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

作　　者：吴中杰 谢连科 王晶辉 黄仁亮 WU Zhongjie;XIE Lianke;WANG Jinghui;HUANG Renliang(Shandong Electric Power Research Institute of Chinese Power Company,Jinan 250002,Shandong,China;School of Marine Science and Technology,Tianjin University,Tianjin 300072,China)

机构地区：[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

出　　处：《化工进展》2023年第1期497-505,共9页Chemical Industry and Engineering Progress

基　　金：国家电网公司科学技术项目(520626190015);国家自然科学基金(21976132)。

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(NO_(3))_(2)溶液反应制备具有漆酶活性的多级结构羟基硝酸铜[H-Cu_(2)(OH)_(3)NO_(3)]纳米酶。其催化活性是传统Cu(NO_(3))_(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-Cu_(2)(OH)_(3)NO_(3)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-Cu_(2)(OH)_(3)NO_(3)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-Cu_(2)(OH)_(3)NO_(3)纳米酶的可能催化机理。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(NO_(3))_(2)solution to prepare hierarchical copper hydroxyl nitrate(H-Cu_(2)(OH)_(3)NO_(3))with laccase-like activity.Its catalytic activity was 1.85 times higher than that of copper hydroxyl nitrate prepared by urea hydrolysis of Cu(NO_(3))_(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-Cu_(2)(OH)_(3)NO_(3).Compared with laccase,H-Cu_(2)(OH)_(3)NO_(3)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-Cu_(2)(OH)_(3)NO_(3)nanozyme was proposed by control experiments and theoretical analysis.

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 

分 类 号：TQ131.21[化学工程—无机化工]