binary Ni-Ce active sites embedded on 3D ordered macro-mesoporous ZrO₂ for boosting coke-resistance dry reforming of methane