氮杂酞菁钴光电催化降解水环境中聚丙烯酰胺

王德军; 李慧; 姜锡仁; 赵朝成; 赵玉慧

doi:10.13801/j.cnki.fhclxb.20200907.002

氮杂酞菁钴光电催化降解水环境中聚丙烯酰胺

doi: 10.13801/j.cnki.fhclxb.20200907.002

王德军^{1, 2, 3,},
李慧^4,,
姜锡仁^{1, 2, ,},
赵朝成^3,,
赵玉慧^{1, 2,}

1.
国家海洋局北海环境监测中心，青岛 266033
2.
山东省海洋生态环境与防灾减灾重点实验室，青岛 266033
3.
中国石油大学(华东)　化学工程学院，青岛 266580
4.
青岛职业技术学院，青岛 266555

基金项目: 青岛市博士后应用研究项目

详细信息

通讯作者:
姜锡仁，本科，研究员，研究方向为海洋化学　E-mail：412689687@qq.com

中图分类号: TB332
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- 文章访问数: 1382
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- 被引次数: 0
出版历程
- 收稿日期: 2019-12-05
- 录用日期: 2020-08-03
- 网络出版日期: 2020-09-09
- 刊出日期: 2021-05-01

Photoelectrocatalytic degradation of polyacrylamide in water by cobalt azaphthalocyanine

WANG Dejun^{1, 2, 3
,},
LI Hui^4
,,
JIANG Xiren^{1, 2
, ,},
ZHAO Chaocheng^3
,,
ZHAO Yuhui^{1, 2
,}

1.
North China Sea Environmental Monitoring Center, State Oceanic Administration, Qingdao 266033, China
2.
Shandong Provincial Key Laboratory of Marine Ecology and Environment & Disaster Prevention and Mitigation, Qingdao 266033, China
3.
College of Chemical Engineering, China University of Petroleum, Qingdao 266580, China
4.
Qingdao Technical College, Qingdao 266555, China

摘要

摘要: 针对水环境中聚丙烯酰胺(HPAM)难以被快速去除的问题，以导电炭黑(CB)为载体，制备了负载型氮杂酞菁钴(NCoPc/CB)和甲基取代氮杂酞菁钴(MeNCoPc/CB)复合材料，并对其光电催化降解HPAM的性能进行了研究。搭建分体式光电协同催化体系，选取50 mg/L HPAM水溶液为目标污染物，以Na₂SO₄为电解质，对NCoPc的理化性能及光电协同催化工艺降解高分子聚合物的性能进行了考察。结果证实，光电协同催化工艺对HPAM去除率不但优于单独光催化和单独电催化工艺，更优于两者的代数和，说明光电联合体系中产生了协同增强效应。其中，以MeNCoPc/CB复合材料效果最佳，污染物去除率达到76.07%，溶液黏度由8.33 mPa·s降至1.81 mPa·s。对协同工艺进行反应动力学分析，证实此过程符合准一级反应动力学，其反应速率常数分别是光催化的6.03倍和电催化的3.97倍。电子自旋共振技术(ESR)证实，反应体系内主要活性物质为·OH和O₂⁻·。
- 氮杂酞菁钴 /
- 光电催化 /
- 降解 /
- 聚丙烯酰胺 /
- 反应机制
Abstract: Supported cobalt azaphthalocyanine (NCoPc/CB) and methyl-substituted cobalt azaphthalocyanine (MeNCoPc/CB) composites were prepared, in which carbon black (CB) was used as a carrier, to solve the problem that polyacrylamide (HPAM) was difficult to be removed in the water. The physical and chemical properties of catalyst and photoelectrocatalytic degradation performance of HPAM was studied in a split photoelectric cooperative catalytic system, with 50 mg/L HPAM aqueous solution as the target pollutant and Na₂SO₄ as the electrolyte. The results confirm that the removal rate of HPAM by the photoelectrocatalysis is not only superior to the photocatalysis and electrocatalysis, but also to the algebraic sum of the two, which shows that the photoelectric combined system has an obvious synergistic enhancement effect. Among them, MeNCoPc/CB composite has the best effect, the pollutant removal rate reaches 76.07%, and the solution viscosity decreases from 8.33 mPa·s to 1.81 mPa·s. The photoelectrocatalytic reaction confirms that the process conforms to the quasi-first-order reaction kinetics, while the reaction rate constants are 6.03 times that of photocatalysis and 3.97 times that of electrocatalysis. Electron spin resonance technology (ESR) confirms that the main active substances in the reaction system are ·OH and O₂·⁻.
- cobalt azaphthalocyanine /
- photoelectrocatalysis /
- degradation /
- polyacrylamide /
- reaction mechanism

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图 1 甲基取代八氮杂金属酞菁(a)和叶绿素A (b)的分子结构示意图

Figure 1. Schematic diagram of structures of nitrogen-doped methyl-substituted phthalocyanine (a) and chlorophyll A (b)

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图 2 光电联合实验装置

1—DC stabilized power supply; 2—Darkroom; 3—Reactor; 4—Stainless steel cathode; 5—Magnetic stirrers; 6—Titanium anode; 7—Xenon lamp; 8—Peristaltic pump; 9—Circulating cooling water

Figure 2. Photoelectric experimental device

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图 3 氮杂酞菁钴(NCoPc) (a)和甲基取代氮杂酞菁钴(MeNCoPc)(b)的紫外-可见光谱

Figure 3. UV-visspectrum of cobalt azaphthalocyanine (NCoPc) (a) and methyl-substituted cobalt azaphthalocyanine (MeNCoPc) (b)

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图 4 NCoPc (a)和MeNCoPc (b)负载前后的XRD图谱

Figure 4. XRD patterns of NCoPc (a) and MeNCoPc (b) before and after loaded

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图 5 炭黑(CB)负载NCoPc (NCoPc/CB)及CB负载MeNCoPc (MeNCoPc/CB)催化剂的SEM图像和EDS图谱

Figure 5. SEM images and EDS spetra of carbon black (CB) supported NCoPc (NCoPc/CB) and CB supported MeNCoPc (MeNCoPc/CB) catalysts

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图 6 NCoPc、MeNCoPc、NCoPc/CB及MeNCoPc/CB催化剂的光催化、电催化及光电协同催化降解聚丙烯酰胺(HPAM)的效果对比

Figure 6. Comparison of photocatalytic, electrocatalytic and photocatalytic degradation of polyacrylamide (HPAM) by NCoPc, MeNCoPc, NCoPc/CB and MeNCoPc/CB catalysts

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图 7 三种催化工艺降解HPAM动力学分析(MeNCoPc/CB催化剂)

Figure 7. Kinetic analysis of three catalytic processes for degradation of HPAM (MeNCoPc/CB catalyst)

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图 8 光电协同催化降解HPAM工艺体系内自由基的电子自旋共振(ESR)检测图谱

Figure 8. Electron spin resonance (ESR) detection spectra of radicals in photoelectrocatalytic process for the degradation of HPAM

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图 9 MeNCoPc/CB催化剂光电协同催化降解HPAM的机制示意图

Figure 9. Catalytic degradation of HPAM mechanism by photoelectrocatalytic degradation of MeNCoPc/CB catalyst

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表 1 三种催化工艺降解HPAM动力学反应速率常数

Table 1. Kinetics reaction rate of three catalytic processes for degradation of HPAM

No.	Voltage/V	Na₂SO₄/(mol·L⁻¹)	Reaction rate/min⁻¹	Correlation coefficient R²	Process
1	—	0.1	3.98×10⁻³	0.9789	Photocatalysis
2	40	0.1	5.05×10⁻³	0.9614	Electrocatalysis
3	40	0.1	2.40×10⁻²	0.9771	Photoelectrocatalysis

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表 2 不同反应阶段HPAM降解水样成分分析

Table 2. Analysis of components of HPAM solution sample degradated in different reaction period

No.	Water sample after 40 min of reaction		Water sample after 80 min of reaction		Water sample after 120 min of reaction
No.	Composition	Content/%	Composition	Content/%	Composition	Content/%
1	Water	99.625	Water	99.611	Water	99.562
2	HPAM	0.035	HPAM	0.008	HPAM	0.002
3	AM	0.020	AM	0.009	AM	0.003
4	Acrylic acid	0.040	Acrylic acid	0.055	Acrylic acid	0.002
5	NO₃⁻	0.040	NO₃⁻	0.063	NO₃⁻	0.128
6	Na₂SO₄	0.230	Na₂SO₄	0.250	2-(2-Hydroxypropoxy)-1-propanol	0.002
7	DMF	0.010	DMF	0.004	2,4,7,9-Tetramethyl-5-decyne-4,7-diol	0.009
8	—	—	—	—	Myristicin	0.002
9	—	—	—	—	Na₂SO₄	0.290
Notes: AM—Acrylamide; DMF—Dimethylformamide.

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