C3H8 oxidation on atomic-scale catalysts: insights into active oxygen species and reaction pathways

IF 12.2 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Journal of Hazardous Materials Pub Date : 2025-05-28 DOI:10.1016/j.jhazmat.2025.138716

Qifeng Zhang, Yuchun Song, Aijie Xu, Zhi-Qiang Wang, Li Wang, Yanglong Guo, Aiyong Wang, Wangcheng Zhan, Yun Guo

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Abstract

Compared to nano-catalysts, atomic-scale dispersed catalysts offer greater potential for elucidating the fundamental nature of catalytic reactions. To investigate the role of ultra-low Ru loading (0.1 wt%) in C₃H₈ oxidation, single-atom (Ru/CeO₂-SA), dual-pair (Ru2/CeO₂), and tetra-atomic cluster (Ru4/CeO₂) catalysts were employed. Loading Ru on CeO₂ suppressed C₃H₈ adsorption while modulated oxygen activation, thereby influencing the reaction intermediates and engineering the propane oxidation pathways. Notably, Ru/CeO₂-SA and Ru4/CeO₂ exhibited superior propane oxidation performance compared to Ru2/CeO₂ under both hydrated and anhydrous conditions. Ru/CeO₂-SA achieved remarkable turnover frequency (TOF) of 43.7 ⁎ 10^-2s^-1 at 280 °C and 50% conversion temperature (T₅₀) as low as 267 °C, which surpassed Ru2/CeO₂ (TOF = 16.7 ⁎10^-2s^-1, T₅₀ = 365 °C) and Ru4/CeO₂ (TOF = 33.1⁎10^-2s^-1, T₅₀ = 330 °C), highlighting the critical role of single-atom architecture in enhancing catalytic efficiency. This enhanced performance was attributed to the formation of acrylic acid intermediates, facilitated by the surface lattice oxygen of CeO₂ adjacent to Ru. In contrast, the propionic acid generated from chemisorbed oxygen on Ru2/CeO₂ demonstrated a weaker promoting effect compared to acrylic acid. Additionally, the rapid oxidation of acetate to formate by lattice oxygen further contributed to the enhanced catalytic activity.

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C3H8在原子级催化剂上氧化：对活性氧种类和反应途径的见解

与纳米催化剂相比，原子级分散催化剂在阐明催化反应的基本性质方面具有更大的潜力。采用单原子（Ru/CeO2- sa）、双对（Ru2/CeO2）和四原子簇（Ru4/CeO2）催化剂研究了超低Ru负载（0.1 wt%）在C3H8氧化中的作用。在CeO2上负载Ru抑制了C3H8的吸附，同时调节了氧的活化，从而影响了反应中间体，改造了丙烷的氧化途径。值得注意的是，Ru/CeO2- sa和Ru4/CeO2在水合和无水条件下均表现出优于Ru2/CeO2的丙烷氧化性能。Ru/CeO2- sa在280℃下的转换频率（TOF）达到了43.7℃- 10-2 s-1, 50%的转化温度（T50）低至267℃，超过了Ru2/CeO2 （TOF = 16.7℃- 10-2 s-1, T50 = 365℃）和Ru4/CeO2 （TOF = 33.1℃- 10-2 s-1, T50 = 330℃），突出了单原子结构在提高催化效率方面的关键作用。这种增强的性能是由于邻近Ru的CeO2表面晶格氧促进了丙烯酸中间体的形成。相比之下，化学吸附氧生成的丙酸对Ru2/CeO2的促进作用弱于丙烯酸。此外，晶格氧对乙酸酯的快速氧化生成甲酸进一步促进了催化活性的增强。

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来源期刊

Journal of Hazardous Materials 工程技术-工程：环境

CiteScore

25.40

自引率

5.90%

发文量

3059

审稿时长

58 days

期刊介绍： The Journal of Hazardous Materials serves as a global platform for promoting cutting-edge research in the field of Environmental Science and Engineering. Our publication features a wide range of articles, including full-length research papers, review articles, and perspectives, with the aim of enhancing our understanding of the dangers and risks associated with various materials concerning public health and the environment. It is important to note that the term "environmental contaminants" refers specifically to substances that pose hazardous effects through contamination, while excluding those that do not have such impacts on the environment or human health. Moreover, we emphasize the distinction between wastes and hazardous materials in order to provide further clarity on the scope of the journal. We have a keen interest in exploring specific compounds and microbial agents that have adverse effects on the environment.