LaCoO3钙钛矿活化过一硫酸盐降解萘普生

doi:10.11949/0438-1157.20191104

摘要/Abstract

摘要：

在催化活化过一硫酸盐(PMS)降解水中污染物的反应中，通过添加钴基钙钛矿提高反应效率。利用溶胶凝胶法制备了LaCoO₃钙钛矿，通过实验评估LaCoO₃/PMS体系对非甾体抗炎药萘普生（NAP）的降解效果。分析了LaCoO₃投加量、PMS投加量、反应初始pH、Cl^-浓度和腐殖酸（HA）对NAP去除率的影响以及该体系的矿化能力。结果表明NAP降解的反应速率随LaCoO₃和PMS投加量增加而增大；反应初始pH在5.0时NAP降解效果最好；溶液中存在Cl^-对降解有促进效果，且Cl^-浓度越大促进效果越明显；腐殖酸（HA）对反应有一定程度的抑制效果；LaCoO₃在重复利用5次时仍有较好的稳定性。此外，自由基淬灭实验结果表明在LaCoO₃/PMS体系中SO₄^·-为主要活性物质。

关键词: LaCoO₃钙钛矿, 催化剂活化, 高级氧化, 过一硫酸盐, 降解

Abstract:

In the reaction of catalytically activated peroxymonosulfate (PMS) degradation of pollutants in water, the reaction efficiency was improved by adding cobalt-based perovskite. The degradation effect of LaCoO₃/PMS on naproxen（NAP） was evaluated by different system experiments. The effects of LaCoO₃ dosing, PMS dosing, initial pH, Cl^- concentration and humic acid (HA) on NAP removal rate and mineralization ability of the system were investigated. The degradation rate of NAP increased with the rising PMS concentration and increasing LaCoO₃ dosage. The best removal efficiency was obtained at pH 5.0. Moreover, the presence of Cl^- in solution slightly promoted the degradation of NAP, however, humic acid (HA) inhibited the reaction to some extent. LaCoO₃ still has good stability after five reuses. In addition, the radical quenching test showed the $S O_{4}^{\cdot -}$ was the main radical specie of LaCoO₃/PMS reaction.

Key words: LaCoO₃ perovskite, catalyst activation, advanced oxidation, peroxymonosulfate, degradation

中图分类号:

X 787

王柯晴, 徐劼, 沈芷璇, 陈家斌, 吴玮. LaCoO₃钙钛矿活化过一硫酸盐降解萘普生[J]. 化工学报, 2020, 71(3): 1326-1334.

Keqing WANG, Jie XU, Zhixuan SHEN, Jiabin CHEN, Wei WU. Degradation of naproxen by peroxymonosulfate activated with LaCoO₃[J]. CIESC Journal, 2020, 71(3): 1326-1334.

图/表 18

图1 LaCoO3的SEM图

Fig.1 SEM images of LaCoO3

图2 LaCoO3的TEM图

Fig.2 TEM images of LaCoO3

图3 LaCoO3的XRD谱图

Fig.3 XRD patterns of LaCoO3

图4 不同体系中NAP的降解效果

Fig.4 Degradation effect of NAP in different systems(pH = 7.0, NAP = 50 μmol·L-1, PMS = 1.0 mmol·L-1, LaCoO3 = 100 mg·L-1)

图5 反应前后LaCoO3钙钛矿中Co 2p（a）和O 1s（b）的XPS光谱

Fig.5 XPS spectra of Co 2p(a), O 1s (b) in LaCoO3 perovskites before and after reaction

图6 不同材料投加量对NAP的降解效果

Fig.6 Influences of LaCoO3 dosage on NAP removal (pH = 7.0, NAP = 50 μmol·L-1, PMS = 1.0 mmol·L-1)

表1 不同LaCoO3投加量的一级反应动力学常数

Table 1 First order kinetic reaction rate constants of different LaCoO3 dosage

LaCoO₃投加量/(mg·L^-1)	K_abs/min^-1
20	0.074
50	0.1315
100	0.2241
200	0.2858

图7 不同氧化剂投加量对NAP降解效果的影响

Fig.7 Influences of PMS dosage on NAP removal (pH = 7.0, NAP = 50 μmol·L-1, LaCoO3 = 100 mg·L-1)

表2 PMS的分解量

Table 2 Decomposition of PMS

n(NAP)∶n(PMS)	反应前/ (mmol·L^-1)	反应后/ (mmol·L^-1)	PMS分解量/ (mmol·L^-1)
1∶5	0.25	0	0.25
1∶10	0.5	0.03	0.47
1∶20	1	0.32	0.68
1∶40	2	0.92	1.08

表3 不同PMS投加量的一级反应动力学常数

Table 3 First order kinetic reaction rate constants with different PMS dosage

n(NAP)∶n(PMS)	K_abs/min^-1
1∶5	0.0262
1∶10	0.0994
1∶20	0.2254
1∶40	0.4558

图8 不同初始pH对NAP降解效果的影响

Fig.8 Effects of different initial pH on degradation of NAP(NAP = 50 μmol·L-1, PMS = 1.0 mmol·L-1, LaCoO3 = 100 mg·L-1)

图9 LaCoO3材料pHpzc的测量

Fig.9 Measurement of pHpzc of LaCoO3 material

图10 反应中不同浓度的Cl-对NAP降解效果的影响

Fig.10 Effects of different concentration of Cl- on degradation of NAP(pH=7.0, NAP = 50 μmol·L-1, PMS = 1.0 mmol·L-1, LaCoO3 = 100 mg·L-1)

图11 反应中不同浓度的HA对NAP降解效果的影响

Fig.11 Effect of different concentration of HA on NAP degradation(pH=7.0, NAP = 50 μmol·L-1, PMS = 1.0 mmol·L-1, LaCoO3 = 100 mg·L-1)

图12 自由基淬灭实验

Fig.12 Effects of MeOH and TBA on NAP degradation(pH=7.0, NAP = 50 μmol·L-1, PMS = 1.0 mmol·L-1, LaCoO3 = 100 mg·L-1)

图13 电子顺磁共振波谱图

Fig.13 EPR spectra of PMS activation by LaCoO3(pH=7.0, NAP = 50 μmol·L-1, PMS = 1.0 mmol·L-1, LaCoO3 = 100 mg·L-1)

图14 材料重复利用性实验

Fig.14 Reusability of LaCoO3 for NAP degradation(pH=7.0, NAP = 50 μmol·L-1, PMS = 1.0 mmol·L-1, LaCoO3 = 100 mg·L-1)

图15 TOC降解趋势

Fig.15 Removal of TOC during NAP degradation (pH=7.0, NAP = 50 μmol·L-1, PMS = 2.0 mmol·L-1, LaCoO3 = 100 mg·L-1)

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LaCoO₃钙钛矿活化过一硫酸盐降解萘普生

Degradation of naproxen by peroxymonosulfate activated with LaCoO₃

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