Mechanistic Investigation of Dimethyl Carbonate Synthesis Over Palladium Chloride Catalyst

IF 2.3 4区化学 Q3 CHEMISTRY, PHYSICAL Catalysis Letters Pub Date : 2024-12-02 DOI:10.1007/s10562-024-04855-z

Zhi-Shen Huang, Zhang-Feng Zhou, Lu-Yang Qiao, Yun-Yun Zeng, Shan-Shan Zong, Yuan-Gen Yao

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Abstract

The production of dimethyl carbonate (DMC) from CO and methyl nitrite (MN) is of great industrial interest for chemicals upgrading. As one of the most efficient catalysts, PdCl₂ based catalyst has been widely investigated and been verified to be highly selective toward DMC yielding. However, the underlying mechanism is unclear so far. Herein, we identified the active sites and corresponding reaction pathway on PdCl₂ (140) surface by the density functional theory (DFT) calculations, combining with X-ray absorption fine structure (XAFS) and in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements. The dissociation of MN resulted in the construction of Cl vacancies on PdCl₂ (140) surface, which are the specific sites for DMC formation. On the other hand, the continuous loss of Cl induced the reduction of PdCl₂ to Pd, leading to changed pathway of reaction and decreased yield of DMC. These insights highlighted the importance of Cl-balance in PdCl₂ based catalyst system, which determined the final products of CO oxidative esterification.

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氯化钯催化合成碳酸二甲酯的机理研究

以CO和亚硝酸盐甲酯（MN）为原料生产碳酸二甲酯（DMC）具有重要的工业意义。作为最高效的催化剂之一，PdCl2基催化剂已被广泛研究，并被证明对DMC的产率具有高选择性。然而，到目前为止，其潜在机制尚不清楚。本文通过密度泛函理论（DFT）计算，结合x射线吸收精细结构（XAFS）和原位漫反射红外傅立叶变换光谱（DRIFTS）测量，确定了PdCl2（140）表面的活性位点和相应的反应途径。MN的解离导致PdCl2（140）表面形成Cl空位，这是DMC形成的特定位点。另一方面，Cl的持续损失诱导PdCl2还原为Pd，导致反应途径改变，DMC产率降低。这些发现强调了基于PdCl2的催化剂体系中cl平衡的重要性，它决定了CO氧化酯化的最终产物。图形抽象

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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.