Abstract
Photocatalytic CH4 coupling into high-valued C2H6 is highly attractive, whereas the photosynthetic rate, especially under oxygen-free system, is still unsatisfying. Here, we designed the negatively charged metal supported on metal oxide nanosheets to activate the inert C–H bond in CH4 and hence accelerate CH4 coupling performance. As an example, the synthetic Au/ZnO porous nanosheets exhibit the C2H6 photosynthetic rate of 1,121.6 µmol gcat−1 h−1 and the CH4 conversion rate of 2,374.6 µmol gcat−1 h−1 under oxygen-free system, 2 orders of magnitude higher than those of previously reported photocatalysts. By virtue of several in situ spectroscopic techniques, it is established that the generated Auδ− and O− species together polarized the C–H bond, while the Auδ− and O− species jointly stabilized the CH3 intermediates, which favored the coupling of CH3 intermediate to photosynthesize C2H6 instead of overoxidation into COx. Thus, the design of dual active species is beneficial for achieving high-efficient CH4-to-C2H6 photoconversion.
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Sattler JJHB, Ruiz-Martinez J, Santillan-Jimenez E, Weckhuysen BM. Chem Rev, 2014, 114: 10613–10653
Qi G, Davies TE, Nasrallah A, Sainna MA, Howe AGR, Lewis RJ, Quesne M, Catlow CRA, Willock DJ, He Q, Bethell D, Howard MJ, Murrer BA, Harrison B, Kiely CJ, Zhao X, Deng F, Xu J, Hutchings GJ. Nat Catal, 2022, 5: 45–54
Song H, Meng X, Wang S, Zhou W, Wang X, Kako T, Ye J. J Am Chem Soc, 2019, 141: 20507–20515
Mao Y, Hu P. Sci China Chem, 2020, 63: 850–859
Song H, Meng X, Wang Z, Liu H, Ye J. Joule, 2019, 3: 1606–1636
Wu Y, Wu M, Zhu J, Zhang X, Li J, Zheng K, Hu J, Liu C, Pan Y, Zhu J.. Sci China Chem,, 2023, 66: 1997–2003
Zheng K, Wu Y, Hu Z, Jiao X, Li L, Zhao Y, Wang S, Zhu S, Liu W, Yan W, Sun Y, Xie Y. Nano Lett, 2021, 21: 10368–10376
An B, Li Z, Wang Z, Zeng X, Han X, Cheng Y, Sheveleva AM, Zhang Z, Tuna F, McInnes EJL, Frogley MD, Ramirez-Cuesta AJ, S. Natrajan L, Wang C, Lin W, Yang S, Schröder M. Nat Mater, 2022, 21: 932–938
Snyder BER, Vanelderen P, Bols ML, Hallaert SD, Böttger LH, Ungur L, Pierloot K, Schoonheydt RA, Sels BF, Solomon EI. Nature, 2016, 536: 317–321
Tan SH, Barton PI. Energy, 2015, 93: 1581–1594
Zhu S, Li X, Pan Z, Jiao X, Zheng K, Li L, Shao W, Zu X, Hu J, Zhu J, Sun Y, Xie Y. Nano Lett, 2021, 21: 4122–4128
Jiang W, Low J, Mao K, Duan D, Chen S, Liu W, Pao CW, Ma J, Sang S, Shu C, Zhan X, Qi Z, Zhang H, Liu Z, Wu X, Long R, Song L, Xiong Y. J Am Chem Soc, 2020, 143: 269–278
Wang P, Zhao G, Wang Y, Lu Y. Sci Adv, 2017, 3: e1603180
Luo L, Gong Z, Xu Y, Ma J, Liu H, Xing J, Tang J. J Am Chem Soc, 2021, 144: 740–750
Latimer AA, Kakekhani A, Kulkarni AR, Nerskov JK. ACS Catal, 2018, 8: 6894–6907
Liang L, Ling P, Li Y, Li L, Liu J, Luo Q, Zhang H, Xu Q, Pan Y, Zhu J, Ye B, Sun Y. Sci China Chem, 2021, 64: 953–958
Serra-Maia R, Michel FM, Kang Y, Stach EA. ACS Catal, 2020, 10: 5115–5123
Yuliati L, Yoshida H. Chem Soc Rev, 2008, 37: 1592–1602
Jiao X, Hu Z, Li L, Wu Y, Zheng K, Sun Y, Xie Y. Sci China Chem, 2022, 65: 428–440
Liang L, Li X, Sun Y, Tan Y, Jiao X, Ju H, Qi Z, Zhu J, Xie Y. Joule, 2018, 2: 1004–1016
Abdel-Mageed AM, Klyushin A, Rezvani A, Knop-Gericke A, Schlögl R, Behm RJ. Angew Chem, 2019, 131: 10431–10436
Sterrer M, Yulikov M, Fischbach E, Heyde M, Rust HP, Pacchioni G, Risse T, Freund HJ. Angew Chem Int Ed, 2006, 45: 2630–2632
He Y, Guo F, Yang KR, Heinlein JA, Bamonte SM, Fee JJ, Hu S, Suib SL, Haller GL, Batista VS, Pfefferle LD. J Am Chem Soc, 2020, 142: 17119–17130
Li R, Hu J, Deng M, Wang H, Wang X, Hu Y, Jiang HL, Jiang J, Zhang Q, Xie Y, Xiong Y. Adv Mater, 2014, 26: 4783–4788
Zheng K, Wu Y, Zhu J, Wu M, Jiao X, Li L, Wang S, Fan M, Hu J, Yan W, Zhu J, Sun Y, Xie Y. J Am Chem Soc, 2022, 144: 12357–12366
Xie P, Ding J, Yao Z, Pu T, Zhang P, Huang Z, Wang C, Zhang J, Zecher-Freeman N, Zong H, Yuan D, Deng S, Shahbazian-Yassar R, Wang C. Nat Commun, 2022, 13: 1375
Leelavathi A, Madras G, Ravishankar N. Phys Chem Chem Phys, 2013, 15: 10795–10802
Carter E, Carley AF, Murphy DM. JPhys Chem C, 2007, 111: 10630–10638
Bai S, Xu Y, Wang P, Shao Q, Huang X. ACS Catal, 2019, 9: 6938–6944
Acknowledgements
This work was supported by the National Key R&D Program of China (2019YFA0210004, 2022YFA1502904, 2021YFA1501502), the National Natural Science Foundation of China (22125503, 21975242, U2032212, 21890754, 22002148), 2023 Synchrotron Radiation Joint Fund of USTC, and the Youth Innovation Promotion Association of CAS (CX2340007003).
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Zheng, K., Zhang, X., Hu, J. et al. High-rate CH4-to-C2H6 photoconversion enabled by Au/ZnO porous nanosheets under oxygen-free system. Sci. China Chem. 67, 869–875 (2024). https://doi.org/10.1007/s11426-023-1792-8
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DOI: https://doi.org/10.1007/s11426-023-1792-8