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通过后合成修饰策略制备的半胱胺锚定金属有机框架用于有效去除水中汞

Cysteamine-Anchored MOF through Post-Synthetic Modification Strategy for the Effective Removal of Mercury from Water.

作者信息

Bagheri Minoo, Amidi Yeganeh, Masoomi Mohammad Yaser

机构信息

Department of Chemistry, Faculty of Science, Arak University, Arak 3848177584, Iran.

出版信息

Inorg Chem. 2024 Jun 17;63(24):11381-11392. doi: 10.1021/acs.inorgchem.4c01462. Epub 2024 Jun 6.

Abstract

The introduction of cysteamine functionality, referred to as Q-ZIF-67-SH, was successfully achieved through postsynthetic modification while maintaining the structural and thermal stability of the quasi metal-organic framework Q-ZIF-67. By subjecting ZIF-67 to controlled partial deligandation at 310 °C under an air atmosphere, a substantial number of unsaturated cobalt sites were generated within the quasi ZIF-67 (Q-ZIF-67) structure. These unsaturated cobalt sites facilitated effective coordination with cysteamine, resulting in the development of the thiol-functionalized framework Q-ZIF-67-SH. The potential of these metal-organic frameworks (MOFs) for the adsorptive removal of hazardous Hg(II) was investigated. Various factors, such as the type of sorbent, pH, adsorbent dosage, initial concentration of Hg(II), and presence of coexisting ions, were thoroughly examined and comprehensively explained. Thiol-anchored MOF significantly enhanced the efficiency of Hg(II) removal, achieving an impressive removal rate of up to 99.2%. Furthermore, it demonstrated a maximum adsorption capacity of 994 mg g and a distribution coefficient of 2.5 × 10 mL g. A good correspondence with pseudo-second-order kinetics and the Langmuir model was observed through the fitting of adsorption kinetics and the isotherm model. The thermodynamic data strongly indicate that the adsorptive removal of Hg(II) is characterized by endothermicity and spontaneity. This signifies that the process is energetically favorable and has potential for efficient Hg(II) removal. Therefore, the Q-ZIF-67-SH sorbent emerges as a promising and advantageous option for the removal of Hg(II) from water.

摘要

通过后合成修饰成功实现了半胱胺功能化,即Q-ZIF-67-SH,同时保持了准金属有机框架Q-ZIF-67的结构和热稳定性。通过在310°C的空气气氛下对ZIF-67进行可控的部分去配体化,在准ZIF-67(Q-ZIF-67)结构中产生了大量不饱和钴位点。这些不饱和钴位点促进了与半胱胺的有效配位,从而形成了硫醇功能化框架Q-ZIF-67-SH。研究了这些金属有机框架(MOF)对吸附去除有害Hg(II)的潜力。对各种因素,如吸附剂类型、pH值、吸附剂用量、Hg(II)的初始浓度以及共存离子的存在等进行了全面研究并作出了综合解释。硫醇锚定的MOF显著提高了Hg(II)的去除效率,去除率高达99.2%,令人印象深刻。此外,它表现出994 mg/g的最大吸附容量和2.5×10 mL/g的分配系数。通过吸附动力学和等温线模型拟合,观察到与准二级动力学和朗缪尔模型有良好的对应关系。热力学数据有力地表明,Hg(II)的吸附去除具有吸热性和自发性。这意味着该过程在能量上是有利的,具有高效去除Hg(II)的潜力。因此,Q-ZIF-67-SH吸附剂成为从水中去除Hg(II)的一种有前景且具有优势的选择。

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