Oxygen vacancy promoted C-H activation enhancing hydrogenolysis of polyethylene plastics over Ru/CeO2 catalyst

doi:10.1016/S1872-2067(25)64897-2

Abstract

Abstract:

Catalytic hydrogenolysis offers a promising route for plastic waste upcycling. Herein, we demonstrate that oxygen vacancies (O_V) in CeO₂ supports dramatically enhanced this process. Reduction-engineered Ru/CeO₂-NH₃-800 exhibits 40% higher activity at 800 °C than untreated counterparts. Comprehensive characterization revealed unchanged Ru metal sites after treatment, but significantly increased oxygen vacancy content in the CeO₂ support. Isotopic C₆-D₂ temperature-programmed surface reaction studies revealed that higher O_V concentrations correlate with lower C-H bond activation temperatures, directly aligning with observed activity trends. We propose a novel Ru-Ce interfacial mechanism: O_V-adjacent Ce³⁺-O sites activate C-H bonds to form *RCCR* intermediates, while dual Ru sites cleave C-C bonds via C-Ru coordination. This work establishes an O_V-driven structure-activity relationship for the first time and reveals support-mediated C-H activation as crucial for advanced catalyst design.

Key words: PE waste, Hydrogenolysis, Oxygen vacancy, C-H bond activation, Pretreatment

Chengyang Sun, Haochen Zhang, Xiaohui Liu, Yanqin Wang. Oxygen vacancy promoted C-H activation enhancing hydrogenolysis of polyethylene plastics over Ru/CeO₂ catalyst[J]. Chinese Journal of Catalysis, 2026, 84: 337-346.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64897-2

https://www.cjcatal.com/EN/Y2026/V84/I5/337

Figures/Tables 14

Fig. 1. Hydrogenolysis products distribution over Ru/CeO2 treated by different reducing gas. Reaction conditions: 2 g C20, 100 mg catalyst, 3 MPa H2, 240 °C, 1 h.

Fig. 2. Comparison of hydrogenolysis reaction behavior over reducible oxides (a,b,c,d) and non-reducible oxides (e,f,g,h), before (a,c,e,g) and after (b,d,f,h) the reducing treatment. Reaction conditions: 2 g C20, 100 mg catalyst, 3 MPa H2, 240 °C, 6 h for (c,d), 1 h for others.

Fig. 3. Effects of different reduction temperature on the hydrogenolysis reaction behavior of catalysts. Reaction conditions: 2 g C20, 100 mg catalyst, 3 MPa H2, 240 °C, 1 h.

Fig. 4. Effects of different reduction temperature on the hydrogenolysis reaction behavior of catalysts by using LDPE plastic as substrate. Reaction conditions: 2 g LDPE, 100 mg catalyst, 3 MPa H2, 240 °C, with respective reaction time labeled on the figure.

Fig. 5. XRD patterns (a) and H2-TPR profiles (b) of four different Ru/CeO2 catalysts.

Table 1 Surface area, Ru content and dispersion of four different Ru/CeO2 catalysts.

Sample	S_BET (m²/g)	Ru content ^a (wt%)	Ru dispersion ^b (%)
Ru-CeO₂	15.84	2.0	72.9
Ru-CeO₂-600	7.62	1.6	69.2
Ru-CeO₂-800	5.50	1.6	73.4
Ru-CeO₂-1000	1.18	1.9	70.5

Fig. 6. TEM images and Ru particle size distributions of four different Ru/CeO2 catalysts.

Fig. 7. CO2-TPD profiles of four different Ru/CeO2 catalysts.

Fig. 8. CO-DRIFT spectra of Ru on four different Ru/CeO2 catalysts.

Fig. 9. XPS spectra of Ru 3p (a), O 1s (b), Ce 3d (c) and N 1s (d) peaks in four different Ru/CeO2 catalysts.

Fig. 10. H2-D2 TPSR profiles of four different Ru/CeO2 catalysts under 35 °C.

Fig. 11. C6-D2 TPSR profiles of four different Ru/CeO2 catalysts.

Fig. 12. Consumption on four different Ru/CeO2 catalysts in the C6-D2 TPSR experiment.

Fig. 13. Proposed hydrogenolysis mechanism on Ru-Ce interface sites.

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Oxygen vacancy promoted C-H activation enhancing hydrogenolysis of polyethylene plastics over Ru/CeO₂ catalyst

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