通过价调制促进萃取氧化脱硫：（TBA）3PMoⅤ4@MOF-808（Zr）优于六价类似物

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel Pub Date : 2025-10-10 DOI:10.1016/j.fuel.2025.137089

Yan Gao , Miao Yan , Xinyu Dong , HuiJuan Jia , Xueli Zhao , Yang He , Lingxin Guo , Jianshe Zhao

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引用次数: 0

摘要

随着对高质量液体燃料的需求不断增长，硫的去除已经成为炼油行业的关键。POM@MOF复合材料结合了聚金属氧酸盐（POM）和金属有机骨架（MOF）的优点，在硫化物氧化中显示出巨大的潜力。研究了（TBA）3PMoⅥ4@MOF-808（Zr）和（TBA）3PMoⅤ4@MOF-808（Zr）的合成、表征及其在萃取氧化脱硫（EODS）中的应用。分别用浸渍法和溶剂热法合成了两种不同价态的钼复合材料。XPS分析证实（TBA）3PMoⅥ4在合成过程中还原为（TBA）3PMoⅤ4。EODS试验表明，（TBA）3PMoⅤ4@MOF-808（Zr）由于活性组分分散均匀，且具有五价钼，具有较好的催化活性。考察了H2O2用量、催化剂用量、反应温度对DBT去除率的影响，并研究了DBT的氧化动力学。提出了一种可能的EODS机制，包括过氧化氢活化、DBT氧化和催化剂再生。催化剂（TBA）3PMoⅤ4@MOF-808（Zr）也表现出良好的可重复使用性和结构稳定性，具有很大的实际脱硫应用潜力。通过浸渍和溶剂热法合成POM@MOF复合材料用于燃料脱硫，减少含硫污染物的排放。高效的（TBA）3PMoⅤ4@MOF-808（Zr）催化剂在温和的条件下减少燃料中的硫化物，其可重复使用性和稳定性最大限度地减少了浪费，有助于可持续的环境保护。

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Boosting extraction oxidation desulfurization via valence modulation: (TBA)3PMoⅤ4@MOF-808(Zr) outperforms its hexavalent analog

With growing demands for high-quality liquid fuels, sulfur removal has become critical for the refining industry. POM@MOF composites, which combine the advantages of polyoxometalate (POM) and metal–organic framework (MOF), show great potential in sulfide oxidation. This study focuses on the synthesis and characterization of (TBA)₃PMo^Ⅵ₄@MOF-808(Zr) and (TBA)₃PMo^Ⅴ₄@MOF-808(Zr), and their applications in extraction oxidation desulfurization (EODS). These two composites with different valence Mo were synthesized via impregnation and solvothermal methods, respectively. XPS analysis confirmed the reduction of (TBA)₃PMo^Ⅵ₄ to (TBA)₃PMo^Ⅴ₄ during the synthesis process. EODS tests showed that (TBA)₃PMo^Ⅴ₄@MOF-808(Zr) possesses better catalytic activity due to its uniform active-component dispersion and pentavalent molybdenum. The effects of H₂O₂ dosage, catalyst amount, and reaction temperature on DBT removal rate were investigated, and the oxidation kinetics of DBT was studied. A possible EODS mechanism was proposed, involving hydrogen-peroxide activation, DBT oxidation, and catalyst regeneration. The catalyst (TBA)₃PMo^Ⅴ₄@MOF-808(Zr) also showed good reusability and structural stability, holding great potential for practical desulfurization applications.

Environmental implication

The synthesis of POM@MOF composites via impregnation and solvothermal methods for fuel desulfurization reduces sulfur-containing pollutants emissions. The efficient (TBA)₃PMo^Ⅴ₄@MOF-808(Zr) catalyst reduces sulfides in fuel under mild conditions, and its reusability and stability minimize waste, contributing to sustainable environmental protection.

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来源期刊

Fuel 工程技术-工程：化工

CiteScore

12.80

自引率

20.30%

发文量

3506

审稿时长

64 days

期刊介绍： The exploration of energy sources remains a critical matter of study. For the past nine decades, fuel has consistently held the forefront in primary research efforts within the field of energy science. This area of investigation encompasses a wide range of subjects, with a particular emphasis on emerging concerns like environmental factors and pollution.