张元杰， 李金凯， 刘宗明

济南大学 材料科学与工程学院， 山东 济南 250022

引用格式：

张元杰， 李金凯， 刘宗明 . MOFs 衍生的 Fe-N-C 纳米酶用于对苯二酚的比色检测［J］. 中国粉体技术， 2024， 30（4）： 128-137. 

ZHZHANG Y J,LI J K， LIU Z M. MOFs-derived Fe-N-C nanozyme for colorimetric detection of hydroquinone［J］. China Powder Science and Technology， 2024， 30（4）：128−137.

DOI：10.13732/j.issn.1008-5548.2024.04.012

收稿日期： 2024-05-13， 修回日期： 2024-06-11， 上线日期： 2024-06-28。

基金项目：国家自然科学基金项目， 编号： 51402125； 山东省自然科学基金项目， 编号： ZR2020ME045， ZR2020ME046； 济南市“新高 校20条”基金项目， 编号： 2021GXRCO99， T202204。

第一作者简介：张元杰（1998—），男，硕士生，研究方向为材料与化工。E-mail：zyj1152995056@163.com。

通信作者简介：刘宗明（1965—），男，教授，博士，博士生导师，全国高校黄大年式教师团队骨干成员、山东省有突出贡献的中青年专家，研究方向为粉体工程。

E-mail:liuzm@ujn.edu.cn 。

摘要：【 目的】 建立一种方便的检测对苯二酚（hydroquinone，HQ）的方法。【方法】 采用化学掺杂法合成 Fe-ZIF-8 前驱 体，对前驱体热解处理，得到Fe-N-C纳米酶粉末；通过活性对比、自由基捕获和动力学实验，系统探究Fe-N-C的类酶活 性；依据HQ具有还原性强、 可将3，3'， 5， 5'-四甲基联苯胺（TMB）显色体系还原为无色状态的特性，构建比色法检测HQ的传感平台。【结果】 Fe-N-C表现出优异的过氧化物酶样活性，可以快速将显色底物TMB催化氧化为蓝色； Fe-N_x是FeN-C主要的活性位点，羟基自由基（•OH）、 超氧自由基（O₂ ^•−）和单线态氧（¹O₂）是起主要作用的活性氧； Fe-N-C纳米酶对TMB的亲和力优于天然辣根过氧化物酶，该方法检测 HQ的线性范围为 0~33 μmol/L，检测限为 0. 356 μmol/L，同时具有 良好的抗干扰能力。【结论】 构建一种用于环境分析的金属有机骨架化合物（metal organic framework，MOFs）衍生物纳米 酶，可实现HQ的简单和灵敏检测。

关键词： 纳米酶； 金属-有机骨架； 比色检测； 对苯二酚

Abstract

Objective Hydroquinone is a phenolic compound widely used in industry. It is difficult to degrade in the aquatic ecological environment and is harmful to human health. Therefore， constructing a simple and sensitive method for the detection of hydroquinone is of great significant.

Methods In this study， an MOFs-derived Fe-N-C catalyst was synthesized through a simple chemical doping method and hightemperature pyrolysis， using an Fe-ZIF-8 precursor. The physicochemical properties of Fe-N-C were characterized in detail through SEM， TEM， XRD， FTIR， and XPS. The effect of the introducing Fe³⁺ on the enzyme activity of the catalyst was studied. The enzyme-like activity， catalytic mechanism， and kinetic parameters of Fe-N-C were systematically investigated. Based on the enzyme-like activity of Fe-N-C， a colorimetric sensor for the detection of hydroquinone was developed.

Results and Discussion Based on the aforementioned characterization and experimental findings， Fe-N-C exhibited excellent peroxidase-like activity and weak oxidase-like activity. In addition， in the presence of hydrogen peroxide， OPD and ABTS as substrates were also oxidized to yellow and blue products by Fe-N-C， with characteristic absorption peaks at 448 nm and 416 nm， respectively. Additionally， the poisoning experiment with KSCN showed that Fe-Nx was the main active site in Fe-N-C catalyst. The study of the catalytic mechanism confirmed that ·OH， O₂^•− and ¹O₂ were active oxygen radicals playing a major role in the catalytic oxidation of TMB. The catalytic activity of Fe-N-C nanozymes was further studied through steady-state kinetic analysis. The K_m and V_max of Fe-N-C for TMB were 0. 134 mmol/L and 0. 754 × 10^-7 M·s^-1， respectively， while those for H₂O₂ were 16. 535 mmol/L and 2. 533 × 10^-7 M·s^-1， respectively. Finally， the colorimetric sensor detected HQ in a linear range of 0~33 μmol/L with a detection limit of 0. 356 μmol/L. Through anti-interference experiments， the established colorimetric sensing platform showed robust anti-interference ability and selectivity in detecting hydroquinone.

Conclusion The introduction of Fe³⁺ significantly improves the enzyme-like activity of N-C nanomaterials. Fe-N-C exhibits excellent peroxidase-like activity， which can rapidly oxidize the chromogenic substrate 3，3'，5，5'-tetramethylbenzidine（ TMB） to blue. Fe-N_x is the main active site of Fe-N-C nanozymes， and hydroxyl radica（•OH）， superoxide radicals（ O₂^•−） and singlet oxygen（ ¹O₂） are the main reactive oxygen species（ROS）. Hydroquinone is a strong reducing organic pollutant that can reduce blue oxTMB to a colorless state. Based on this， a sensing platform for colorimetric detection of HQ was constructed. This method has good sensitivity and selectivity for hydroquinone， which expands the application of MOFs-based nanozymes in the field of environmental pollutant detection.

Keywords： nanozyme； metal-organic framework； colorimetric detection； hydroquinone

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