Non-Linear Arrhenius Behavior of m-Cresol Hydrogenation over Platinum

IF 2.3 4区化学 Q3 CHEMISTRY, PHYSICAL Catalysis Letters Pub Date : 2024-08-17 DOI:10.1007/s10562-024-04776-x

Nhung N. Duong, Camila A. Teles, Fabio B. Noronha, Daniel E. Resasco

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Abstract

The hydrogenation of m-cresol was studied across a wide temperature range, revealing complex variations in product distribution and reaction mechanisms. It has been found that the hydrogenation process predominantly yields 3-methylcyclohexanone and 3-methylcyclohexanol as primary products through ring hydrogenation (HYD) within the 140–250 ℃ temperature range. Conversely, the hydrodeoxygenation (HDO) products, toluene and methylcyclohexane, remain insignificant. More interestingly, the HYD yield is observed to diminish at elevated temperatures, with HDO becoming more dominant beyond 270 ℃. Further exploration of potential factors influencing the observed reduction in HYD yield at elevated temperatures—namely site deactivation, equilibrium limitations, and variations in surface coverage—revealed that changes in the surface adsorption of m-cresol play a critical role in the observed decrease in HYD activity, rather than site deactivation or equilibrium constraints. The order of 3-methylcyclohexanone formation with respect to m-cresol increases from 0 to 1 across the examined temperature range, suggesting m-cresol adsorption follows a simple Langmuir–Hinshelwood adsorption model where \(r \sim k{K}_{C}{P}_{C}/(1+{K}_{C}{P}_{C})\). This analysis not only advances our understanding of the temperature-dependent behavior in m-cresol hydrogenation but also lays the groundwork for future kinetic modeling, offering deeper insight into the complex dynamics of m-cresol hydrogenation.

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间甲酚在铂上的非线性阿伦尼乌斯氢化行为

研究人员在很宽的温度范围内对间甲酚的氢化过程进行了研究，揭示了产物分布和反应机理的复杂变化。研究发现，在 140-250 ℃ 的温度范围内，氢化过程主要通过环氢化（HYD）生成 3-甲基环己酮和 3-甲基环己醇作为主要产物。相反，氢脱氧（HDO）产物甲苯和甲基环己烷仍然微不足道。更有趣的是，观察到 HYD 产物在温度升高时会减少，而 HDO 在 270 ℃ 以上会变得更加主要。对影响观察到的 HYD 产率在温度升高时降低的潜在因素（即位点失活、平衡限制和表面覆盖率变化）的进一步探索表明，间甲酚表面吸附的变化在观察到的 HYD 活性降低中起了关键作用，而不是位点失活或平衡限制。在所考察的温度范围内，3-甲基环己酮的形成与间甲酚有关的顺序从 0 增加到 1，这表明间甲酚的吸附遵循一个简单的 Langmuir-Hinshelwood 吸附模型，其中 \(r \sim k{K}_{C}{P}_{C}/(1+{K}_{C}{P}_{C})\).这一分析不仅加深了我们对间苯二酚加氢过程中温度依赖性行为的理解，而且为今后的动力学建模奠定了基础，使我们对间苯二酚加氢的复杂动力学过程有了更深入的了解。

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来源期刊

Catalysis Letters 化学-物理化学

CiteScore

5.70

自引率

3.60%

发文量

327

审稿时长

1 months

期刊介绍： Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis. The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.