钴基催化剂的合成及其活化过一硫酸盐的研究进展

doi:10.3969/j.issn.1006-396X.2022.05.002

摘要/Abstract

摘要：

钴基催化剂活化过一硫酸盐（PMS）具有催化活性高、操作简便、易回收和成本较低等优点，因此近年来在高级氧化技术领域备受关注。综述了钴基催化剂的典型合成方法，包括固相法、气相法和液相法等；介绍了用于活化PMS的钴基催化剂的类型，包括具有特殊形貌的钴氧化物、负载型钴氧化物和钴基复合金属氧化物；阐述了钴基催化剂活化PMS在环境修复中降解有机染料、内分泌干扰物以及药物和个人护理品的研究进展；总结了目前钴基催化剂活化PMS存在的一些不足，并对该领域今后的研究提出了展望。

关键词: 钴基催化剂, 合成方法, 多相催化, 过一硫酸盐活化, 环境修复

Abstract:

The activation of peroxymonosulfate (PMS) by cobalt?based catalysts has the advantages of high catalytic activity, simple operation, easy recyclability, and low cost. Hence, it has attracted much attention in the field of advanced oxidation processes in recent years. This paper reviewed typical methods for the synthesis of cobalt?based catalysts, including solid phase, gas phase, and liquid phase methods. Several types of cobalt?based catalysts for PMS activation, including cobalt oxides with special morphologies, supported cobalt catalysts, and cobalt?based composite metal oxides, were summarized. The applications of these cobalt?based catalysts in environmental remediation via PMS activation were also elaborated, such as the degradation of organic dyes, endocrine?disrupting chemicals, and pharmaceutical and personal care products. Finally, the current shortcomings of cobalt?based catalysts in PMS activation were summarized, and some future research directions in this area were proposed.

Key words: Cobalt?based catalyst, Synthesis, Heterogeneous catalysis, Peroxymonosulfate activation, Environmental remediation

中图分类号:

TQ426

吕玉, 王晓宁, 吴张雄. 钴基催化剂的合成及其活化过一硫酸盐的研究进展[J]. 石油化工高等学校学报, 2022, 35(5): 12-24.

Lü Yu, Xiaoning Wang, Zhangxiong Wu. Research Progress in Synthesis of Cobalt⁃Based Catalysts and Peroxymonosulfate Activation[J]. Journal of Petrochemical Universities, 2022, 35(5): 12-24.

图/表 8

图1 利用钴基MOFs制备中空多孔Co3O4纳米盒的示意图

Fig.1 Schematic illustration of hollow porous Co3O4 nanoboxes prepared using cobalt?based MOFs

图2 超声波喷雾热分解法合成干梅状、多孔状和榴莲状Co3O4颗粒示意图

Fig.2 Schematic illustration of the synthetic process of dried plum?like, porous, and durian?like microsphere morphology Co3O4 particles via ultrasonic spray pyrolysis

图3 水热法合成不同形貌的Co3O4纳米材料的示意图

Fig.3 Schematic illustration of the synthetic process of Co3O4 with different morphologies by the hydrothermal method

图4 HSO5-的分子结构示意图

Fig.4 The molecular structure of HSO5-

图5 不同Co3O4的形貌示意图

Fig.5 Illustration of the morphologies of different Co3O4 materials

图6 蛋黄壳状Co3O4@MOFs纳米反应器中4?CP降解的可能机制示意图

Fig.6 Schematic illustration of possible mechanism of 4?CP degradation in the egg?yolk?shell Co3O4@MOFsnanoreactor

表1 代表性钴基催化剂活化PMS在环境修复中的应用

Table 1 Applications of some typical cobalt?based catalysts in environmental remediation via PMS activation

污染物	$ρ$ （污染物）/（mg $⋅$ L^-1）	催化剂	$ρ$ （催化剂）/(g $⋅$ L^-1)	c（PMS）/（mmol $⋅$ L^-1)	$ρ$ （PMS）/(g $⋅$ L^-1)	pH	温度/ ℃	时间/min	去除率/%	参考文献
酸性橙7	20	NT⁃Co₃O₄	0.05	0.100		8.00	25	30	89.0	[61]
酸性橙7	20	CoFe₂O₄	0.50	0.800		6.30	27	40	96.0	[62]
罗丹明B	20	Co₃O₄⁃0.5RHA	0.10		0.50	6.00	20	60	96.3	[63]
罗丹明B	20	CoFe₂O₄/Ag	0.20		1.00	6.50	-	14	100.0	[30]
4⁃氯酚	50	MS⁃V_O⁃Co₃O₄	0.05		0.20	-	20	20	98.4	[64]
双酚A	25	Co₃O₄⁃MnO₂/BC	0.10	1.000		7.00	25	25	91.0	[65]
双酚A	20	(Co、Mn)₃O₄	0.10	0.325		9.70	25	5	99.0	[66]
2,4⁃二氯酚	50	FCO_VNPs	0.20		1.00	6.80	25±1	90	97.3	[67]
磺基水杨酸	10	Co₃O₄	0.15		0.15	7.00	25	120	100.0	[51]
氯霉素	50	Co₃O₄/BC	0.20	10.000		7.00	-	10	97.6±1.2	[53]
环丙沙星	20	Co₃O₄/CB	0.20		0.50	5.98	25	30	93.0	[68]
三氯生	10	Co₂Mn₁O₄	0.02		0.05	6.80	25	30	96.4	[69]
诺氟沙星	20	NiCo₂O₄	0.05	0.670		7.00	25	90	97.5	[70]

表1 代表性钴基催化剂活化PMS在环境修复中的应用

Table 1 Applications of some typical cobalt?based catalysts in environmental remediation via PMS activation

污染物	$ρ$ （污染物）/（mg $⋅$ L^-1）	催化剂	$ρ$ （催化剂）/(g $⋅$ L^-1)	c（PMS）/（mmol $⋅$ L^-1)	$ρ$ （PMS）/(g $⋅$ L^-1)	pH	温度/ ℃	时间/min	去除率/%	参考文献
酸性橙7	20	NT⁃Co₃O₄	0.05	0.100		8.00	25	30	89.0	[61]
酸性橙7	20	CoFe₂O₄	0.50	0.800		6.30	27	40	96.0	[62]
罗丹明B	20	Co₃O₄⁃0.5RHA	0.10		0.50	6.00	20	60	96.3	[63]
罗丹明B	20	CoFe₂O₄/Ag	0.20		1.00	6.50	-	14	100.0	[30]
4⁃氯酚	50	MS⁃V_O⁃Co₃O₄	0.05		0.20	-	20	20	98.4	[64]
双酚A	25	Co₃O₄⁃MnO₂/BC	0.10	1.000		7.00	25	25	91.0	[65]
双酚A	20	(Co、Mn)₃O₄	0.10	0.325		9.70	25	5	99.0	[66]
2,4⁃二氯酚	50	FCO_VNPs	0.20		1.00	6.80	25±1	90	97.3	[67]
磺基水杨酸	10	Co₃O₄	0.15		0.15	7.00	25	120	100.0	[51]
氯霉素	50	Co₃O₄/BC	0.20	10.000		7.00	-	10	97.6±1.2	[53]
环丙沙星	20	Co₃O₄/CB	0.20		0.50	5.98	25	30	93.0	[68]
三氯生	10	Co₂Mn₁O₄	0.02		0.05	6.80	25	30	96.4	[69]
诺氟沙星	20	NiCo₂O₄	0.05	0.670		7.00	25	90	97.5	[70]

图7 Co3O4纳米线在无CO32-和有CO32-体系中活化PMS降解BPA的示意图

Fig.7 Schematic diagram of Co3O4 nanowire?catalyzed PMS activation for BPA degradation in the systems with?out and with CO32-

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