Reducing the Surface Acidity of Pd/NaY Catalyst by Alkali Phosphates Modification to Improve the Selectivity of Dimethyl Carbonate

IF 2.3 4区化学 Q3 CHEMISTRY, PHYSICAL

Catalysis Letters Pub Date : 2025-02-21 DOI:10.1007/s10562-025-04952-7

Bo-Wei Shi, Xiao-Yuan Tan, Ming-Sheng Wang, Jing Sun, Zhong-Ning Xu, Guo-Cong Guo

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Abstract

CO esterification to dimethyl carbonate (DMC) routes holds significant economic and environmental value. Nevertheless, industrial routes suffer from drawbacks, such as raw material methyl nitrite (MN) was decomposed into by-products dimethoxymethane (DMM) and methyl formate (MF), which caused subsequent separation problem for the product/reactant mixture, which results in additional production cost. Previous studies have demonstrated that the acid site of NaY play an essential role in promoting the decomposition of MN. Herein, a series of Na₂HPO₄ -modified Pd/NaY catalysts were prepared to solve these problems. The results indicated that the introduction of Na₂HPO₄ increased the DMC selectivity (from 55% to 83%) and decreased the by-products selectivity [DMM (from 22% to 10%), MF (from 23% to 7%)] of Pd/PNaY-12 significantly. Based on the results of Py-IR, the amounts of Lewis acidic sites decreased, and NH₃-TPD analysis shown that the amounts of weak acid sites (from 0.33 mmol/g to 0.14 mmol/g) and medium strong acid sites (from 0.46 mmol/g to 0.10 mmol/g) also reduced obviously. The outstanding performance should be attributed to the fact that the important intermediate *COOCH₃ was more readily obtained after Na₂HPO₄ was incorporated. This work provides a convenient strategy for developing catalysts with high selectivity and low by-products.

Graphical Abstract

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碱磷酸盐改性降低Pd/NaY催化剂表面酸度以提高碳酸二甲酯的选择性

CO酯化制碳酸二甲酯（DMC）路线具有重要的经济和环境价值。然而，工业路线存在一些缺点，如原料亚硝酸盐甲酯（MN）分解为副产物二甲氧基甲烷（DMM）和甲酸甲酯（MF），导致产品/反应物混合物的后续分离问题，导致生产成本增加。以往的研究表明，NaY的酸位在促进MN的分解中起着至关重要的作用。本文制备了一系列Na2HPO4修饰的Pd/NaY催化剂来解决这些问题。结果表明，Na2HPO4的引入使Pd/PNaY-12的DMC选择性从55%提高到83%，副产物选择性[DMM（从22%提高到10%），MF（从23%降低到7%）]显著降低。从pi - ir分析结果来看，Lewis酸位点数量减少，NH3-TPD分析结果显示，弱酸位点（从0.33 mmol/g减少到0.14 mmol/g）和中强酸位点（从0.46 mmol/g减少到0.10 mmol/g）的数量也明显减少。这种优异的性能应该归功于加入Na2HPO4后更容易得到重要的中间体*COOCH3。本研究为开发高选择性、低副产物的催化剂提供了一种方便的策略。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.