CNMs/PS体系降解水中有机污染物的研究进展

doi:10.19965/j.cnki.iwt.2020-0860

摘要/Abstract

摘要：

作为一种新型高级氧化技术，碳纳米材料活化过硫酸盐（CNMs/PS）被广泛用于去除水中各类有机污染物。通过对CNMs/PS降解有机污染物的反应机理进行分类，系统介绍了自由基反应和表面催化氧化的活性氧组分（ROS）、反应特点与表征方法，总结了CNMs类型、溶液pH、无机盐离子、背景有机物和反应操作方式等因素对体系处理效能的影响。提出通过开展CNMs功能化设计、强化表面催化氧化，以提高CNMs/PS在复杂环境下选择性进行反应的可行方法。认为基于CNMs复合膜的原位催化氧化体系能够在快速降解目标物的同时，完成催化剂的截留再生，更适用于实际处理的连续操作。在未来，与传统工艺的组合使用以及催化剂稳定性提升等将是该领域重要的研究方向。

关键词: 碳纳米材料, 过硫酸盐, 有机污染物, 自由基, 表面催化氧化

Abstract:

As a novel advanced oxidation process, persulfate activation with carbon nanomaterials (CNMs/PS) was widely used to remove various organic contaminants in water. The mechanisms of CNMs/PS system were classified into free radical reaction and surface catalytic oxidation, and the reactive oxygen species, oxidation capacity and characterization methods of different reaction pathways were interpreted. The influences of CNMs type, solution pH, inorganic ions, coexisting organics and operating mode etc. on the treatment efficiency of system were summarized. And a feasible method was proposed to improve the reaction selectivity of CNMs/PS in complex water matrix through CNMs functional design and surface-related catalysis enhancement. In addition, the in-situ catalytic oxidation process based on CNMs composite membranes could result in the efficient removal of target compounds and the separation and regeneration of carbonaceous catalysts, which was suitable for the real treatment in continuous operation mode. In the future, the combined application with conventional treatment processes and the stability improvement of catalysts are considered as the important research directions.

Key words: carbon nanomaterials, persulfate, organic contaminants, free radical, surface catalytic oxidation

中图分类号:

X703

殷红桂,钱飞跃,谈颖,沈耀良. CNMs/PS体系降解水中有机污染物的研究进展[J]. 工业水处理, 2021, 41(11): 23-31.

Honggui YIN,Feiyue QIAN,Ying TAN,Yaoliang SHEN. Degradation of organic contaminants in water using CNMs/PS: A review[J]. Industrial Water Treatment, 2021, 41(11): 23-31.

https://www.iwt.cn/CN/Y2021/V41/I11/23

图/表 8

参考文献 76

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项目	自由基反应	表面催化氧化
活性氧组分（ROS）	SO₄^·-、·OH	表面活性络合物、络合态SO₄^·-、¹O₂和电子转移等
ROS氧化性	SO₄^·-，E⁰为2.5~3.1 V；HO·，E⁰为1.8~2.8 V	氧化性普遍弱于自由基
ROS稳定性	SO_·-⁴，半衰期t_1/2为30~40 μs；·OH，半衰期t_1/2 < 1 μs	¹O₂：半衰期t_1/2约4 μs
目标物选择性	SO₄^·-，部分芳香类化合物；·OH，非选择性	富电子芳香类有机物
常用掩蔽剂	甲醇、乙醇、叔丁醇、异丙醇、HCO₃^-、Cl^-等	络合态SO₄^·-、苯酚、I^-
ROS表征方法	电子自旋共振（EPR），SO₄^·-和·OH捕捉剂5，5-二甲基-1-吡咯啉-N-氧化物（DMPO）；高效液相色谱（HPLC），·OH捕捉剂p-氯苯甲酸（p-CBA）等；荧光光度计，·OH捕捉剂对苯二甲酸等；分光光度计，N，N-二甲基-p-亚硝基苯胺（RNO）等	计时电流法，表面活性络合物、电子转移；电子自旋共振（EPR），¹O₂捕捉剂2，2，6，6-四甲基-4-哌啶酮（TMP）；液质联用（LC/MS），¹O₂捕捉剂二甲基蒽；线性扫描伏安法（LSV），电子转移

项目	自由基反应	表面催化氧化
活性氧组分（ROS）	SO₄^·-、·OH	表面活性络合物、络合态SO₄^·-、¹O₂和电子转移等
ROS氧化性	SO₄^·-，E⁰为2.5~3.1 V；HO·，E⁰为1.8~2.8 V	氧化性普遍弱于自由基
ROS稳定性	SO_·-⁴，半衰期t_1/2为30~40 μs；·OH，半衰期t_1/2 < 1 μs	¹O₂：半衰期t_1/2约4 μs
目标物选择性	SO₄^·-，部分芳香类化合物；·OH，非选择性	富电子芳香类有机物
常用掩蔽剂	甲醇、乙醇、叔丁醇、异丙醇、HCO₃^-、Cl^-等	络合态SO₄^·-、苯酚、I^-
ROS表征方法	电子自旋共振（EPR），SO₄^·-和·OH捕捉剂5，5-二甲基-1-吡咯啉-N-氧化物（DMPO）；高效液相色谱（HPLC），·OH捕捉剂p-氯苯甲酸（p-CBA）等；荧光光度计，·OH捕捉剂对苯二甲酸等；分光光度计，N，N-二甲基-p-亚硝基苯胺（RNO）等	计时电流法，表面活性络合物、电子转移；电子自旋共振（EPR），¹O₂捕捉剂2，2，6，6-四甲基-4-哌啶酮（TMP）；液质联用（LC/MS），¹O₂捕捉剂二甲基蒽；线性扫描伏安法（LSV），电子转移

目标物名称	CNMs类型	优势ROS种类	实验条件	目标物去除率
苯酚	AC^〔10〕	SO ₄ ^·-	AC 0.2 g/L，PDS 6.5 mmol/L，苯酚20 mg/L，反应180 min	44.9%
	ND^〔10〕	—	ND 0.2 g/L，PDS 6.5 mmol/L，苯酚20 mg/L，反应180 min	39.5%
	退火纳米金刚石（AND-1000）^〔29〕	·OH、络合态SO ₄ ^·-	AND-1000 0.2 g/L，PDS 6.5 mmol/L，苯酚20 mg/L，反应180 min	> 99%
	CNTs^〔16〕	表面活性络合物	CNTs 0.1 g/L，PMS 1 mmol/L，苯酚0.1 mmol/L，反应60 min	> 99%
	CMK-8^〔28〕	SO ₄ ^·-、络合态SO ₄ ^·-	CMK-8 0.2 g/L，PDS 6.5 mmol/L，苯酚20 mg/L，反应60 min	> 99%
2，4，4’-三羟基二苯甲酮（2，4，4'-HBP）	羟基化CNTsCNTs-OH）^〔30〕	·OH、络合态SO ₄ ^·-	CNTs-OH 0.1 g/L，PDS 21.7 mmol/L，2，4，4’-HBP 43.5 μmol/L，反应120 min	约89%
2，4，4’-三羟基二苯甲酮（2，4，4'-HBP）	氮掺杂羟基化CNTs（NH ₄NO ₃- CNTs-OH）^〔30〕	·OH、络合态SO ₄ ^·-	NH ₄NO ₃-CNTs-OH 0.1 g/L，PDS 21.7 mmol/L，2，4，4’-HBP 43.5 μmol/L，反应120 min	> 99%
磺胺氯哒嗪（SCP）	rGO^〔31〕	SO ₄ ^·-、·OH	rGO 0.2 g/L，PDS 2 g/L，SCP 20 mg/L，反应180 min	> 50%
磺胺氯哒嗪（SCP）	N-rGO^〔31〕	SO ₄ ^·-、·OH	N-rGO 0.2 g/L，PDS 2 g/L，SCP 20 mg/L，反应180 min	> 99%
活性黑5（RBK5）	石墨烯（GE）^〔32〕	络合态SO ₄ ^·-、·OH	GE 1.5 g/L，PMS 0.3 g/L，RBK5 5 mg/L，反应15 min	约91.5%
活性黑5（RBK5）	氮掺杂石墨烯（NG）^〔32〕	络合态SO ₄ ^·-、·OH	NG 1.5 g/L，PMS 0.3 g/L，RBK5 5 mg/L，反应15 min	约97.9%
四环素（TeC）	700 ℃氮硫掺杂多孔碳（SNCs-700）^〔33〕	¹O ₂、电子转移	SNCs-700 0.4 g/L，PDS 2 mmol/L，TeC 0.02 mmol/L，反应60 min	约81.4%
四环素（TeC）	800 ℃氮硫掺杂多孔碳（SNCs-800）^〔33〕	¹O ₂、电子转移	SNCs-800 0.4 g/L，PDS 2 mmol/L，TeC 0.02 mmol/L，反应60 min	> 90%
4-氯苯酚（4-CP）	CNTs^〔34〕	¹O ₂、络合态SO ₄ ^·-	CNTs 0.2 g/L，PMS 1 mmol/L，4-CP 0.1 mmol/L，反应60 min	> 90%
4-氯苯酚（4-CP）	800℃硫掺杂多孔碳（SDAC-800）^〔35〕	表面活性络合物	SDAC-800 0.1 g/L，PDS 15 mmol/L，4-CP 80 mg/L，反应90 min	> 99%

目标物名称	CNMs类型	优势ROS种类	实验条件	目标物去除率
苯酚	AC^〔10〕	SO ₄ ^·-	AC 0.2 g/L，PDS 6.5 mmol/L，苯酚20 mg/L，反应180 min	44.9%
	ND^〔10〕	—	ND 0.2 g/L，PDS 6.5 mmol/L，苯酚20 mg/L，反应180 min	39.5%
	退火纳米金刚石（AND-1000）^〔29〕	·OH、络合态SO ₄ ^·-	AND-1000 0.2 g/L，PDS 6.5 mmol/L，苯酚20 mg/L，反应180 min	> 99%
	CNTs^〔16〕	表面活性络合物	CNTs 0.1 g/L，PMS 1 mmol/L，苯酚0.1 mmol/L，反应60 min	> 99%
	CMK-8^〔28〕	SO ₄ ^·-、络合态SO ₄ ^·-	CMK-8 0.2 g/L，PDS 6.5 mmol/L，苯酚20 mg/L，反应60 min	> 99%
2，4，4’-三羟基二苯甲酮（2，4，4'-HBP）	羟基化CNTsCNTs-OH）^〔30〕	·OH、络合态SO ₄ ^·-	CNTs-OH 0.1 g/L，PDS 21.7 mmol/L，2，4，4’-HBP 43.5 μmol/L，反应120 min	约89%
2，4，4’-三羟基二苯甲酮（2，4，4'-HBP）	氮掺杂羟基化CNTs（NH ₄NO ₃- CNTs-OH）^〔30〕	·OH、络合态SO ₄ ^·-	NH ₄NO ₃-CNTs-OH 0.1 g/L，PDS 21.7 mmol/L，2，4，4’-HBP 43.5 μmol/L，反应120 min	> 99%
磺胺氯哒嗪（SCP）	rGO^〔31〕	SO ₄ ^·-、·OH	rGO 0.2 g/L，PDS 2 g/L，SCP 20 mg/L，反应180 min	> 50%
磺胺氯哒嗪（SCP）	N-rGO^〔31〕	SO ₄ ^·-、·OH	N-rGO 0.2 g/L，PDS 2 g/L，SCP 20 mg/L，反应180 min	> 99%
活性黑5（RBK5）	石墨烯（GE）^〔32〕	络合态SO ₄ ^·-、·OH	GE 1.5 g/L，PMS 0.3 g/L，RBK5 5 mg/L，反应15 min	约91.5%
活性黑5（RBK5）	氮掺杂石墨烯（NG）^〔32〕	络合态SO ₄ ^·-、·OH	NG 1.5 g/L，PMS 0.3 g/L，RBK5 5 mg/L，反应15 min	约97.9%
四环素（TeC）	700 ℃氮硫掺杂多孔碳（SNCs-700）^〔33〕	¹O ₂、电子转移	SNCs-700 0.4 g/L，PDS 2 mmol/L，TeC 0.02 mmol/L，反应60 min	约81.4%
四环素（TeC）	800 ℃氮硫掺杂多孔碳（SNCs-800）^〔33〕	¹O ₂、电子转移	SNCs-800 0.4 g/L，PDS 2 mmol/L，TeC 0.02 mmol/L，反应60 min	> 90%
4-氯苯酚（4-CP）	CNTs^〔34〕	¹O ₂、络合态SO ₄ ^·-	CNTs 0.2 g/L，PMS 1 mmol/L，4-CP 0.1 mmol/L，反应60 min	> 90%
4-氯苯酚（4-CP）	800℃硫掺杂多孔碳（SDAC-800）^〔35〕	表面活性络合物	SDAC-800 0.1 g/L，PDS 15 mmol/L，4-CP 80 mg/L，反应90 min	> 99%

最佳pH	CNMs类型	目标物名称	优势ROS种类	实验条件	目标物去除率
酸性条件	氮硫掺杂rGO（N，S-rGO）^〔50〕	双酚A（BPA）	SO ₄ ^·-、·OH	N，S-rGO 0.05 g/L，PDS 0.9 mmol/L，BPA 20 μg/L，反应60 min	pH=3，>85% pH=6，>95% pH=11，>55%
酸性条件	氮掺CNTs（N-CNTs）^〔51〕	酸性橙7（AO7）	络合态SO ₄ ^·-	N-CNTs 0.2 g/L，n（PMS）/n（AO7）=40/1，AO7 20 mg/L，反应30 min	pH=3，>95% pH=7，>80% pH=9，>70%
中性条件	CNTs^〔52〕	AO7	·OH、络合态SO ₄ ^·-	CNTs 0.2 g/L，n（PDS）/n（AO7）=20/1，AO7 20 mg/L，反应90 min	pH=3，>70% pH=7，>85% pH=9，>80%
	超细石墨烯（PureG）^〔53〕	对羟基苯甲酸酯（PP）	SO ₄ ^·-、·OH	PureG 0.5 g/L，PDS 20 mg/L，PP 1 mg/L，反应120 min	pH=3，>50% pH=6.5，>80% pH=9，>40%
	氮硫掺杂rGO（N，S-rGO）^〔50〕	BPA	SO ₄ ^·-、·OH	N，S-rGO 0.05 g/L，PDS 0.9 mmol/L，BPA 20 μg/L，反应60 min	pH=3，>85% pH=6.6，>95% pH=11，>55%
碱性条件	CNTs^〔27〕	2，4-二氯苯酚（2，4-DCP）	¹O ₂、电子转移	CNTs 0.1 g/L，PDS 0.05 mmol/L，2，4-DCP 0.05 mmol/L，反应10 min	pH=3，>80% pH=7，>95% pH=9，>99%

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