整体型大孔/介孔PDA/SiO2复合材料固定化漆酶及其在染料降解中的应用

doi:10.16085/j.issn.1000-6613.2018-0926

化工进展 ›› 2019, Vol. 38 ›› Issue (02): 1018-1026.DOI: 10.16085/j.issn.1000-6613.2018-0926

整体型大孔/介孔PDA/SiO₂复合材料固定化漆酶及其在染料降解中的应用

庞乾辉(),吴一鑫,俞丽萍,张辉,梁云霄()

宁波大学材料科学与化学工程学院，新型功能材料及其制备科学国家重点实验室培育基地，浙江宁波 315211

收稿日期:2018-05-07 修回日期:2018-08-07 出版日期:2019-02-05 发布日期:2019-02-05
通讯作者: 梁云霄
作者简介:<named-content content-type="corresp-name">庞乾辉</named-content>（1994—），男，硕士研究生，研究方向为多孔材料的制备及应用。E-mail：<email>768829184@qq.com</email>。|梁云霄，教授，硕士生导师，研究方向为功能多孔材料。E-mail：<email>liangyunxiao@nbu.edu.cn</email>。
基金资助:
宁波市科技惠民项目(2017C50033);浙江省公益项目(2014C31130);宁波大学王宽诚幸福基金(XKL072)

Immobilization of laccase on monolithic macroporous/mesoporous PDA/SiO₂ composite and its application in dye degradation

Qianhui PANG(),Yixin WU,Liping YU,Hui ZHANG,Yunxiao LIANG()

State Key Laboratory Base of Novel Functional Materials and Preparation Science，Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, Zhejiang, China

Received:2018-05-07 Revised:2018-08-07 Online:2019-02-05 Published:2019-02-05
Contact: Yunxiao LIANG

摘要/Abstract

摘要：

用硬模板法制得具有三维连续贯通孔道结构的整体型大孔/介孔SiO₂，通过多巴胺（DA）在大孔/介孔SiO₂孔道表面的原位氧化聚合，制得聚多巴胺（PDA）功能化修饰的整体型大孔/介孔复合材料（PDA/SiO₂）。应用SEM、BET、FTIR和TG等技术对修饰前后的材料进行表征。以PDA/SiO₂为载体固定诺维信工业级漆酶，系统研究了pH、固定化时间、漆酶初始浓度及温度对漆酶固定化的影响；以偶氮荧光桃红作为模拟污染物，研究了固定化漆酶对染料的催化降解性能。结果显示，在漆酶浓度为80mg/mL、pH为4.0、固定化时间为6h及固定化温度为25℃时，固定化漆酶酶活达到最高（348.9U/g）。在偶氮荧光桃红浓度为10mg/L、pH为7.0、温度为30℃、降解时间为8h时，固定化漆酶对偶氮荧光桃红脱色率 ≥ 99.9%，且固定化漆酶易从反应体系中分离，重复使用性能良好。

关键词: 整体型, 大孔/介孔PDA/SiO₂, 固定化, 漆酶, 降解, 偶氮荧光桃红

Abstract:

A monolithic macroporous/mesoporous SiO₂ with three-dimensional (3D) continuous pass-through pore structure was prepared by the hard template method. It was the surface functionalized with polydopamine (PDA) by the in situ oxidation polymerization of dopamine in its micro-channels to obtain the macroporous/mesoporous composite PDA/SiO₂. Samples were characterized by SEM，BET，FTIR and TG. PDA/SiO₂ was used to immobilize commercial Novozymes laccase; and the effects of pH，immobilizing time，initial concentration of laccase and temperature on laccase immobilization were investigated. Using azophloxine as a simulated pollutant, the catalytic performance of the immobilized laccase for the degradation of dye was studied. The results showed that the activity of immobilized laccase reached the maximum (348.9U/g) under conditions of initial laccase concentration 80mg/mL，pH of 4.0，immobilizing time of 6h and temperature of 25℃. Up to 99.9% of azophloxine was decolored under azophloxine concentration 10mg/L，pH of 7.0，temperature of 30℃, and degradation time of 8h. The immobilized laccase exhibited good reusability and it can be easily recovered from the reaction system.

Key words: monolithic, macroporous/mesoporous SiO₂, immobilization, laccase, degradation, azophloxine

中图分类号:

Q814.9

庞乾辉, 吴一鑫, 俞丽萍, 张辉, 梁云霄. 整体型大孔/介孔PDA/SiO₂复合材料固定化漆酶及其在染料降解中的应用[J]. 化工进展, 2019, 38(02): 1018-1026.

Qianhui PANG, Yixin WU, Liping YU, Hui ZHANG, Yunxiao LIANG. Immobilization of laccase on monolithic macroporous/mesoporous PDA/SiO₂ composite and its application in dye degradation[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 1018-1026.

图/表 18

图1 大孔/介孔SiO2、PDA/SiO2及Lac-PDA/SiO2的SEM图及实物光学图

图2 大孔/介孔SiO2、PDA/SiO2和Lac-PDA/SiO2 的

图3 大孔/介孔SiO2、PDA/SiO2和Lac-PDA/SiO2的

图4 大孔/介孔SiO2和PDA/SiO2红外光谱图

图5 大孔/介孔SiO2和PDA/SiO2的TG曲线

图6 固定化时间对漆酶固定化的影响

图7 固定化漆酶的操作稳定性

图8 pH对漆酶固定化的影响

图9 初始浓度对漆酶固定化的影响

图10 温度对漆酶固定化的影响

图11 pH对脱色率的影响

图12 脱色时间对脱色率的影响

图13 偶氮荧光桃红初始浓度对脱色率的影响

图14 温度对脱色率的影响

图15 固定化漆酶的热稳定性

图16 固定化漆酶的重复使用性

图17 固定化漆酶和游离漆酶的储存稳定性

图18 漆酶的Lineweaver-Burk双倒数图

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整体型大孔/介孔PDA/SiO₂复合材料固定化漆酶及其在染料降解中的应用

Immobilization of laccase on monolithic macroporous/mesoporous PDA/SiO₂ composite and its application in dye degradation

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