Dynamic coordination transformation from single-to dual-metal sites in MOFs for cascaded photoreforming of plastics into CO

doi:10.1016/S1872-2067(26)65013-9

Abstract

Abstract:

Building on the success of catalytic single-metal sites (SMSs) in various model reaction systems, dual-metal sites (DMSs) could provide further breakthrough on catalysing complex reactions especially for those involving multiple cascading steps. Specifically, photocatalytic waste plastic conversion requires bond cleavage into small molecules followed by site-dependent transformations, where DMSs photocatalysts can, in principle, be highly active and selective through efficient charge separation and dual-site synergy. However, related studies remain rare since difficulty on efficient waste plastic photodegradation usually hinders subsequent catalytic conversion. Herein, we report for the first time that dual-metal sites are developed in a two-dimensional metal-organic framework (MOF) (Cu₂-DMSs/MOF) derived from single-metal sites in bulk MOF (Cu₁-SMSs/MOF) via dynamic coordination-driven transformation. The Cu₂-DMSs/MOF catalyst exhibits enhanced photocatalytic performance without sacrificial agents, catalysing the cascading polyethylene-to-CO₂ and CO₂-to-CO reactions in one step. The polyethylene-to-CO₂ degradation rate is 2.32 mmol·g^‒1·h^‒1 and the subsequent CO₂-to-CO conversion proceeds at 0.29 mmol·g^‒1·h^‒1 with 100% selectivity, representing an order-of-magnitude enhancement compared with previous reports. The *O₂^‒ and *OH radicals formed from O₂ and H₂O oxidative cleave C‒C and C‒H bonds in polyethylene to CO₂, which is subsequentially selective reduced to CO via multi-electron proton-coupling. This work offers a conceptual advance in designing dual-metal site catalysts, opening new avenues for cascading photocatalytic conversion of white pollution into valuable chemicals.

Key words: Metal-organic framework, Dual-metal sites, Phase transformation, Photocascade, Plastic-to-fuel conversion

Jian Li, Zhenfa Wu, Xinru Zhang, Tongan Yan, Jin Luo, Wenjuan Xue, Zhaolin Lv, Hongliang Huang, Chongli Zhong. Dynamic coordination transformation from single-to dual-metal sites in MOFs for cascaded photoreforming of plastics into CO[J]. Chinese Journal of Catalysis, 2026, 84: 314-323.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65013-9

https://www.cjcatal.com/EN/Y2026/V84/I5/314

Figures/Tables 6

Scheme 1. Schematic illustration for photocatalytic cascade conversion of waste plastics over DMSs.

Fig. 1. Phase transformation process. (a) Schematic diagram of the transformation from Cu1-SMSs/MOF to Cu2-DMSs/MOF. (b) Energy diagram for the formation of Cu1-SMSs/MOF and Cu2-DMSs/MOF (ΔG is the energy change). In-situ FTIR spectra (c) and in-situ TEM images (d) of the transformation from single-metal sites into dual-metal sites by the dynamic coordination chemistry of MOFs.

Fig. 2. Structural characterization of SMSs and DMSs. HAADF-STEM images of Cu1-SMSs/MOF (a) and Cu2-DMSs/MOF (b). (c) The EDS mapping images of Cu2-DMSs/MOF. Cu K-edge XANES spectra (d) and FT-EXAFS spectra (e) of Cu1-SMSs/MOF and Cu2-DMSs/MOF with other reference compounds. DFT-optimized structure of the Cu site coordinated in Cu1-SMSs/MOF (f) and Cu2-DMSs/MOF (g) (Only the partial framework is shown for the clarity). (h?l) WT-EXAFS of Cu1-SMSs/MOF and Cu2-DMSs/MOF with other reference compounds.

Fig. 3. Photocascade catalytic performance. The yield of CO2 (a) and CO (b) during the photoconversion of PE over the Cu1-SMSs/MOF and Cu2-DMSs/MOF. (c) The control experiments of photocascade catalytic over Cu2-DMSs/MOF under altered conditions.

Fig. 4. Photocascade catalytic mechanisms over Cu2-DMSs/MOF. DMPO spin trapping ESR spectra of DMPO-*O2? (a) and DMPO-*OH (b) adducts over Cu2-DMSs/MOF. In-situ DRIFTS spectra at 3500?3800 cm?1 (c) and at 1000?2100 cm?1 (d) for detecting the reaction intermediates in the photocascade catalytic process from PE to CO over Cu2-DMSs/MOF (Reaction conditions: room temperature, O2 and H2O atmosphere, 300 W Xe lamp illumination, spectra collected with a 20-min time resolution). (e) Gibbs free energy profile of CO2 reduction reaction over Cu1-SMSs/MOF and Cu2-DMSs/MOF (inset for the optimized structures of corresponding reaction intermediates. Only the partial framework is shown for the clarity.)

Fig. 5. The proposed photocascade catalytic mechanism from PE into CO.

References

[1]	B. Qiao, A. Wang, X. Yang, L. F. Allard, Z. Jiang, Y. Cui, J. Liu, J. Li, T. Zhang, Nat. Chem., 2011, 3, 634-641.
[2]	X. Liang, N. Fu, S. Yao, Z. Li, Y. Li, J. Am. Chem. Soc., 2022, 144, 18155-18174.
[3]	J. Li, K. Zhang, N. Wang, Q. Sun, Chem. J. Chin. Univ., 2022, 43, 20220032.
[4]	H. Zhang, W. Tian, X. Duan, H. Sun, Y. Huang, Y. Fang, S. Wang, Chin. J. Catal., 2022, 43, 2301-2315.
[5]	J. Li, M. Du, Z. Wu, X. Zhang, W. Xue, H. Huang, C. Zhong, Angew. Chem. Int. Ed., 2024, 63, e202407975.
[6]	M. Xu, Z. Li, R. Shen, X. Zhang, Z. Zhang, P. Zhang, X. Li, Chin. J. Catal., 2025, 70, 431-443.
[7]	Z. Li, Y. Yang, C. Zhang, W. Fan, G. Li, J. Fang, L. Lu, Chem Catal., 2024, 4, 100902.
[8]	K. Cheng, D. Shen, Y. Xia, K. Dai, C. Shao, Y. Jiang, Y. Chen, Angew. Chem. Int. Ed., 2025, 64, e202508932.
[9]	J. Li, H. Huang, W. Xue, K. Sun, X. Song, C. Wu, L. Nie, Y. Li, C. Liu, Y. Pan, H.-L. Jiang, D. Mei, C. Zhong, Nat. Catal., 2021, 4, 719-729.
[10]	M. Zhang, P. Che, H. Ma, X. Liu, S. Zhang, Y. Luo, J. Xu, Chin. J. Catal., 2024, 67, 144-156.
[11]	S. Wang, J. Ma, L. Chen, X. Zhang, Acta Chim. Sin., 2021, 79, 216.
[12]	S. Yue, Z. Zhao, Y. Liu, M. Yang, T. Zhang, F. Li, K. Liu, P. Wang, S. Zhan, Adv. Funct. Mater., 2025, 35, 09766.
[13]	Y. Li, B. Wei, M. Zhu, J. Chen, Q. Jiang, B. Yang, Y. Hou, L. Lei, Z. Li, R. Zhang, Y. Lu, Adv. Mater., 2021, 33, 2102212.
[14]	Y. Ling, H. Su, R.-Y. Zhou, Q. Feng, X. Zheng, J. Tang, Y. Li, M. Zhang, Q. Wang, J.-F. Li, Chin. J. Catal., 2025, 73, 347-357.
[15]	Y. Wu, W. Jiang, W. Xu, F. Lv, S. Song, L. Hu, C. Wang, L. Zheng, W. Gu, R. Zhang, S. Guo, C. Zhu, J. Am. Chem. Soc., 2025, 147, 1, 1356-1363.
[16]	H. Liu, S. He, J. Qu, Y. Cai, X. Yang, C.-M. Li, J. Hu, Chin. J. Catal., 2024, 65, 1-39.
[17]	J. Tian, C. Guan, H. Hu, E. Liu, D. Yang, Acta Phys.-Chim. Sin., 2025, 41, 100068.
[18]	T. Uekert, M. F. Kuehnel, D. W. Wakerley, E. Reisner, Energy Environ. Sci., 2018, 11, 2853-2857.
[19]	T. Uekert, H. Kasap, E. Reisner, J. Am. Chem. Soc., 2019, 141, 15201-15210.
[20]	J. Lv, H. Chu, C. Shao, L. Sun, G. Dawson, K. Dai, Chin. J. Catal., 2025, 78, 75-99.
[21]	J. Xiao, Sci. Bull., 2023, 68, 2498-2499.
[22]	Z. Ya, S. Zhang, D. Xu, H. Wang, M. Li, ACS Catal., 2025, 15, 5339-5369.
[23]	H. Ran, X. Sun, M. Zheng, Y. Jing, ACS Catal., 2025, 15, 8551-8585.
[24]	H. Yang, Y. Su, J. Liu, J. Liu, D. Fang, F. Liu, J. Colloid Interface Sci., 2026, 703, 139127.
[25]	Y. Yan, L. Hao, Z. Ren, R. Shen, G. Liang, P. Zhang, Y. Teng, D. Xu, X. Li, J. Mater. Sci. Technol., 2026, 249, 305-332.
[26]	Y. Shao, R. Shen, S. Wang, S. Li, P. Zhang, X. Li, Acta Phys.-Chim. Sin., 2025, 41, 100176.
[27]	W. Yu, Chin. J. Catal., 2025, 73, 8-11.
[28]	M. G. Campbell, D. Sheberla, S. F. Liu, T. M. Swager, M. Dincă, Angew. Chem. Int. Ed., 2015, 54, 4349-4352.
[29]	M. Song, X. Song, X. Liu, W. Zhou, P. Huo, Chin. J. Catal., 2023, 51, 180-192.
[30]	S. Krause, N. Hosono, S. Kitagawa, Angew. Chem. Int. Ed., 2020, 59, 15325-15341.
[31]	B. Zhong, J. Hu, X. Yang, Y. Shu, Y. Cai, C.-M. Li, J. Qu, Chin. J. Catal., 2025, 68, 177-203.
[32]	A. Schneemann, V. Bon, I. Schwedler, I. Senkovska, S. Kaskel, R. A. Fischer, Chem. Soc. Rev., 2014, 43, 6062-6096.
[33]	J. Li, X. Yu, W. Xue, L. Nie, H. Huang, C. Zhong, AlChE J., 2023, 69, e17906.
[34]	Z. Chang, D.-H. Yang, J. Xu, T.-L. Hu, X.-H. Bu, Adv. Mater., 2015, 27, 5432-5441.
[35]	Z. Wang, P. Yeary, X. Feng, W. Lin, J. Am. Chem. Soc., 2023, 145, 8647-8655.
[36]	X. Yu, J. Li, M. Du, X. Song, H. Huang, L. Nie, Cell Rep. Phys. Sci., 2023, 4, 101657.
[37]	H. Fang, X.-Y. Liu, H.-J. Ding, M. Mulcair, B. Space, H. Huang, X.-W. Li, S.-M. Zhang, M.-H. Yu, Z. Chang, X.-H. Bu, J. Am. Chem. Soc., 2024, 146, 14357-14367.
[38]	N. Yanai, K. Kitayama, Y. Hijikata, H. Sato, R. Matsuda, Y. Kubota, M. Takata, M. Mizuno, T. Uemura, S. Kitagawa, Nat. Mater., 2011, 10, 787-793.
[39]	X.-C. Sun, X.-C. Li, Z.-W. Xie, C.-Y. Yuan, D.-J. Wang, Q. Zhang, X.-Y. Guo, H. Dong, H.-C. Liu, Y.-W. Zhang, J. Energy Chem., 2024, 91, 475-483.
[40]	K. Sun, Y. Huang, F. Sun, Q. Wang, Y. Zhou, J. Wang, Q. Zhang, X. Zheng, F. Fan, Y. Luo, J. Jiang, H.-L. Jiang, Nat. Chem., 2024, 16, 1638-1646.
[41]	H. Deng, M. A. Olson, J. F. Stoddart, O. M. Yaghi, Nat. Chem., 2010, 2, 439-443.
[42]	D. J. Cerasale, D. C. Ward, T. L. Easun, Nat. Rev. Chem., 2022, 6, 9-30.
[43]	L.-J. Ji, T.-Y. Yang, G.-Q. Feng, S. Li, W. Li, X.-H. Bu, Adv. Mater., 2024, 36, 2404756.
[44]	L.-J. Ji, Y. Qin, D. Gui, W. Li, Y. Li, X. Li, P. Lu, Chem. Mater., 2018, 30, 8732-8738.
[45]	J. Xu, X. Jiao, K. Zheng, W. Shao, S. Zhu, X. Li, J. Zhu, Y. Pan, Y. Sun, Y. Xie, Natl. Sci. Rev., 2022, 9, nwac011.
[46]	S. Deng, R. Cao, X. Wang, Y. Zhou, J. Liang, H. Tang, X. Feng, S. Yang, Y. Shangguan, Y. Li, H. Chen, Nano Lett., 2024, 24, 14082-14090.
[47]	M. Jiang, J. Li, X. Wan, J. Qiu, T. Yao, W. Zhang, S. Ma, H. Tan, A. Han, C. Chen, G. Liu, Nat. Commun., 2025, 16, 4136.
[48]	M. Li, S. Zhang, ACS Catal., 2024, 14, 6717-6727.
[49]	Y. Miao, Y. Zhao, J. Gao, J. Wang, T. Zhang, J. Am. Chem. Soc., 2024, 146, 4842-4850.
[50]	M. Bertoldo, S. Bronco, C. Cappelli, T. Gragnoli, L. Andreotti, J. Phys. Chem. B, 2003, 107, 11880-11888.
[51]	J. Shang, M. Chai, Y. Zhu, Environ. Sci. Technol., 2003, 37, 4494-4499.
[52]	X. Zhao, Z. Li, Y. Chen, L. Shi, Y. Zhu, Appl. Surf. Sci., 2008, 254, 1825-1829.
[53]	X. Jiao, K. Zheng, Q. Chen, X. Li, Y. Li, W. Shao, J. Xu, J. Zhu, Y. Pan, Y. Sun, Y. Xie, Angew. Chem. Int. Ed., 2020, 59, 15497-15501.
[54]	K. Su, T. Gao, C. H. Tung, L. Z. Wu, Angew. Chem. Int. Ed., 2024, 63, e202407464.
[55]	S.-L. Meng, C. Ye, X.-B. Li, C.-H. Tung, L.-Z. Wu, J. Am. Chem. Soc., 2022, 144, 16219-16231.
[56]	Z. Huang, M. Shanmugam, Z. Liu, A. Brookfield, E. L. Bennett, R. Guan, D. E. Vega Herrera, J. A. Lopez-Sanchez, A. G. Slater, E. J. L. McInnes, X. Qi, J. Xiao, J. Am. Chem. Soc., 2022, 144, 6532-6542.
[57]	T.-C. Chou, C.-C. Chang, H.-L. Yu, W.-Y. Yu, C.-L. Dong, J.-J. Velasco-Vélez, C.-H. Chuang, L.-C. Chen, J.-F. Lee, J.-M. Chen, H.-L. Wu, J. Am. Chem. Soc., 2020, 142, 2857-2867.