Enhanced metal-support interaction over Pd-Au/TiO2 catalysts for vinyl acetate synthesis

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL Journal of Catalysis Pub Date : 2024-11-22 DOI:10.1016/j.jcat.2024.115854

Minhua Zhang, Wen Tian, Guochao Yang, Haoxi Jiang, Lingtao Wang

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Abstract

The reaction of ethylene and acetic acid to produce vinyl acetate (VAM) was investigated on Pd-Au nanoparticles (NPs) supported on TiO₂. Compared with the commercial catalyst Pd-Au/SiO₂, Pd-Au/TiO₂ exhibited a higher turnover frequency (TOF), likely due to the formation of smaller Pd-Au NPs (∼1.9 nm) and metal support interactions (MSI) between TiO₂ with Pd-Au NPs. We found that the oxygen vacancies (OVs) of the TiO₂ were regulated by adjusting the reduction temperature, facilitating electron transfer from TiO₂ to the Pd-Au NPs, leading to enhanced MSI. In situ diffuse reflectance infrared Fourier transform spectroscopy (In situ DRIFTs) and density functional theory (DFT) calculations indicated that the electron-rich Pd-Au NPs of Pd-Au/TiO₂ catalyst enhanced O₂ activation for increased TOF, and also promoted AcOH dehydrogenation and the key reaction of ethylene and acetate coupling. Our findings demonstrated that reducible supports could effectively influence the electronic properties of Pd-Au NPs through the construction of MSI, thereby enhancing catalytic activity.

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用于合成醋酸乙烯酯的 Pd-Au/TiO2 催化剂上增强的金属-支撑相互作用

研究了乙烯与醋酸反应生成醋酸乙烯酯（VAM）的过程，该反应是在 TiO2 上支撑的钯金纳米粒子（NPs）上进行的。与商用催化剂 Pd-Au/SiO2 相比，Pd-Au/TiO2 表现出更高的翻转频率 (TOF)，这可能是由于形成了更小的 Pd-Au NPs（1.9 纳米）以及 TiO2 与 Pd-Au NPs 之间的金属支撑相互作用 (MSI)。我们发现，通过调节还原温度可以调节 TiO2 的氧空位（OVs），促进电子从 TiO2 转移到 Pd-Au NPs，从而增强 MSI。原位漫反射红外傅立叶变换光谱（In situ DRIFTs）和密度泛函理论（DFT）计算表明，Pd-Au/TiO2 催化剂中富含电子的 Pd-Au NPs 增强了 O2 的活化，从而提高了 TOF，还促进了 AcOH 脱氢以及乙烯和醋酸酯偶联的关键反应。我们的研究结果表明，可还原支撑物可通过构建 MSI 有效影响钯金氮氧化物的电子特性，从而提高催化活性。

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.