Hydride-mediated chemoselective C–H bond formation during benzoic acid hydrodeoxygenation on anatase TiO2†

IF 3.1 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Reaction Chemistry & Engineering Pub Date : 2025-03-04 DOI:10.1039/D4RE00561A

Mikyung Hwang, Jeremy Hu, Michael J. Janik and Konstantinos Alexopoulos

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Abstract

The chemoselective hydrogenation of benzoic acid to aromatic products such as benzaldehyde, benzyl alcohol, toluene, and benzene is studied on anatase TiO₂ (001) using density functional theory (DFT) and microkinetic modeling (MKM). Oxygen vacancy (O_vac) sites are more active for benzoic acid hydrogenation than fully oxidized surface regions, with a nearly 2.5 eV lower energy for the first C–H bond formation reaction to occur near O_vac. This favorable C–H bond formation mechanism on anatase TiO₂ occurs between hydrides (H⁻) and monoanionic intermediates coadsorbed in O_vac. A steady-state microkinetic model is constructed using computed reaction energies and activation barriers to determine rates of product formation at different reaction temperatures. Product selectivities differ in distinct temperature ranges, caused by competition among reaction and product desorption steps. Sensitivity analysis shows which elementary steps significantly affect the overall benzoic acid hydrogenation activity and selectivity.

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锐钛矿TiO2†上苯甲酸加氢脱氧过程中氢化物介导的化学选择性C-H键形成

利用密度泛函数理论（DFT）和微动力学模型（MKM）研究了在锐钛矿TiO2（001）上苯甲酸化学选择性加氢制苯甲醛、苯甲醇、甲苯和苯等芳香族产物。氧空位（Ovac）位点比完全氧化的表面区域对苯甲酸加氢反应更活跃，在Ovac附近发生的第一个C-H键形成反应的能量低近2.5 eV。这种有利的C-H键形成机制发生在氢化物（H−）和Ovac共吸附的单阴离子中间体之间。利用计算的反应能和激活势垒建立了稳态微动力学模型，以确定不同反应温度下的产物生成速率。产物的选择性在不同的温度范围内是不同的，这是由反应和产物脱附步骤之间的竞争引起的。敏感性分析表明，基本步骤对苯甲酸加氢活性和选择性有显著影响。

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来源期刊

Reaction Chemistry & Engineering Chemistry-Chemistry (miscellaneous)

CiteScore

6.60

自引率

7.70%

发文量

227

期刊介绍： Reaction Chemistry & Engineering is a new journal reporting cutting edge research into all aspects of making molecules for the benefit of fundamental research, applied processes and wider society. From fundamental, molecular-level chemistry to large scale chemical production, Reaction Chemistry & Engineering brings together communities of chemists and chemical engineers working to ensure the crucial role of reaction chemistry in today’s world.