光活化过硫酸钾体系下直接蓝15降解动力学及其降解机制

doi:10.13475/j.fzxb.20201004308

纺织学报 ›› 2021, Vol. 42 ›› Issue (10): 99-106.doi: 10.13475/j.fzxb.20201004308

光活化过硫酸钾体系下直接蓝15降解动力学及其降解机制

胡倩, 阳海(), 李鑫, 陈聘婷, 陈镇, 易兵

湖南工程学院环境催化与废弃物再生化湖南省重点实验室, 湖南湘潭 411104

收稿日期:2020-10-21 修回日期:2021-07-12 出版日期:2021-10-15 发布日期:2021-10-29
通讯作者: 阳海
作者简介:胡倩(1992—),女,实验师,硕士。主要研究方向为纺织化学与染整工程。
基金资助:
湖南省教育厅项目(18C0698);湖南省教育厅项目(19K024);湖南省杰出青年基金项目(2021JJ10001);湖南省科技人才托举工程项目(2020TJ-Q12);国家自然科学基金项目(21772035)

Degradation kinetics and mechanism of Direct Blue 15 in photoactivated potassium persulfate system

HU Qian, YANG Hai(), LI Xin, CHEN Pinting, CHEN Zhen, YI Bing

Hunan Provincial Key Laboratory of Environmental Catalysis & Waste Recycling, Hunan Institute of Engineering, Xiangtan, Hunan 411104, China

Received:2020-10-21 Revised:2021-07-12 Published:2021-10-15 Online:2021-10-29
Contact: YANG Hai

摘要/Abstract

摘要：

为探索双偶氮染料直接蓝15(DB15)在水中的降解可行性及在活性氧物种作用下可能的反应位点和迁移转化机制,利用紫外光活化过硫酸钾(UV/K₂S₂O₈)技术研究了DB15在活性氧物种作用下的降解动力学和反应机制。结果表明,双偶氮染料DB15在UV/K₂S₂O₈体系中降解符合假一级动力学,其动力学常数速率为0.010 7 min^-1, K₂S₂O₈质量浓度、底物初始浓度和反应温度对其降解动力学影响显著。利用气相色谱-质谱法对DB15在UV/K₂S₂O₈体系下降解中间产物进行初步的分离与分析,并结合DB15前线电子云密度(FEDs)的理论计算结果对其降解途径进行推导。研究发现:DB15在硫酸根自由基($SO_4^-$·)、羟基自由基(·OH)等活性氧物种作用下N₁₁、N₂₄、N₄₁、N₄₂和C₂₈等活性位点易被自由基直接攻击或者发生电子转移反应,从而引起DB15分子中N=N和C—N键断裂,然后中间产物再进一步羟基化是其主要的降解途径。

关键词: 直接蓝15, 光活化, 降解动力学, 机制, 活性氧物种

Abstract:

In order to explore the degradation feasibility of bisazo dye Direct Blue 15 (DB15) and its transformation mechanism under attack of reactive oxygen species (ROSs), the degradation kinetics and mechanism of DB15 was studied in UV/K₂S₂O₈ system. The results show that the degradation of the bisazo dye DB15 in the UV/K₂S₂O₈ system conforms to pseudo-first-order kinetics, with a kinetic constant rate of 0.010 7 min^-1. Different K₂S₂O₈ concentration, initial substrate concentration and reaction temperature have significant effects on its degradation kinetics. Finally, the degradation intermediates of DB15 were identified by gas chromatography-mass spectrometry. Combined with the frontier electron densities (FEDs) of DB15, the positions of N₁₁, N₂₄, N₄₁, N₄₂, and C₂₈ are likely to be attacked or occurred the single electron transfer under the attack of $SO_4^-$·, ·OH and so on, which resulted in the cleavage of N=N and C—N bonds and further hydroxylation and mineralization of the degradation intermediates under the attack of the ROSs.

Key words: Direct Blue 15, photo-activated, degradation kinetics, mechanism, reactive oxygen specie

中图分类号:

X131

胡倩, 阳海, 李鑫, 陈聘婷, 陈镇, 易兵. 光活化过硫酸钾体系下直接蓝15降解动力学及其降解机制[J]. 纺织学报, 2021, 42(10): 99-106.

HU Qian, YANG Hai, LI Xin, CHEN Pinting, CHEN Zhen, YI Bing. Degradation kinetics and mechanism of Direct Blue 15 in photoactivated potassium persulfate system[J]. Journal of Textile Research, 2021, 42(10): 99-106.

图/表 10

图1

图2

图3

图4

图5

图6

图7

表1

表2

DB15的前线电子云密度(FDEs)计算结果"

原子序号	$2 FE D HOMO 2$	$2 FED LUMO 2$	$FED HOMO 2$ + $FE D LUMO 2$	原子序号	$2 FE D HOMO 2$	$2 FE D LUMO 2$	$FE D HOMO 2$ + $FE D LUMO 2$
C₁	0.128 6	0.046 9	0.087 8	C₃₂	0.002 3	0.007 8	0.005 1
C₂	0.076 2	0.031 0	0.053 6	C₃₃	0.023 1	0.040 0	0.031 6
C₃	0.014 9	0.059 6	0.037 3	C₃₄	0.016 2	0.028 3	0.022 2
C₄	0.000 8	0.119 7	0.060 2	C₃₅	0.004 5	0.018 6	0.011 5
C₅	0.152 5	0.000 3	0.076 4	C₃₆	0.032 9	0.048 2	0.040 6
C₆	0.037 1	0.103 7	0.070 4	C₃₇	0.006 5	0.020 9	0.013 7
C₇	0.082 2	0.105 3	0.093 7	C₃₈	0.012 7	0.025 3	0.019 0
C₈	0.165 0	0.075 4	0.120 2	O₃₉	0.001 4	0.002 5	0.001 9
C₉	0.015 9	0.102 5	0.059 2	C₄₀	0.000 5	0.004 6	0.002 6
C₁₀	0.105 3	0.001 8	0.053 5	N₄₁	0.006 4	0.036 5	0.121 4
N₁₁	0.035 7	0.210 2	0.123 0	N₄₂	0.015 0	0.045 3	0.130 2
O₁₂	0.051 5	0.024 3	0.037 9	C₄₃	0.010 3	0.025 2	0.017 7
N₁₃	0.148 5	0.012 2	0.080 4	C₄₄	0.000 6	0.024 1	0.012 4
S₁₄	0.000 3	0.002 7	0.001 5	C₄₅	0.006 9	0.001 1	0.004 0
O₁₅	0.001 1	0.005 8	0.003 5	C₄₆	0.002 5	0.020 9	0.011 7
O₁₆	0.001 4	0.004 9	0.003 1	C₄₇	0.000 3	0.019 0	0.009 6
O₁₇	0.001 3	0.001 5	0.001 4	C₄₈	0.010 3	0.021 6	0.016 0
S₁₉	0.000 3	0.004 2	0.002 2	C₄₉	0.002 1	0.004 7	0.003 4
O₂₀	0.001 4	0.001 7	0.001 5	C₅₀	0.003 8	0.026 4	0.015 1
O₂₁	0.002 5	0.007 4	0.004 9	C₅₁	0.001 6	0.004 0	0.002 8
O₂₂	0.000 8	0.004 4	0.002 6	C₅₂	0.003 9	0.009 9	0.006 9
N₂₄	0.071 9	0.247 2	0.159 6	O₅₃	0.007 3	0.004 7	0.006 0
C₂₅	0.058 0	0.080 8	0.069 4	N₅₄	0.000 8	0.000 6	0.000 7
C₂₆	0.016 8	0.106 5	0.061 7	S₅₅	0.000 0	0.000 8	0.000 4
C₂₇	0.025 6	0.012 2	0.018 9	O₅₆	0.000 0	0.000 5	0.000 2
C₂₈	0.050 8	0.121 8	0.086 3	O₅₇	0.000 0	0.000 7	0.000 4
C₂₉	0.006 0	0.045 8	0.025 9	O₅₈	0.000 1	0.000 2	0.000 1
C₃₀	0.029 9	0.087 0	0.058 5	S₆₀	0.000 0	0.001 2	0.000 6
C₃₁	0.010 4	0.005 8	0.008 1	O₆₁	0.000 2	0.001 8	0.001 0

表2

图8

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降解产物编号	质荷比 m/z	保留时间/ min	质谱主要碎片的质荷比m/z	可能的降解产物名称	谱库相似度/%	萃取剂
P1	111	9.3	55,83,84	对苯二酚	81	EA
P2	192	18.6	152,165,179	多羟基取代产物	80	EA
P3	219	22.1	97,165	联苯四醇	83	EA
P4	139	23.6	57,97	4-氨基-3-甲氧基苯酚	87	EA
P5	155	24.9	83,141	4-硝基苯-1,3-二醇	85	EA
P6	331	25.4	207,279,281	N N键断裂产物	86	EA
P7	126	27.8	59,83	1,2,4-苯三醇	88	EA
P8	112	5.4	71,84,99	邻二苯酚	90	DCM
P9	191	13.3	115,163,173	7-氨基萘-1,3,5-三醇	87	DCM
P10	223	17.4	83,111,149	7-硝基萘-1,3,5-三醇	93	DCM
P11	125	23.6	57,71,111	4-氨基苯-1,3-二醇	80	DCM

光活化过硫酸钾体系下直接蓝15降解动力学及其降解机制

Degradation kinetics and mechanism of Direct Blue 15 in photoactivated potassium persulfate system

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