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

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, 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. 另外还提出在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假设, 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, DOI: 10.1016/S1872-2067(25)64897-2.

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, DOI: 10.1016/S1872-2067(25)64897-2.

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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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