氧空位促进C-H键活化提高Ru/CeO2上聚乙烯氢解活性

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

催化学报 ›› 2026, Vol. 84: 337-346.DOI: 10.1016/S1872-2067(25)64897-2

氧空位促进C-H键活化提高Ru/CeO₂上聚乙烯氢解活性

孙承阳, 张浩晨, 刘晓晖, 王艳芹()

华东理工大学化学与分子工程学院, 上海市功能材料化学重点实验室, 上海 200237

收稿日期:2025-09-15 接受日期:2025-10-12 出版日期:2026-05-18 发布日期:2026-04-16
通讯作者: *电子信箱: wangyanqin@ecust.edu.cn (王艳芹).
作者简介:第一联系人：¹共同第一作者.
基金资助:
国家重点研发计划(2022YFA1504903);国家自然科学基金(22172048)

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

Chengyang Sun, Haochen Zhang, Xiaohui Liu, Yanqin Wang()

Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2025-09-15 Accepted:2025-10-12 Online:2026-05-18 Published:2026-04-16
Contact: *E-mail: wangyanqin@ecust.edu.cn (Y. Wang).
About author:First author contact:¹Contributed equally to this work.
Supported by:
National Key Research and Development Program of China(2022YFA1504903);National Natural Science Foundation of China(22172048)

摘要/Abstract

摘要：

塑料因其成本低、易加工和耐用性好等优点被广泛应用, 然而, 大量废弃塑料难以高效回收, 加之其原料依赖不可再生化石资源, 限制了塑料产业的可持续发展. 开发废弃塑料的化学回收方法,不仅有助于缓解环境污染, 还能将其转化为聚合物单体或高附加值化学品, 从而替代部分石油原料, 为发展可再生塑料与能源争取时间. 在各类塑料中, C-C键连接型塑料使用量最大, 但其解聚通常面临反应温度高、产物复杂及附加值低等挑战.

本文聚焦于C-C键连接型塑料的高效催化转化研究. 针对聚乙烯(PE)氢解反应, 本文从C-H键活化及氧化物载体调控两方面入手, 通过对CeO₂载体进行高温还原处理提升其表面氧空位浓度, 进而增强C-H键活化能力. 所制备的Ru/CeO₂-NH₃-800催化剂在PE氢解反应中的活性相较于未经处理的Ru/CeO₂提高了40%. 系统表征结果表明, 还原处理前后Ru物种的分散度、颗粒尺寸及电子状态基本一致, 表明金属位点并非活性提升的主要因素. 进一步对CeO₂载体分析发现, 随着还原温度升高, 载体氧空位含量显著增加, 且该变化趋势与催化剂氢解活性高度吻合. 在排除NH₃处理引入表面新物种的可能性后, 确认氧空位的增加是Ru/CeO₂-NH₃-800催化剂氢解活性提高的关键原因. 通过C₆-D₂程序升温表面反应实验, 确认烷烃氢解反应中C-H键的解离活化为反应决速步, 并成功建立载体氧空位与C-H键活化之间的关联. 此外, 提出在Ru-Ce界面位点上发生PE氢解反应的机理: 氧空位邻近的Ce³⁺-O位点促进C-H键活化生成关键中间体*RCCR*, 该中间体在相邻Ru原子作用下发生C-C键断裂, 二者协同完成氢解过程.

综上, 本研究通过在CeO₂载体中构建氧空位, 显著提升了Ru/CeO₂催化PE氢解的性能. 该工作不仅凸显了C-H键活化在PE氢解中的关键作用, 建立了载体氧空位与催化性能之间的构效关系, 还为理解金属-载体界面在氢解反应中的作用机制提供了实验依据与理论支撑, 为设计高效PE氢解催化剂提供新思路.

关键词: 聚乙烯, 氢解, 氧空位, C-H键活化, 预处理

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

孙承阳, 张浩晨, 刘晓晖, 王艳芹. 氧空位促进C-H键活化提高Ru/CeO₂上聚乙烯氢解活性[J]. 催化学报, 2026, 84: 337-346.

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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图/表 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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氧空位促进C-H键活化提高Ru/CeO₂上聚乙烯氢解活性

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

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