调控电荷动力学与表面反应性用于Au/Ti-CeO2光催化甲烷选择性氧化制乙烷

doi:10.1016/j.actphy.2025.100153

Abstract

Abstract:

The selective oxidation of methane to value-added chemicals under mild conditions presents a sustainable yet challenging route, hindered by sluggish CH₄ activation and overoxidation. Herein, we report a delicate strategy combining Ti doping and Au loading to construct a high-performance Au/Ti−CeO₂ photocatalyst for ethane production from oxidative methane coupling. The optimized catalyst achieves a C₂H₆ production rate of 2971.4 μmol·g⁻¹·h⁻¹ with 85.1% C₂₊ selectivity, stably operating over 20 reaction cycles. In situ X-ray photoelectron spectroscopy, electron paramagnetic resonance, and diffuse reflectance infrared Fourier transform spectroscopy analyses reveal that Ti doping introduces impurity energy levels into CeO₂, promoting directional electron migration to surface Au nanoparticles (NPs) via a built-in electric field. The Au NPs act as electron accumulation sites to activate O₂, facilitate *CH₃ radical coupling into C₂H₆, and stabilize reactive intermediates, thus enhancing charge separation and suppressing intermediate overoxidation. This study highlights the significance of synergistic modulation via elemental doping and cocatalyst engineering in tuning charge dynamics and surface reactivity for efficient photocatalytic methane conversion.

Key words: Photocatalysis, Methane oxidation, Ethane production, Ti doping, CeO₂, Charge separation

Xinyu Xu, Jiale Lu, Bo Su, Jiayi Chen, Xiong Chen, Sibo Wang. Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂[J]. Acta Phys. -Chim. Sin. 2025, 41(11), 100153. doi: 10.1016/j.actphy.2025.100153

Figures/Tables 5

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

References 59

1	Saha D.; Grappe H. A.; Chakraborty A.; Orkoulas G. Chem. Rev. 2016, 116, 11436. doi: 10.1021/acs.chemrev.5b00745
2	Meng X.; Cui X.; Rajan N. P.; Yu L.; Deng D.; Bao X. Chem 2019, 5, 2296. doi: 10.1016/j.chempr.2019.05.008
3	Li X.; Wang C.; Tang J. Nat. Rev. Mater 2022, 7, 617. doi: 10.1038/s41578-022-00422-3
4	Jiang Y.; Li S.; Fan Y.; Tang Z. Angew. Chem. Int. Ed. 2024, 63, e202404658. doi: 10.1002/anie.202404658
5	Song H.; Meng X.; Wang Z. J.; Liu H.; Ye J. Joule 2019, 3, 1606. doi: 10.1016/j.joule.2019.06.023
6	Nie S.; Wu L.; Wang X. J. Am. Chem. Soc. 2023, 145, 23681. doi: 10.1021/jacs.3c07984
7	Wang G.; Mu X.; Tan R.; Pan Z.; Li J.; Zhan Q.; Fu R.; Song S.; Li L. ACS Catal. 2023, 13, 11666. doi: 10.1021/acscatal.3c02192
8	Fu W.; Wang S.; Zhang Y.; Cheng B.; Wu Y. J. Mater. Sci. Technol. 2025, 232, 181. doi: 10.1016/j.jmst.2024.12.081
9	Ran H.; Liu X.; Ye L.; Fan J.; Zhu B.; Xu Q.; Wei Y. J. Mater. Sci. Technol. 2025, 234, 24. doi: 10.1016/j.jmst.2024.12.089
10	Tian J.; Guan C.; Zhang Q.; Sun T.; Hu H.; Liu E. J. Mater. Sci. Technol. 2025, 231, 308. doi: 10.1016/j.jmst.2024.12.102
11	Zhong W.; Meng A.; Su Y.; Yu H.; Han P.; Yu J. Angew. Chem. Int. Ed. 2025, 64, e202425038. doi: 10.1002/anie.202425038
12	Li W.; Ni Z.; Akdim O.; Liu T.; Zhu B.; Kuang P.; Yu J. Adv. Mater. 2025, 37, 2503742. doi: 10.1002/adma.202503742
13	Chen W.; Lin S.-Z.; Song Z.; Huang G.-B.; Zhang M. J. Mater. Sci. Technol. 2025, 232, 246. doi: 10.1016/j.jmst.2024.12.092
14	Li H.; Zhang J.; Zhou X.; Wu Z.; Zhang L. J. Mater. Sci. Technol. 2025, 231, 1. doi: 10.1016/j.jmst.2024.12.076
15	Xu X.; Shao C.; Zhang J.; Wang Z.; Dai K. Acta Phys. Chim. Sin. 2024, 40, 2309031. doi: 10.3866/PKU.WHXB202309031
16	Cao S.; Zhong B.; Bie C.; Cheng B.; Xu F. Acta Phys. Chim. Sin. 2024, 40, 2307016. doi: 10.3866/PKU.WHXB202307016
17	Zhang X.; Xu J.; Long H.; Yu J.; Yu H. ACS Catal. 2024, 14, 18669. doi: 10.1021/acscatal.4c05674
18	Zhao Y.; Zhang Y.; Wang L.; Ai C.; Zhang J. J. Mater. Sci. Technol. 2025, 229, 213. doi: 10.1016/j.jmst.2024.12.040
19	Deng X.; Zhang J.; Qi K.; Liang G.; Xu F.; Yu J. Nat. Commun 2024, 15, 4807. doi: 10.1038/s41467-024-49004-7
20	Wan S.; Wang W.; Cheng B.; Luo G.; Shen Q.; Yu J.; Zhang J.; Cao S.; Zhang L. Nat. Commun 2024, 15, 9612. doi: 10.1038/s41467-024-53951-6
21	Deng X.; Wen Z.; Li X.; Macyk W.; Yu J.; Xu F. Small 2024, 20, 2305410. doi: 10.1002/smll.202305410
22	Meng K.; Zhang J.; Zhu B.; Jiang C.; García H.; Yu J. Adv. Mater. 2025, 37, 2505088. doi: 10.1002/adma.202505088
23	Meng Z.; Zhang J.; Long H.; García H.; Zhang L.; Zhu B.; Yu J. Angew. Chem. Int. Ed. 2025, 64, e202505456. doi: 10.1002/anie.202505456
24	He H.; Wang Z.; Zhang J.; Mamatkulov S.; Ruzimuradov O.; Dai K.; Low J.; Li Y. Energy Environ. Sci. 2025, 18, 6191. doi: 10.1039/D5EE01295C
25	Cui Y.; Zhang J.; Chu H.; Sun L.; Dai K. Acta Phys. Chim. Sin. 2024, 40, 2405016. doi: 10.3866/PKU.WHXB202405016
26	Chen C.; Zhang J.; Chu H.; Sun L.; Dawson G.; Dai K. Chin. J. Catal. 2024, 63, 81. doi: 10.1016/S1872-2067(24)60072-0
27	Li P.; Cui Y.; Wang Z.; Dawson G.; Shao C.; Dai K. Acta Phys. Chim. Sin. 2025, 41, 100065. doi: 10.1016/j.actphy.2025.100065
28	Yang T.; Wang J.; Wang Z.; Zhang J.; Dai K. Chin. J. Catal. 2024, 58, 157. doi: 10.1016/S1872-2067(23)64607-8
29	Liu Y.; Chen C.; Dawson G.; Zhang J.; Shao C.; Dai K. J. Mater. Sci. Technol. 2025, 233, 10. doi: 10.1016/j.jmst.2024.12.094
30	Che Y.; Wang K.; Wang C.; Weng B.; Chen S.; Meng S. J. Mater. Sci. Technol. 2026, 243, 228. doi: 10.1016/j.jmst.2025.04.030
31	Liu Z.; Bian Y.; Dawson G.; Zhu J.; Dai K. Chin. Chem. Lett. 2025, 36, 111272. doi: 10.1016/j.cclet.2025.111272
32	Su B.; Wang S.; Xing W.; Liu K.; Hung S. F.; Chen X.; Fang Y.; Zhang G.; Zhang H.; Wang X. Angew. Chem. Int. Ed. 2025, 64, e202505453. doi: 10.1002/anie.202505453
33	Luo L.; Gong Z.; Xu Y.; Ma J.; Liu H.; Xing J.; Tang J. J. Am. Chem. Soc. 2022, 144, 740. doi: 10.1021/jacs.1c09141
34	Zheng K.; Li Y.; Liu B.; Jiang F.; Xu Y.; Liu X. Angew. Chem. Int. Ed. 2022, 61, e202210991. doi: 10.1002/anie.202210991
35	Han B.; Wei W.; Li M.; Sun K.; Hu Y. H. Chem. Commun. 2019, 55, 7816. doi: 10.1039/C9CC04193A
36	Shimura K.; Kawai H.; Yoshida T.; Yoshida H. ACS Catal. 2012, 2, 2126. doi: 10.1021/cs2006229
37	Pan X.; Chen X.; Yi Z. PCCP 2016, 18, 31400. doi: 10.1039/C6CP04604E
38	Li P.; Xin Y.; Li Q.; Wang Z.; Zhang Z.; Zheng L. Environ. Sci. Technol. 2012, 46, 9600. doi: 10.1021/es301661r
39	Huang Q.; Cai J.; Wei F.; Fan Y.; Liang Z.; Liu K.; Lu X. F.; Ding Z.; Wang S. J. Mater. Chem. A 2024, 12, 21334. doi: 10.1039/D4TA02049A
40	Wang Y. F.; Qi M. Y.; Conte M.; Tang Z. R.; Xu Y. J. Angew. Chem. Int. Ed. 2024, 63, e202407791. doi: 10.1002/anie.202407791
41	Su B.; Zheng M.; Lin W.; Lu X. F.; Luan D.; Wang S.; Lou X. W. Adv. Energy Mater. 2023, 13, 2203290. doi: 10.1002/aenm.202203290
42	Su B.; Kong Y.; Wang S.; Zuo S.; Lin W.; Fang Y.; Hou Y.; Zhang G.; Zhang H.; Wang X. J. Am. Chem. Soc. 2023, 145, 27415. doi: 10.1021/jacs.3c08311
43	Bie C.; Jiang C.; Yang J.; Sun X.; Zeng X.; Zhang J.; Zhu B. J. Mater. Sci. Technol. 2025, 229, 48. doi: 10.1016/j.jmst.2024.12.047
44	Zhang C.; Tao X.; Jiang W.; Guo J.; Zhang P.; Li C.; Li R. Acta Phys. Chim. Sin. 2024, 40, 2303034. doi: 10.3866/PKU.WHXB202303034
45	Su J.; Zhang J.; Chai S.; Wang Y.; Wang S.; Fang Y. Acta Phys. Chim. Sin. 2024, 40, 2408012. doi: 10.3866/PKU.WHXB202408012
46	Lu E.; Tao J.; Yang C.; Hou Y.; Zhang J.; Wang X.; Fu X. Acta Phys. Chim. Sin. 2023, 39, 2211029. doi: 10.3866/PKU.WHXB202211029
47	Gao D.; Deng P.; Zhang J.; Zhang L.; Wang X.; Yu H.; Yu J. Angew. Chem. Int. Ed. 2023, 62, e202304559. doi: 10.1002/anie.202304559
48	Zhou M.; Wang H.; Liu R.; Liu Z.; Xiao X.; Li W.; Gao C.; Lu Z.; Jiang Z.; Shi W.; et al Angew. Chem. Int. Ed. 2024, 63, e202407468. doi: 10.1002/anie.202407468
49	Wang Y. F.; Qi M. Y.; Conte M.; Tang Z. R.; Xu Y. J. Angew. Chem. Int. Ed. 2023, 62, e202304306. doi: 10.1002/anie.202304306
50	Sun F.; Luo Y.; Kuang S.; Zhou M.; Ho W. K.; Tang H. J. Mater. Sci. Technol. 2025, 229, 287. doi: 10.1016/j.jmst.2024.12.060
51	Liu F.; Deng J.; Su B.; Peng K.-S.; Liu K.; Lin X.; Hung S.-F.; Chen X.; Lu X. F.; Fang Y.; et al ACS Catal. 2025, 15, 1018. doi: 10.1021/acscatal.4c06685
52	Cai J.; Li X.; Su B.; Guo B.; Lin X.; Xing W.; Lu X. F.; Wang S. J. Mater. Sci. Technol. 2025, 234, 82. doi: 10.1016/j.jmst.2025.01.050
53	Xia X.; Jia Y.; Wang W.; Zhang J.; Wang L.; Liu Q. J. Mater. Sci. Technol. 2025, 236, 301. doi: 10.1016/j.jmst.2024.12.093
54	Xiao M.; Wang L.; Wang H.; Yuan J.; Chen X.; Zhang Z.; Fu X.; Dai W. Catal. Sci. Technol. 2023, 13, 4148. doi: 10.1039/D3CY00515A
55	Sun M.; Chen Y.; Fan X.; Li D.; Song J.; Yu K.; Zhao Z. Nat. Commun. 2024, 15, 9900. doi: 10.1038/s41467-024-54226-w
56	Wang C.; Xu Y.; Xiong L.; Li X.; Chen E.; Miao T. J.; Zhang T.; Lan Y.; Tang J. Nat. Commun. 2024, 15, 7535. doi: 10.1038/s41467-024-51690-2
57	Liu Y.; Xue W.; Liu X.; Wei F.; Lin X.; Lu X. F.; Lin W.; Hou Y.; Zhang G.; Wang S. Small 2024, 20, 2402004. doi: 10.1002/smll.202402004
58	Wei F.; Zhao J.; Liu Y. C.; Hsu Y. H.; Hung S. F.; Fu J.; Liu K.; Lin W.; Yu Z.; Tan L.; et al Nat. Commun. 2025, 16, 6586. doi: 10.1038/s41467-025-61634-z
59	Li J.; Zhao J.; Wang S.; Peng K. S.; Su B.; Liu K.; Hung S. F.; Huang M.; Zhang G.; Zhang H.; et al J. Am. Chem. Soc. 2025, 147, 14705. doi: 10.1021/jacs.5c03098

[1]	Yu Liu, Pengfei Li, Yize Liu, Zaicheng Sun. Recent advances in carbon dots as a single photocatalyst [J]. Acta Phys. -Chim. Sin., 2026, 42(2): 100167-.
[2]	Yuhang Zhang, Yi Li, Yuehan Cao, Yingjie Shuai, Yu Zhou, Ying Zhou. Regulating the formation type by Ir of intermediates to suppress product overoxidation in photocatalytic methane conversion [J]. Acta Phys. -Chim. Sin., 2026, 42(2): 100173-.
[3]	Shiyi Chen, Jialong Fu, Jianping Qiu, Guoju Chang, Shiyou Hao. Waste medical mask-derived carbon quantum dots enhance the photocatalytic degradation of polyethylene terephthalate (PET) over BiOBr/g-C₃N₄ S-scheme heterojunction [J]. Acta Phys. -Chim. Sin., 2026, 42(1): 100135-.
[4]	Chengxiao Zhao, Zhaolin Li, Dongfang Wu, Xiaofei Yang. SBA-15 templated covalent triazine frameworks for boosted photocatalytic hydrogen production [J]. Acta Phys. -Chim. Sin., 2026, 42(1): 100149-.
[5]	Menglan Wei, Xiaoxia Ou, Yimeng Wang, Mengyuan Zhang, Fei Teng, Kaixuan Wang. S-scheme heterojunction g-C₃N₄/Bi₂WO₆ highly efficient degradation of levofloxacin: performance, mechanism and degradation pathway [J]. Acta Phys. -Chim. Sin., 2025, 41(9): 100105-.
[6]	Jingping Li, Suding Yan, Jiaxi Wu, Qiang Cheng, Kai Wang. Improving hydrogen peroxide photosynthesis over inorganic/organic S-scheme photocatalyst with LiFePO₄ [J]. Acta Phys. -Chim. Sin., 2025, 41(9): 100104-.
[7]	Fengying Zhang, Yanglin Mei, Yuman Jiang, Shenshen Zheng, Kaibo Zheng, Ying Zhou. Research progress of transient absorption spectroscopy in solar energy conversion and utilization [J]. Acta Phys. -Chim. Sin., 2025, 41(9): 100118-.
[8]	Jiajie Cai, Chang Cheng, Bowen Liu, Jianjun Zhang, Chuanjia Jiang, Bei Cheng. CdS/DBTSO-BDTO S-scheme photocatalyst for H₂ production and its charge transfer dynamics [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100084-.
[9]	Lewang Yuan, Yaoyao Peng, Zong-Jie Guan, Yu Fang. Insights into the development of 2D covalent organic frameworks as photocatalysts in organic synthesis [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100086-.
[10]	Yu Wang, Haiyang Shi, Zihan Chen, Feng Chen, Ping Wang, Xuefei Wang. Hollow AgPt@Pt core-shell cocatalyst with electron-rich Pt^δ− shell for boosting selectivity of photocatalytic H₂O₂ production for faceted BiVO₄ [J]. Acta Phys. -Chim. Sin., 2025, 41(7): 100081-.
[11]	Yadan Luo, Hao Zheng, Xin Li, Fengmin Li, Hua Tang, Xilin She. Modulating reactive oxygen species in O, S co-doped C₃N₄ to enhance photocatalytic degradation of microplastics [J]. Acta Phys. -Chim. Sin., 2025, 41(6): 100052-.
[12]	Peng Li, Yuanying Cui, Zhongliao Wang, Graham Dawson, Chunfeng Shao, Kai Dai. Efficient interfacial charge transfer of CeO₂/Bi₁₉Br₃S₂₇ S-scheme heterojunction for boosted photocatalytic CO₂ reduction [J]. Acta Phys. -Chim. Sin., 2025, 41(6): 100065-.
[13]	Yuchen Zhou, Huanmin Liu, Hongxing Li, Xinyu Song, Yonghua Tang, Peng Zhou. Designing thermodynamically stable noble metal single-atom photocatalysts for highly efficient non-oxidative conversion of ethanol into high-purity hydrogen and value-added acetaldehyde [J]. Acta Phys. -Chim. Sin., 2025, 41(6): 100067-.
[14]	Hui Wang, Abdelkader Labidi, Menghan Ren, Feroz Shaik, Chuanyi Wang. Recent Progress of Microstructure-Regulated g-C₃N₄ in Photocatalytic NO Conversion: The Pivotal Roles of Adsorption/Activation Sites [J]. Acta Phys. -Chim. Sin., 2025, 41(5): 100039-.
[15]	Qin Li, Huihui Zhang, Huajun Gu, Yuanyuan Cui, Ruihua Gao, Wei-Lin Dai. In situ Growth of Cd_0.5Zn_0.5S Nanorods on Ti₃C₂ MXene Nanosheet for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution [J]. Acta Phys. -Chim. Sin., 2025, 41(4): 100031-.

Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂

RichHTML

Full text @ ScienceDirect

Like

Supplement

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 59

Related Articles 15

Metrics

Recommended 0

Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO2

RichHTML

Full text @ ScienceDirect

Like

Supplement

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 59

Related Articles 15

Metrics

Recommended 0

Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂