多级结构羟基硝酸铜纳米酶的制备及其对酚类污染物的降解

doi:10.16085/j.issn.1000-6613.2022-0550

化工进展 ›› 2023, Vol. 42 ›› Issue (1): 497-505.DOI: 10.16085/j.issn.1000-6613.2022-0550

多级结构羟基硝酸铜纳米酶的制备及其对酚类污染物的降解

吴中杰¹(), 谢连科¹, 王晶辉²(), 黄仁亮²

^1.国网山东省电力公司电力科学研究院，山东济南 250002
^2.天津大学海洋科学与技术学院，天津 300072

收稿日期:2022-04-04 修回日期:2022-05-17 出版日期:2023-01-25 发布日期:2023-02-20
通讯作者: 王晶辉
作者简介:吴中杰（1987—），男，博士研究生，研究方向为电力系统的环境污染防治。E-mail: 414699594@qq.com。
基金资助:
国家电网公司科学技术项目(520626190015);国家自然科学基金(21976132)

Preparation of hierarchical copper hydroxyl nitrate nanozyme for degradation of phenolic pollutants

WU Zhongjie¹(), XIE Lianke¹, WANG Jinghui²(), HUANG Renliang²

^1.Shandong Electric Power Research Institute of Chinese Power Company, Jinan 250002, Shandong, China
^2.School of Marine Science and Technology, Tianjin University, Tianjin 300072, China

Received:2022-04-04 Revised:2022-05-17 Online:2023-01-25 Published:2023-02-20
Contact: WANG Jinghui

摘要/Abstract

摘要：

漆酶是一种多铜氧化酶，在空气条件下即可催化氧化多胺、多酚类有机物，被认为是水处理及土壤修复领域的绿色催化剂。纳米酶是一种具有酶催化活性的纳米材料，因其具有多功能性、低成本、高稳定性等优点，近年来引起广泛关注。因此，本文以尿素水解过程中产生的异氰酸根离子为模板剂，与Cu(NO₃)₂溶液反应制备具有漆酶活性的多级结构羟基硝酸铜[H-Cu₂(OH)₃NO₃]纳米酶。其催化活性是传统Cu(NO₃)₂与尿素水解法制备的羟基硝酸铜的1.85倍，其最大反应速率是漆酶的1.27倍。H-Cu₂(OH)₃NO₃纳米酶在不同pH、温度、储存时间和盐浓度条件下体现良好的催化稳定性。在重复利用12次后，保持58%的催化活性，体现出良好的重复利用性。而且H-Cu₂(OH)₃NO₃纳米酶具有降解土壤与地下水中常见的2,4-二氯苯酚、对苯二酚、2,6-二甲氧基苯酚和邻氨基苯酚等酚类污染物的能力，其降解效率接近甚至优于漆酶。此外，通过对照实验与理论分析，提出H-Cu₂(OH)₃NO₃纳米酶的可能催化机理。

关键词: 漆酶, 纳米酶, 羟基硝酸铜, 酚类污染物, 土壤与地下水修复

Abstract:

Laccases are members of the multi-copper oxidases, which are able to catalyze the oxidation of polyamines and polyphenols under ambient conditions. It is also considered as green catalyst in water treatment and soil remediation. Nanozymes, defined as nanomaterials with enzyme-like activity, have attracted extensive interest, because of their versatility, low cost and high stability. In this paper, the isocyanate ions in the hydrolysis of urea were used as template and reacted with Cu(NO₃)₂ solution to prepare hierarchical copper hydroxyl nitrate (H-Cu₂(OH)₃NO₃) with laccase-like activity. Its catalytic activity was 1.85 times higher than that of copper hydroxyl nitrate prepared by urea hydrolysis of Cu(NO₃)₂ and its v_max was 1.27 times higher than that of laccase. It also displayed high stability under various pH, high temperature, long-term storage and high salinity. It remained 58% of catalytic activity after 12 cycles. These results indicated good catalytic stability and reusability of H-Cu₂(OH)₃NO₃. Compared with laccase, H-Cu₂(OH)₃NO₃ nanozyme showed equal or even higher catalytic performance for the degradation of common phenolic pollutants in soil and groundwater, such as 2,4-dichlorophenol, hydroquinone, 2,6-dimethoxyphenol and o-aminophenol. In addition, the possible catalytic mechanism of H-Cu₂(OH)₃NO₃ nanozyme was proposed by control experiments and theoretical analysis.

Key words: laccase, nanozyme, copper hydroxyl nitrate, phenolic pollutants, soil and groundwater remediation

中图分类号:

TQ131.2⁺1

吴中杰, 谢连科, 王晶辉, 黄仁亮. 多级结构羟基硝酸铜纳米酶的制备及其对酚类污染物的降解[J]. 化工进展, 2023, 42(1): 497-505.

WU Zhongjie, XIE Lianke, WANG Jinghui, HUANG Renliang. Preparation of hierarchical copper hydroxyl nitrate nanozyme for degradation of phenolic pollutants[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 497-505.

图/表 10

图1 多级结构羟基硝酸铜[H-Cu2(OH)3NO3]纳米酶的合成示意图

图2 H-Cu2(OH)3NO3的TEM图和SEM图

图3 H-Cu2(OH)3NO3的结构表征

图4 H-Cu2(OH)3NO3纳米酶的催化活性

图5 H-Cu2(OH)3NO3和漆酶室温下催化2,4-二氯苯酚（2,4-DP）和4-氨基安替吡啉反应的Lineweaver-Burk图

表1 常温下H-Cu2(OH)3NO3和漆酶催化2,4-二氯苯酚和4-氨基安替吡啉反应的动力学常数

催化剂	K_m/mmol·L^-1	v_max/10^-6mmol·L^-1·s^-1
H-Cu₂(OH)₃NO₃	0.272	0.141
漆酶	0.149	0.111

图6 相同质量浓度下H-Cu2(OH)3NO3和漆酶在不同pH、温度、储存时间、NaCl浓度、乙醇等条件下的催化稳定性及H-Cu2(OH)3NO3的重复利用性

图7 H-Cu2(OH)3NO3与漆酶催化降解2,4-二氯苯酚和对苯二酚的反应转化率

图8 H-Cu2(OH)3NO3与漆酶催化降解2,6-二甲氧基苯酚和邻氨基苯酚的反应转化率

图9 H-Cu2(OH)3NO3纳米酶的催化机理示意图

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多级结构羟基硝酸铜纳米酶的制备及其对酚类污染物的降解

Preparation of hierarchical copper hydroxyl nitrate nanozyme for degradation of phenolic pollutants

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