Citation: Jiadong Li, Yanduo Liu, Yang Qu. Highly efficient methane-to-low alcohols conversion via ZnO based photocatalysis in aqueous medium[J]. Chinese Chemical Letters, ;2026, 37(1): 111741. doi: 10.1016/j.cclet.2025.111741 shu

Highly efficient methane-to-low alcohols conversion via ZnO based photocatalysis in aqueous medium

Jiadong Li ^{a, c, *,} ,
Yanduo Liu ^{b, *,} ,
Yang Qu ^{c, *,}

a.
School of New Energy, Ningbo University of Technology, Ningbo 315336, China
b.
School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, China
c.
Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education), School of Chemistry and Materials Science, International Joint Research Center for Catalytic Technology, Heilongjiang University, Harbin 150080, China

lijd@nbut.edu.cn

liuyd0608@163.com

quyang@hlju.edu.cn

Received Date: 2 April 2025
Revised Date: 28 June 2025
Accepted Date: 18 August 2025
Available Online: 18 August 2025

Figures(5)

The photocatalytic oxidation of methane (CH₄) to valuable chemicals like low alcohols (CH₃OH and C₂H₅OH) represents a significant technological advancement with implications for energy conversion and environmental purification. A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes, which can lead to over-oxidation and reduced selectivity and efficiency. To address these issues, we have developed a sodium-doped zinc oxide (Na-ZnO) modified with cobalt oxide (CoO) catalyst. This catalyst has demonstrated excellent performance in converting methane to low alcohols, achieving a yield of 130 µmol g⁻¹ h⁻¹ and a selectivity of up to 96 %. The doping of Na in ZnO significantly enhances methane adsorption, while the surface-modified CoO effectively captures photogenerated holes, activates water molecules, and uses hydroxyl radicals to activate methane, thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products. This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols, offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
- ZnO nanosheets,
- Photocatalytic oxidation methane,
- Sodium-doped zinc oxide,
- Cobalt oxide,
- Hydroxyl radicals
1. [1]
  C.Q. Han, Y.H. Cao, W. Yu, et al., J. Am. Chem. Soc. 145 (2023) 8609–8620. doi: 10.1021/jacs.3c01317
2. [2]
  J. Duan, S.Y. Fan, X.Y. Li, et al., Chem. Eng. J. 485 (2024) 149904.
3. [3]
  Z.S. Yang, Q.Q. Zhang, H. Song, et al., Chin. Chem. Lett. 35 (2024) 108418.
4. [4]
  Y.H. Jiang, Y.Y. Fan, X.L. Liu, et al., J. Am. Chem. Soc. 146 (2024) 16039–16051. doi: 10.1021/jacs.4c03083
5. [5]
  L.Q. Li, X.W. Shi, L.Y. Liu, et al., Small 21 (2025) 2500835.
6. [6]
  R.X. Zhang, J.L. Shi, L. Fu, et al., ACS Nano. 18 (2024) 12994–13005. doi: 10.1021/acsnano.4c01318
7. [7]
  Z.Y. Huang, C. Guo, Q.X. Zheng, et al., Chin. Chem. Lett. 35 (2024) 109580.
8. [8]
  Y.H. Zhi, C. Gu, H.C. Ji, et al., Chin. Chem. Lett. 36 (2025) 110234.
9. [9]
  S.Y. Nie, L. Wu, X. Wang. J. Am. Chem. Soc. 145 (2023) 23681–23690. doi: 10.1021/jacs.3c07984
10. [10]
  J. Ding, Z.Y. Teng, X.Z. Su, et al., Chem 9 (2023) 1017–1035.
11. [11]
  Q. Zhang, C. Yang, Y.S. Chen, et al., Angew. Chem. Int. Ed. 64 (2025) e202419282.
12. [12]
  T. Luo, Y. Peng, L. Chen, et al., Environ. Sci. Technol. 54 (2020) 10261–10269. doi: 10.1021/acs.est.9b07078
13. [13]
  Y.D. Liu, Y.H. Chen, W.B. Jiang, et al., Research 2022 (2022) 9831340. doi: 10.34133/2022/9831340
14. [14]
  E. Han, Y.G. Kim, H.M. Yang, et al., Chem. Mater. 30 (2018) 5777–5785. doi: 10.1021/acs.chemmater.8b02782
15. [15]
  T. Ito, J.X. Wang, C.H. Lin, et al., J. Am. Chem. Soc. 107 (1985) 5062–5068. doi: 10.1021/ja00304a008
16. [16]
  W.F. Kong, Z.P. Xing, B. Fang, et al., Appl. Catal. B: Environ. 304 (2022) 120969.
17. [17]
  Q.Y. Wang, M.Y. Dai, H.M. Li, et al., Adv. Mater. 35 (2023) 2300695.
18. [18]
  W.Y. Zhang, A. Mehmood, G. Ali, et al., Angew. Chem. Int. Ed. 64 (2025) e202424552.
19. [19]
  Q.Y. Wang, T. Luo, X.Y. Cao, et al., Nat. Commun. 16 (2025) 2985.
20. [20]
  D.X. Song, M.X. Li, F. Yang, et al., Chin. Chem. Lett. 35 (2024) 108591.
21. [21]
  Y. Hu, X.B. Li, W.W. Wang, et al., Chin. J. Struct. Chem. 41 (2022) 2206069–2206078.
22. [22]
  G.Y. Zhai, S.Y. Yang, Y.H. Chen, et al., J. Am. Chem. Soc. 147 (2025) 2444–2454. doi: 10.1021/jacs.4c12758
23. [23]
  Z.L. Ma, Y.H. Chen, C. Gao, et al., Chem. Commun. 60 (2024) 1132–1135. doi: 10.1039/d3cc04645a
24. [24]
  X.Y. Li, C. Wang, J.W. Tang. Nat. Rev. Mater. 7 (2022) 617–632.
25. [25]
  X.Z. Deng, Y. Ke, J.W. Ding, et al., Chin. Chem. Lett. 35 (2024) 109064.
26. [26]
  B.T. Song, Y.H. Li, X.P. Wu, et al., J. Am. Chem. Soc. 144 (2022) 23340–23351. doi: 10.1021/jacs.2c08356
27. [27]
  X.L. Zhou, Y.R. Zhong, M. Yang, et al., ACS Appl. Mater. Interfaces 7 (2015) 12022–12029. doi: 10.1021/acsami.5b02152
28. [28]
  Y.F. Li, L. Lin, L.J. Gao, et al., J. Phys. Chem. C. 125 (2021) 7990–7998. doi: 10.1021/acs.jpcc.1c01203
29. [29]
  Y.D. Liu, M.W. Li, J.N. Guo, et al., J. Colloid. Interface Sci. 667 (2024) 23–31.
30. [30]
  D. Saikia, J.R. Deka, Y.C. Chen, et al., Ceram. Int. 51 (2025) 22498–22510.
31. [31]
  J.D. Li, X.L. Zhang, F. Raziq, et al., Appl. Catal. B: Environ. 218 (2017) 60–67. doi: 10.3901/JME.2017.17.060
32. [32]
  J.T. Lu, H.W. Zhang, S. Li, et al., Inorg. Chem. 59 (2020) 3152–3159. doi: 10.1021/acs.inorgchem.9b03512
33. [33]
  X. Guo, X.J. Sun, Z.Y. Wang, et al., Fuel 343 (2023) 128004.
34. [34]
  Y.D. Liu, N. Sun, S.Y. Chen, et al., Nano Res. 11 (2018) 1612–1624. doi: 10.1007/s12274-017-1776-z
35. [35]
  Y.D. Liu, J.D. Li, X.L. Dong, et al., Inorg. Chem. Front. 11 (2024) 5310–5318. doi: 10.1039/d4qi01381f
36. [36]
  H. Wang, Y.S. Hu, Y.L. Shen, et al., ACS Catal. 14 (2024) 10712–10727. doi: 10.1021/acscatal.4c02608
37. [37]
  J.A. Rodriguez, N. Rui, F. Zhang, et al., ACS Catal. 12 (2022) 5470–5488. doi: 10.1021/acscatal.2c00941
38. [38]
  S. Kim, J. Lauterbach, E. Sasmaz. ACS Catal. 11 (2021) 8247–8260. doi: 10.1021/acscatal.1c01223
39. [39]
  R. Davì, G. Carraro, M. Stojkovska, et al., Phys. Chem. Chem. Phys. 24 (2022) 28486–28494. doi: 10.1039/d2cp03441g
40. [40]
  E.J. Jang, J. Lee, D.G. Oh, et al., ACS Catal. 11 (2021) 5894–5905. doi: 10.1021/acscatal.1c00156
41. [41]
  W.B. Jiang, J.X. Low, K.K. Mao, et al., J. Am. Chem. Soc. 143 (2021) 269–278. doi: 10.1021/jacs.0c10369
42. [42]
  W.Q. Zhang, D.W. Xi, Y.H. Chen, et al., Nat. Commun. 14 (2023) 3047.
1. [1]
  Yanjie Li , Chaoqun Qu , Siqi Meng , Jiaqi Hu , Ze Gao , Hongji Xu , Rui Gao , Ming Feng . Revealing electronic state evolution of Co(Ⅱ)/Co(Ⅲ) in CoO (111) plane during OER process through magnetic measurement. Chinese Chemical Letters, 2025, 36(3): 109872-. doi: 10.1016/j.cclet.2024.109872
2. [2]
  Haoyu Luo , Jinsong Chen , Mengfei Luo , Hui Ma , Shengyan Pu . Heterogeneous Fenton catalytic degradation of nitrobenzene by controlled-release nano calcium peroxide. Chinese Chemical Letters, 2025, 36(6): 110367-. doi: 10.1016/j.cclet.2024.110367
3. [3]
  Xifeng Lu , Pei Su . Design and application of metal-organic frameworks derivatives as 3-electron ORR electrocatalysts for ^•OH generation in wastewater treatment: A review. Chinese Chemical Letters, 2025, 36(11): 110909-. doi: 10.1016/j.cclet.2025.110909
4. [4]
  Guanjun Chen , Jiayi Yang , Zheming Huang , Long Chen , Wenyuan Duan , Tong Wang , Xingang Kong , Haibo Yang . Engineering the interlayer sodium density in layered sodium cobalt oxide for boosted chlorine evolution reaction. Chinese Chemical Letters, 2025, 36(12): 111662-. doi: 10.1016/j.cclet.2025.111662
5. [5]
  Wenjing Dai , Lan Luo , Zhen Yin . Interface reconstruction of hybrid oxide electrocatalysts for seawater oxidation. Chinese Journal of Structural Chemistry, 2025, 44(3): 100442-100442. doi: 10.1016/j.cjsc.2024.100442
6. [6]
  Yang Li , Xiaoxu Liu , Tianyi Ji , Man Zhang , Xueru Yan , Mengjie Yao , Dawei Sheng , Shaodong Li , Peipei Ren , Zexiang Shen . Potassium ion doped manganese oxide nanoscrolls enhanced the performance of aqueous zinc-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109551-. doi: 10.1016/j.cclet.2024.109551
7. [7]
  Jiayu Bai , Songjie Hu , Lirong Feng , Xinhui Jin , Dong Wang , Kai Zhang , Xiaohui Guo . Manganese vanadium oxide composite as a cathode for high-performance aqueous zinc-ion batteries. Chinese Chemical Letters, 2024, 35(9): 109326-. doi: 10.1016/j.cclet.2023.109326
8. [8]
  Tian TIAN , Meng ZHOU , Jiale WEI , Yize LIU , Yifan MO , Yuhan YE , Wenzhi JIA , Bin HE . Ru-doped Co₃O₄/reduced graphene oxide: Preparation and electrocatalytic oxygen evolution property. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 385-394. doi: 10.11862/CJIC.20240298
9. [9]
  Chunrui Zhao , Tianren Li , Jiage Li , Yansong Liu , Zian Fang , Xinyu Wang , Mingxin Huo , Shuangshi Dong , Mingyu Li . Doped cobalt for simultaneously promoting active (001) facet exposure of MIL-68(In) and acting as reactive sites in peroxymonosulfate-mediated photocatalytic decontamination. Chinese Chemical Letters, 2025, 36(5): 110201-. doi: 10.1016/j.cclet.2024.110201
10. [10]
  Yan-Jiang Li , Shu-Lei Chou , Yao Xiao . Detecting dynamic structural evolution based on in-situ high-energy X-ray diffraction technology for sodium layered oxide cathodes. Chinese Chemical Letters, 2025, 36(2): 110389-. doi: 10.1016/j.cclet.2024.110389
11. [11]
  Yaxuan Jin , Chao Zhang , Guigang Zhang . Atomically dispersed low-valent Au on poly(heptazine imide) boosts photocatalytic hydroxyl radical production. Chinese Journal of Structural Chemistry, 2024, 43(12): 100414-100414. doi: 10.1016/j.cjsc.2024.100414
12. [12]
  Shimei Wu , Yining Li , Lantao Chen , Yufei Zhang , Lingxing Zeng , Haosen Fan . Hexapod cobalt phosphosulfide nanorods encapsulating into multiple hetero-atom doped carbon frameworks for advanced sodium/potassium ion battery anodes. Chinese Chemical Letters, 2025, 36(4): 109796-. doi: 10.1016/j.cclet.2024.109796
13. [13]
  Yining Li , Shimei Wu , Lantao Chen , Haosen Fan , Yufei Zhang , Lingxing Zeng . Multiple yolks-shell cobalt phosphosulfide nanocrystals encapsulating into rich heteroatoms co-doped carbon frameworks for advanced sodium/potassium ion batteries. Chinese Chemical Letters, 2025, 36(9): 110371-. doi: 10.1016/j.cclet.2024.110371
14. [14]
  Peng Wang , Daijie Deng , Suqin Wu , Li Xu . Cobalt-based deep eutectic solvent modified nitrogen-doped carbon catalyst for boosting oxygen reduction reaction in zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100199-100199. doi: 10.1016/j.cjsc.2023.100199
15. [15]
  Sikai Wu , Xuefei Wang , Huogen Yu . Hydroxyl-enriched hydrous tin dioxide-coated BiVO4 with boosted photocatalytic H2O2 production. Chinese Journal of Structural Chemistry, 2024, 43(12): 100457-100457. doi: 10.1016/j.cjsc.2024.100457
16. [16]
  Zili Ma , Zeyu Li , Jun Lv . Shortening the formation time of oxide thin film photoelectrodes from hours to seconds. Chinese Journal of Structural Chemistry, 2025, 44(4): 100450-100450. doi: 10.1016/j.cjsc.2024.100450
17. [17]
  Chen-Xin Wang , Guang-Lei Li , Yu Hang , Dan-Feng Lu , Jian-Qi Ye , Hao Su , Bing Hou , Tao Suo , Dan Wen . Shock-resistant wearable pH sensor based on tungsten oxide aerogel. Chinese Chemical Letters, 2025, 36(7): 110502-. doi: 10.1016/j.cclet.2024.110502
18. [18]
  Guo-Hong Gao , Run-Ze Zhao , Ya-Jun Wang , Xiao Ma , Yan Li , Jian Zhang , Ji-Sen Li . Core–shell heterostructure engineering of CoP nanowires coupled NiFe LDH nanosheets for highly efficient water/seawater oxidation. Chinese Chemical Letters, 2024, 35(8): 109181-. doi: 10.1016/j.cclet.2023.109181
19. [19]
  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
20. [20]
  Xing Xiao , Yunling Jia , Wanyu Hong , Yuqing He , Yanjun Wang , Lizhi Zhao , Huiqin An , Zhen Yin . Sulfur-defective ZnIn2S4 nanosheets decorated by TiO2 nanosheets with exposed {001} facets to accelerate charge transfer for efficient photocatalytic hydrogen evolution. Chinese Journal of Structural Chemistry, 2024, 43(12): 100474-100474. doi: 10.1016/j.cjsc.2024.100474

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(6)
HTML views(1)

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