Linker-driven tuning of pore structure and acidity in Zr-MOFs for paraoxon-methyl hydrolysis and efficient oxidative desulfurization

IF 6.9 3区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of the Taiwan Institute of Chemical Engineers Pub Date : 2026-05-01 Epub Date: 2025-12-26 DOI:10.1016/j.jtice.2025.106588

Manh B Nguyen , Le Van Dung , Tan Le Hoang Doan , Pham Tung Son , Sanjit Nayak , Thi Hai Yen Pham , Valeska P. Ting , Huan V. Doan

{"title":"Linker-driven tuning of pore structure and acidity in Zr-MOFs for paraoxon-methyl hydrolysis and efficient oxidative desulfurization","authors":"Manh B Nguyen , Le Van Dung , Tan Le Hoang Doan , Pham Tung Son , Sanjit Nayak , Thi Hai Yen Pham , Valeska P. Ting , Huan V. Doan","doi":"10.1016/j.jtice.2025.106588","DOIUrl":null,"url":null,"abstract":"<div><h3>Background</h3><div>Zirconium-based metal-organic frameworks are promising candidates for catalytic applications due to their high structural stability, tunable porosity, and acidity. However, the influence of organic linkers on their acid site distribution, pore structure, and catalytic activity, particularly in hydrolysis and oxidative desulfurization reactions, has not been fully explored.</div></div><div><h3>Methods</h3><div>A series of Zr-MOFs was synthesized using a microwave-assisted solvothermal method at 100 °C for 30 minutes, reducing reaction times by 20–50 times compared to conventional solvothermal approaches. Structural, textural properties, acidity and defect content were characterized using TEM, BET, NH<sub>3</sub>-TPD, FTIR-CD<sub>3</sub>CN, ESR and XPS. The catalytic activity was evaluated for the hydrolysis of paraoxon-methyl (PM) and the oxidative desulfurization of dibenzothiophene (DBT) under mild conditions. The ODS mechanism of DBT and hydrolysis mechanism of PM are proposed based on the identified degradation products by GC–MS/LC-MC, nuclear magnetic resonance and the role of the Lewis acid sites.</div></div><div><h3>Significant findings</h3><div>Organic linker variation significantly affected the pore size (0.83–3.68 nm), surface area (1332–1762 m<sup>2</sup> g<sup>-1</sup>), and acid site distribution. Zr-BTC exhibited the highest Lewis acidity (0.311 mmol g<sup>-1</sup>) and defect content, achieving complete PM hydrolysis in 2.5 min and 100 % DBT removal within 30 min. Catalytic efficiency strongly correlated with Lewis acid site density modulated by the choice of linker.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"182 ","pages":"Article 106588"},"PeriodicalIF":6.9000,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the Taiwan Institute of Chemical Engineers","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1876107025006406","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/12/26 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}

引用次数: 0

Abstract

Background

Zirconium-based metal-organic frameworks are promising candidates for catalytic applications due to their high structural stability, tunable porosity, and acidity. However, the influence of organic linkers on their acid site distribution, pore structure, and catalytic activity, particularly in hydrolysis and oxidative desulfurization reactions, has not been fully explored.

Methods

A series of Zr-MOFs was synthesized using a microwave-assisted solvothermal method at 100 °C for 30 minutes, reducing reaction times by 20–50 times compared to conventional solvothermal approaches. Structural, textural properties, acidity and defect content were characterized using TEM, BET, NH₃-TPD, FTIR-CD₃CN, ESR and XPS. The catalytic activity was evaluated for the hydrolysis of paraoxon-methyl (PM) and the oxidative desulfurization of dibenzothiophene (DBT) under mild conditions. The ODS mechanism of DBT and hydrolysis mechanism of PM are proposed based on the identified degradation products by GC–MS/LC-MC, nuclear magnetic resonance and the role of the Lewis acid sites.

Significant findings

Organic linker variation significantly affected the pore size (0.83–3.68 nm), surface area (1332–1762 m² g^-1), and acid site distribution. Zr-BTC exhibited the highest Lewis acidity (0.311 mmol g^-1) and defect content, achieving complete PM hydrolysis in 2.5 min and 100 % DBT removal within 30 min. Catalytic efficiency strongly correlated with Lewis acid site density modulated by the choice of linker.

Abstract Image

查看原文本刊更多论文

链接器驱动的zr - mof的孔结构和酸度调节对氧氧甲基的水解和高效氧化脱硫

锆基金属有机骨架由于其高结构稳定性、可调节的孔隙度和酸度而成为催化应用的有希望的候选者。然而，有机连接剂对其酸位分布、孔结构和催化活性的影响，特别是在水解和氧化脱硫反应中，尚未得到充分的探讨。方法采用微波辅助溶剂热法，在100℃条件下反应30 min，合成一系列zr - mof，反应时间比传统溶剂热法缩短20 ~ 50倍。采用TEM、BET、NH3-TPD、FTIR-CD3CN、ESR和XPS表征了其结构、织构性能、酸度和缺陷含量。在温和条件下考察了对氧磷-甲基（PM）水解和二苯并噻吩（DBT）氧化脱硫的催化活性。基于GC-MS /LC-MC、核磁共振鉴定的降解产物和Lewis酸位点的作用，提出了DBT的ODS机理和PM的水解机理。有机连接剂的变化显著影响了孔隙大小（0.83-3.68 nm）、表面积（1332-1762 m2 g-1）和酸位点分布。Zr-BTC具有最高的Lewis酸度（0.311 mmol g-1）和缺陷含量，在2.5 min内完全水解PM，在30 min内100%去除DBT。催化效率与通过选择连接剂调节的路易斯酸位点密度密切相关。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Journal of the Taiwan Institute of Chemical Engineers 工程技术-工程：化工

CiteScore

9.10

自引率

14.00%

发文量

362

审稿时长

35 days

期刊介绍： Journal of the Taiwan Institute of Chemical Engineers (formerly known as Journal of the Chinese Institute of Chemical Engineers) publishes original works, from fundamental principles to practical applications, in the broad field of chemical engineering with special focus on three aspects: Chemical and Biomolecular Science and Technology, Energy and Environmental Science and Technology, and Materials Science and Technology. Authors should choose for their manuscript an appropriate aspect section and a few related classifications when submitting to the journal online.