Au/Sr-ZnO双位点工程用于晶格氧活化甲烷高选择性偶联制乙烷-CSCIED科技核心评价数据库-手机版

Au/Sr-ZnO双位点工程用于晶格氧活化甲烷高选择性偶联制乙烷

Dual-site engineering of Au/Sr-ZnO photocatalysts for lattice oxygen-activated methane coupling to ethane with high selectivity

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DOI	10.1016/j.apcatb.2025.125437
刊名	Applied Catalysis B: Environment and Energy
年，卷(期)	2025, 375()
作者	王萍, 冯晓燕, 梁军 * , 张金宇, 牛涛涛, 李莉 *,
作者单位	宁夏大学
摘要	光驱动甲烷氧化偶联制乙烷是一种可持续生产高附加值化学品的前沿策略，但其C-H键断裂的高活化能垒带来显著挑战。本研究展示了一种双位点工程设计的金/锶掺杂氧化锌（Au/Sr-ZnO）光催化剂，通过协同的晶格氧活化与甲基转移调控，实现了高效的甲烷氧化偶联反应活性和催化耐久性。综合表征表明，Sr掺杂ZnO弱化了Sr-O键并增强了电子供体能力，从而有效激活ZnO晶格氧作为甲烷解离的局域氧化剂。同时，金纳米颗粒促进了甲基脱附，抑制了过度氧化并加速了C-C偶联过程。优化后的1%Au/Sr0.05-ZnO催化剂实现了6083.7μmol·g?1·h?1的乙烷产率，选择性高达85.8%。机理研究证实了Sr掺杂介导的Mars-van Krevelen型晶格氧循环机制，其中消耗的晶格氧可通过引入氧气持续补充，确保了催化体系的长期稳定性。该研究为选择性C-H键活化的多功能光催化剂理性设计提供了新的思路。
Abstract	Light-driven oxidative coupling of methane (OCM) to ethane represents a promising strategy for sustainableproduction of value-added chemicals, yet faces challenges due to high activation barriers of C-H bond cleavage. Herein, we demonstrate a dual-site engineered Au/Sr-doped ZnO (Au/Sr-ZnO) photocatalyst that achievesexceptional conversion rates and catalytic durability for OCM through synergistic lattice oxygen activation andmethyl transfer modulation. Comprehensive characterization reveals that Sr doping ZnO weakens Sr-O bondsand enhances electron donation, effectively activating ZnO lattice oxygen as localized oxidants for methanedissociation. Concurrently, Au nanoparticles promote methyl desorption, suppressing over-oxidation while facilitating C-C coupling. The optimized 1%Au/Sr0.05-ZnO catalyst exhibits an ethane production rate of 6083.7 μmol g-1 h-1 with 85.8% selectivity. Mechanistic studies confirm the Mars-van Krevelen-type latticeoxygen cycling mediated by Sr doping, where consumed lattice oxygen is replenished via O2 introduction, ensuring sustained catalytic stability. This work provides new insights into the rational design of multifunctional photocatalysts for selective C-H bond activation.
关键词	光催化；C-H键活化；甲烷氧化偶联；Au/Sr-ZnO；乙烷
KeyWord	Photocatalysis ; C-H activation ; Oxidative coupling of methane; Au/Sr-ZnO; Ethane
基金项目
页码	1-8

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[1] X. Li, C. Wang, J. Tang, Methane transformation by photocatalysis, Nat. Rev. Mater. 7(2022)617-632, https://doi.org/10.1038/s41578-022-00422-3.

[2] Y. Chai, S. Tang, Q. Wang, Q. Wu, J. Liang, L. Li, Gold nanoparticles supported on ZnGa2O4 nanosheets as efficient photocatalysts for selective oxidation of methane to ethane under ambient conditions, Appl. Catal. B. 338(2023)123012, https://doi.org/10.1016/j.apcatb.2023.123012.

[3] P. Zhang, J. Li, H. Huang, X. Sui, H. Zeng, H. Lu, Y. Wang, Y. Jia, J. A. Steele, Y. Ao, M. B. J. Roeffaers, S. Dai, Z. Zhang, L. Wang, X. Fu, J. Long, Platinum Single-Atom Nests Boost Solar-Driven Photocatalytic Non-Oxidative Coupling of Methane to Ethane, J. Am. Chem. Soc. 146(2024)24150-24157, https://doi.org/10.1021/jacs.4c08901.

[4] P. Schwach, X. Pan, X. Bao, Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects, Chem. Rev. 117(2017)8497-8520, https://doi.org/10.1021/acs.chemrev.6b00715.

[5] X. Li, C. Wang, J. Yang, Y. Xu, Y. Yang, J. Yu, J. J. Delgado, N. Martsinovich, X. Sun, X.-S. Zheng, W. Huang, J. Tang, PdCu nanoalloy decorated photocatalysts for efficient and selective oxidative coupling of methane in flow reactors, Nat. Commun. 14(2023)6343, https://doi.org/10.1038/s41467-023-41996-y.

[6] J. Yang, L. Xiong, C. Wang, L. Luo, L. Jing, N. Martsinovich, J. Tang, Selective Synthesis of Ethane from Methane by a Photocatalytic Chemical Cycle Process, Adv. Energy Mater. 15(2025)2404202, https://doi.org/10.1002/aenm.202404202.

[7] Y. Zhang, Y. Zhang, H. Wu, Y. Wang, Q. Gu, Tandem dual-heterojunctions in Au/ZnGa2O4/ZnO for promoted photocatalytic nonoxidative coupling of methane, Appl. Catal. B. 358(2024)124427, https://doi.org/10.1016/j.apcatb.2024.124427.

[8] X. Li, C. Li, Y. Xu, Q. Liu, M. Bahri, L. Zhang, N. D. Browning, A. J. Cowan, J. Tang, Efficient hole abstraction for highly selective oxidative coupling of methane by Au-sputtered TiO2 photocatalysts, Nat. Energy. 8(2023)1013-1022, 10.1038/s41560-023-01317-5.

[9] M. Fei, B. Williams, L. Wang, H. Li, Y. Yuan, J. R. Wilkes, T. Liu, Y. Mu, J. Huang, J. Nyakuchena, J. Huang, W. Li, D. Wang, Highly Selective Photocatalytic Methane Coupling by Au-Modified Bi2WO6, ACS. Catal. 14(2024)1855-1861, https://doi.org/10.1021/acscatal.3c05534.

[10] Y. Chen, Y. Zhao, D. Liu, G. Wang, W. Jiang, S. Liu, W. Zhang, Y. Li, Z. Ma, T. Shao, H. Liu, X. Li, Z. Tang, C. Gao, Y. Xiong, Continuous Flow System for Highly Efficient and Durable Photocatalytic Oxidative Coupling of Methane, J. Am. Chem. Soc. 146(2024)2465-2473, https://doi.org/10.1021/jacs.3c10069.

[11] G. Zhai, L. Cai, J. Ma, Y. Chen, Z. Liu, S. Si, D. Duan, S. Sang, J. Li, X. Wang, Y.-A. Liu, B. Qian, C. Liu, Y. Pan, N. Zhang, D. Liu, R. Long, Y. Xiong, Highly efficient, selective, and stable photocatalytic methane coupling to ethane enabled by lattice oxygen looping, Sci. Adv. 10(2024)eado4390, https://doi.org/10.1126/sciadv.ado4390.

[12] A. Zanina, V. A. Kondratenko, H. Lund, J. Li, J. Chen, Y. Li, G. Jiang, E. V. Kondratenko, The Role of Adsorbed and Lattice Oxygen Species in Product Formation in the Oxidative Coupling of Methane over M2WO4/SiO2 (M = Na, K, Rb, Cs), ACS. Catal. 12(2022)15361-15372, https://doi.org/10.1021/acscatal.2c04916.

[13] Z. Chen, Y. Ye, X. Feng, Y. Wang, X. Han, Y. Zhu, S. Wu, S. Wang, W. Yang, L. Wang, J. Zhang, High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling, Nat. Commun. 14(2023)2000, https://doi.org/10.1038/s41467-023-37663-x.

[14] Y. Chai, S. Tang, Q. Wang, Q. Wu, L. Li, J. Liang, Nickel phosphide nanoparticles as a noble-metal-free co-catalyst for the selective photocatalytic aerobic oxidation of CH4 into CO and H2, J. Catal. 425(2023)306-313, https://doi.org/10.1016/j.jcat.2023.06.027.

[15] S. Song, H. Song, L. Li, S. Wang, W. Chu, K. Peng, X. Meng, Q. Wang, B. Deng, Q. Liu, Z. Wang, Y. Weng, H. Hu, H. Lin, T. Kako, J. Ye, A selective Au-ZnO/TiO2 hybrid photocatalyst for oxidative coupling of methane to ethane with dioxygen, Nat. Catal. 4(2021)1032-1042, https://doi.org/10.1038/s41929-021-00708-9.

[16] H. Wang, W. Zheng, W. Li, F. Tian, S. Kuang, Y. Bu, J.-P. Ao, Control the energy band potential of ZnMgO solid solution with enhanced photocatalytic hydrogen evolution capacity, Appl. Catal. B. 217(2017)523-529, https://doi.org/10.1016/j.apcatb.2017.04.079.

[17] C. Liu, B. Qian, T. Xiao, C. Lv, J. Luo, J. Bao, Y. Pan, Illustrating the Fate of Methyl Radical in Photocatalytic Methane Oxidation over Ag?ZnO by in situ Synchrotron Radiation Photoionization Mass Spectrometry, Angew. Chem. Int. Ed. 62(2023)e202304352, https://doi.org/10.1002/anie.202304352.

[18] M. Wang, X. Ge, Z. Cui, S. Wu, S. Zhu, Y. Liang, Z. Li, W. W. Lu, Influences of strontium on the phase composition and lattice structure of biphasic calcium phosphate, Ceram. Int. 47(2021)16248-16255, https://doi.org/10.1016/j.ceramint.2021.01.295.

[19] S. Muthukumaran, R. Gopalakrishnan, Structural, FTIR and photoluminescence studies of Cu doped ZnO nanopowders by co-precipitation method, Opt. Mater. 34(2012)1946-1953, https://doi.org/10.1016/j.optmat.2012.06.004.

[20] M. Yarahmadi, H. Maleki-Ghaleh, M. E. Mehr, Z. Dargahi, F. Rasouli, M. H. Siadati, Synthesis and characterization of Sr-doped ZnO nanoparticles for photocatalytic applications, J. Alloy. Compd. 853(2021)157000, https://doi.org/10.1016/j.jallcom.2020.157000.

[21] F. Chen, H. Zhou, D. Liu, X. Qin, Y. Jing, L. Chen, R. Shi, Y. Liu, J. Zhang, Y. Zhu, J. Wang, Defective ZnO Nanoplates Supported AuPd Nanoparticles for Efficient Photocatalytic Methane Oxidation to Oxygenates, Adv. Energy Mater. 14(2024)2303642, https://doi.org/10.1002/aenm.202303642.

[22] C. Zhang, Y. Hao, X. Wang, D. Hu, N. Sun, W. Wei, Efficient photocatalytic oxidation of CH4 over Ag-modified ZnO nanorods, Catal. Sci. Technol. 14(2024)935-944, https://doi.org/10.1039/d3cy01629c.

[23] M. Katai, P. Edalati, J. Hidalgo-Jimenez, Y. Shundo, T. Akbay, T. Ishihara, M. Arita, M. Fuji, K. Edalati, Black brookite rich in oxygen vacancies as an active photocatalyst for CO2 conversion: Experiments and first-principles calculations, Journal of Photochemistry and Photobiology A: Chemistry. 449(2024)115409, https://doi.org/10.1016/j.jphotochem.2023.115409.

[24] H. Li, J. Ding, S. Cai, W. Zhang, X. Zhang, T. Wu, C. Wang, M. Foss, R. Yang, Plasmon-enhanced photocatalytic properties of Au/ZnO nanowires, Appl. Surf. Sci. 583(2022)152539, https://doi.org/10.1016/j.apsusc.2022.152539.

[25] L. Luo, Z. Gong, Y. Xu, J. Ma, H. Liu, J. Xing, J. Tang, Binary Au–Cu Reaction Sites Decorated ZnO for Selective Methane Oxidation to C1 Oxygenates with Nearly 100% Selectivity at Room Temperature, J. Am. Chem. Soc. 144(2022)740-750, https://doi.org/10.1021/jacs.1c09141.

[26] I. Mansouri, F. Saib, S. Boulahlib, A. Laachachi, M. ?zacar, Y. Bessekhouad, Effect of Sr-doping toward the optoelectrical ZnO properties, Inorg. Chem. Commun. 162(2024)112236, https://doi.org/10.1016/j.inoche.2024.112236.

[27] J. Hidalgo-Jiménez, T. Akbay, X. Sauvage, T. Ishihara, K. Edalati, Photocatalytic carbon dioxide methanation by high-entropy oxides: Significance of work function, Appl. Catal. B. 371(2025)125259, https://doi.org/10.1016/j.apcatb.2025.125259.

[28] J. Zhang, X. Feng, L. Li, P. Wang, J. Liang, Selective photocatalytic oxidative coupling of methane via directional activation of oxygen over Au-loaded ZnSn-LDH with defect structure, Appl. Catal. B. 361(2025)124670, https://doi.org/10.1016/j.apcatb.2024.124670.

[29] J. T. Mefford, X. Rong, A. M. Abakumov, W. G. Hardin, S. Dai, A. M. Kolpak, K. P. Johnston, K. J. Stevenson, Water electrolysis on La1?xSrxCoO3?δ perovskite electrocatalysts, Nat. Commun. 7(2016)11053, https://doi.org/10.1038/ncomms11053.

[30] U. L. Bernard, E. I. Izgorodina, D. R. MacFarlane, New Insights into the Relationship between Ion-Pair Binding Energy and Thermodynamic and Transport Properties of Ionic Liquids, J. Phys. Chem. C. 114(2010)20472-20478, https://doi.org/10.1021/jp1048875.

[31] Y. Chen, S. Tang, L. Li, X. Liu, J. Liang, Selective Photocatalytic Conversion of Methane Induced by Lewis Acid–Base Pair on the Surface of In2O3/TiO2 Heterojunction Photocatalyst, ACS Sustain. Chem. Eng. 11(2023)3568-3575, https://doi.org/10.1021/acssuschemeng.2c05045.

[32] M. Sun, Y. Chen, X. Fan, D. Li, J. Song, K. Yu, Z. Zhao, Electronic asymmetry of lattice oxygen sites in ZnO promotes the photocatalytic oxidative coupling of methane, Nat. Commun. 15(2024)9900, https://doi.org/10.1038/s41467-024-54226-w.

[33] M. Breedon, M. J. S. Spencer, I. Yarovsky, Adsorption of NO2 on Oxygen Deficient ZnO(21?1?0) for Gas Sensing Applications: A DFT Study, J. Phys. Chem. C. 114(2010)16603-16610, https://doi.org/10.1021/jp105733p.

[34] L.-L. Zheng, L. Tian, L.-S. Zhang, J. Yu, Y. Chen, Q. Fu, X.-Z. Liu, D.-S. Wu, J.-P. Zou, Defect-Induced Synergetic Effect of Bi-Based Compounds for One-Pot Conversion of Organic Pollutants into CO via Coupling Photodegradation of Carbamazepine with Photoreduction of CO2, ACS. Catal. 14(2024)2134-2143, https://doi.org/10.1021/acscatal.3c04820.

[35] I. Derkaoui, M. Achehboune, I. Boukhoubza, E. m. El Allam, Z. El Adnani, L. Henrard, A. Rezzouk, Effect of strontium (Sr) doping on the structural, electronic and optical properties of ZnO, by first-principles calculations, Phys. B Condens. Matter. 660(2023)414903, https://doi.org/10.1016/j.physb.2023.414903.

[36] Q. Tang, B. Wu, X. Huang, W. Ren, L. Liu, L. Tian, Y. Chen, L.-S. Zhang, Q. Sun, Z. Kang, T. Ma, J.-P. Zou, Electron transfer mediated activation of periodate by contaminants to generate O2 by charge-confined single-atom catalyst, Nat. Commun. 15(2024)9549, https://doi.org/10.1038/s41467-024-53941-8.

[37] T. Pinheiro Araújo, J. Morales-Vidal, T. Zou, M. Agrachev, S. Verstraeten, P. O. Willi, R. N. Grass, G. Jeschke, S. Mitchell, N. López, J. Pérez-Ramírez, Design of Flame-Made ZnZrO Catalysts for Sustainable Methanol Synthesis from CO2, Adv. Energy Mater. 13(2023)2204122, https://doi.org/10.1002/aenm.202204122.

[38] Y. Shundo, T. Tam Nguyen, S. Akrami, P. Edalati, Y. Itagoe, T. Ishihara, M. Arita, Q. Guo, M. Fuji, K. Edalati, Oxygen vacancy-rich high-pressure rocksalt phase of zinc oxide for enhanced photocatalytic hydrogen evolution, J. Colloid Interface Sci. 666(2024)22-34, https://doi.org/10.1016/j.jcis.2024.04.010.

[39] D. Maryenko, M. Kawamura, A. Ernst, V. K. Dugaev, E. Y. Sherman, M. Kriener, M. S. Bahramy, Y. Kozuka, M. Kawasaki, Interplay of spin–orbit coupling and Coulomb interaction in ZnO-based electron system, Nat. Commun. 12(2021)3180, https://doi.org/10.1038/s41467-021-23483-4.

[40] L.-L. Zheng, J.-L. Chen, J. Yu, T. Lei, D. Wang, T. Dai, Y. Chen, Q. Fu, J.-P. Zou, Microenvironment engineering of BiVO4 for efficient photocatalytic cascade reaction to selectively convert the pollutants into multi-carbon alcohol, Appl. Catal. B. 371(2025)125162, https://doi.org/10.1016/j.apcatb.2025.125162.

[41] M. Altomare, N. T. Nguyen, S. Hejazi, P. Schmuki, A Cocatalytic Electron‐Transfer Cascade Site‐Selectively Placed on TiO2 Nanotubes Yields Enhanced Photocatalytic H2 Evolution, Adv. Funct. Mater. 28(2017)1704259, https://doi.org/10.1002/adfm.201704259.

[42] X. Sun, G. Liu, T. Shen, Y. Hu, Z. Song, Z. Wu, Q. Li, L. Zheng, W. Chen, Y.-F. Song, Directional Activation of Oxygen by the Au-Loaded ZnAl-LDH with Defect Structure for Highly Efficient Photocatalytic Oxidative Coupling of Methane, Small. 20(2024)2310857, https://doi.org/10.1002/smll.202310857.

[43] Y.-F. Wang, M.-Y. Qi, M. Conte, Z.-R. Tang, Y.-J. Xu, Bimetallic Single Atom/Nanoparticle Ensemble for Efficient Photochemical Cascade Synthesis of Ethylene from Methane, Angew. Chem. Int. Ed. 63(2024)e202407791, https://doi.org/10.1002/anie.202407791.

[44] P. Wang, X. Zhang, R. Shi, J. Zhao, G. I. N. Waterhouse, J. Tang, T. Zhang, Photocatalytic ethylene production by oxidative dehydrogenation of ethane with dioxygen on ZnO-supported PdZn intermetallic nanoparticles, Nat. Commun. 15(2024)789, https://doi.org/10.1038/s41467-024-45031-6.

[45] Q. Huang, J. Cai, F. Wei, Y. Fan, Z. Liang, K. Liu, X. F. Lu, Z. Ding, S. Wang, Selective oxidative coupling of methane to ethane with oxygen using an Au/Zn2Ti3O8 photocatalyst under mild conditions, J. Mater. Chem. A. 12(2024)21334-21340, https://doi.org/10.1039/d4ta02049a.

引用本文

王萍, 冯晓燕, 梁军 * , 张金宇, 牛涛涛, 李莉 *. Au/Sr-ZnO双位点工程用于晶格氧活化甲烷高选择性偶联制乙烷 [J]. Applied Catalysis B: Environment and Energy. 2025; 375; (). 1 - 8.

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