基于碳基催化剂活化过二硫酸盐降解有机污染物的研究进展

doi:10.16085/j.issn.1000-6613.2020-0883

摘要/Abstract

摘要：

碳基催化剂作为一种绿色催化材料，可以有效防止有毒金属离子的浸出和二次污染。本文首先对碳基催化剂活化过二硫酸盐（PDS）降解有机污染物存在的三种反应机制进行了具体的阐述，对自由基机制和非自由基机制的优缺点进行了对比和讨论，对使用不同碳基材料（包括活性炭、石墨烯、碳纳米管、中孔炭、纳米金刚石、生物炭）作为催化剂活化过二硫酸盐降解有机污染物的研究进展进行了梳理，比较了不同碳基催化剂对有机污染物的选择性和降解效果，并对各种碳基材料存在的问题进行了总结；然后探讨了碳基催化剂掺杂改性对催化活性的影响及其机理，针对碳基催化剂存在稳定性和重复利用性差的问题介绍了几种碳催化剂再生方法，最后对碳催化剂用于活化PDS降解实际有机废水的前景做出了展望。

关键词: 碳基催化剂, 过二硫酸盐, 污染物降解, 掺杂改性, 非自由基

Abstract:

As an eco-friendly catalytic material, carbon-based catalyst can effectively prevent undesirable leaching and secondary pollution of toxic metal ions. Three reaction mechanisms of carbon-based catalysts for activating persulfate (PDS) to degrade organic pollutants are elaborated and the advantages and disadvantages of the radical and nonradical mechanisms are compared and discussed in this review. The research process of using of different carbon materials, such as activated carbon, graphene, carbon nanotubes, mesoporous carbon, nano-diamonds, and biochar as the catalyst to activate persulfate to degrade organic pollutants are summarized. The selectivity and efficiency of different carbon-based materials for degradation of organic pollutants are compared and the problems of various carbon-based materials have also been briefly summarized. Then, the effects of doping modification on the catalytic activity are evaluated. For the weakness of poor stability and low reusability of carbon-catalyst, some regeneration methods are summarized in this paper. Finally,the prospects of carbon catalysts used to activate PDS to degrade organic contaminants in real wastewater are given.

Key words: carbon-based catalyst, persulfate, pollutants degradation, doping modification, non-radical

中图分类号:

X523

孙金龙, 张宇, 刘福跃, 田浩然, 刘崎峰. 基于碳基催化剂活化过二硫酸盐降解有机污染物的研究进展[J]. 化工进展, 2021, 40(3): 1653-1666.

SUN Jinlong, ZHANG Yu, LIU Fuyue, TIAN Haoran, LIU Qifeng. Research progress in degradation of organic pollutants by activation of persulfates with carbon-based catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1653-1666.

图/表 6

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催化剂	催化剂来源	目标污染物	反应机制	催化活性评价	参考文献
活性炭	商业购买	对氯苯胺（PCA）	非自由基机制	在0.5mmol·L^-1 PCA，2.5mmol·L^-1 PDS，5g·L^-1 AC和 pH=7.0的条件下，120min内PDS/AC系统的PCA降解效率为98.03%，TOC去除率约41% 在30min内实现PCA快速脱氯，并且在初始pH 3～9时PCA去除无明显影响	[52]
煤质活性炭、木质活性炭、椰壳活性炭	商业购买	偶氮染料橙黄G	非自由基机制	3个体系对染料的去除率在120min内均可达到97%以上活性炭/过硫酸盐体系对1～100mmol·L^-1氯化钠有很强的耐受作用，适用于高盐废水中有机污染物的去除	[53]
表面改性活性炭ACNH	硝酸氧化联合高温处理	苯酚	非自由基机制	苯酚浓度80mg·L^-1，活性炭投加量0.4g·L^-1，PDS与苯酚摩尔比3∶1，初始pH=6.6，ACNH/PS体系反应2h苯酚的降解率达到100% 改性后苯酚的降解速率是未改性的5倍，ACNH的pH适用范围宽	[54]
原始石墨烯、氧化石墨烯、纳米石墨粉末	商业购买	对羟基苯甲酸酯（PP）	自由基机制	在pH=9,PP浓度1mg·L^-1，催化剂量500mg·L^-1，PDS投加量20mg·L^-1，原始石墨烯，纳米石墨粉末在20min内PP降解率超过95%，GO在20min内PP降解约为70%	[28]
还原氧化石墨烯rGO-900	改良Hummers法	苯酚、2,4-二氯苯酚、邻苯二酚、1,4-二羟基苯、亚甲基蓝	自由基机制	催化剂投加量0.2g·L^-1，6.5mmol·L^-1 PDS，苯酚浓度20μg·g^-1，30min内可使苯酚完全降解。催化活性：rGO-900>CMK-8>SWCNT>g-C₃N₄>C₆₀ 对其他有机污染物（2,4-二氯苯酚，邻苯二酚和 1,4-二羟基苯，亚甲基蓝）均表现出极大的催化氧化效率	[35]
多壁碳纳米管	商业购买	2,4-二氯苯酚、邻苯二甲酸二甲酯、双酚A、邻苯二甲酸二乙酯、己烯雌酚	非自由基机制	催化剂量0.1g·L^-1，PDS和2,4-DCP量为0.031mmol·L^-1，在30min时PDS/CNTs系统中2,4-DCP的降解率高达95.9%，实现了40%的矿化对酚类化合物产生选择性降解，BPA、DES、苯酚和 2,4-DCP 30min内得到有效降解	[45]
单壁碳纳米管SWCNT多壁碳纳米管MWCNT	商业购买	苯酚、对乙酰氨基酚、三氯苯酚、磺胺甲唑、普萘洛尔、卡马西平、 4-氯苯酚、双酚A、苯甲酸、硝基苯、糠醇	非自由基机制	催化剂量0.1g·L^-1，PDS量为1mmol·L^-1，苯酚为0.1mmol·L^-1，MWCNT/PDS和SWCNT/PDS系统在20min内完全降解苯酚，其他碳材料，如活性炭和石墨，在PDS存在下对苯酚的降解无效酚类化合物和某些药物（即卡马西平、普萘洛尔、磺胺甲唑和对乙酰氨基酚）在CNT/PDS系统中可实现有效降解，硝基苯、苯甲酸和糠醇的化合物对降解具有抗性	[39]
中孔炭CMK-3和CMK-8	二氧化硅作为硬模板合成	苯酚	自由基机制非自由基机制	在催化剂投加量0.2g·L^-1，苯酚浓度为20mg·L^-1，PDS投加量为6.5mmol·L^-1条件下，CMK-3和CMK-8在20min和45min内实现了完全的苯酚氧化，分别具有0.209min^-1和0.104min^-1的高速率常数中孔炭比均相Ag⁺/PS和Fe²⁺/PS具有更好的去除苯酚的性能	[26]
中孔炭CMK-3	浸渍法	2,4-二氯苯酚	自由基机制非自由基机制	2,4-DCP浓度为200mg·L^-1，催化剂用量和PDS用量的分别为0.2μg·L^-1和2μg·L^-1条件下，20min内去除率为90% 与其他碳基催化剂相比，如碳纳米管、立方有序介孔碳（CMK-8）、活性炭、还原氧化石墨烯（rGO），CMK-3稳定性更好且与纳米金刚石（AND）相似，具有更好的可重复使用性	[33]
退火纳米金刚石（ANDs）	N₂下于600~1000℃退火	苯酚	自由基机制	在催化剂量为0.2g·L^-1，PDS投加量为6.5mmol·L^-1，苯酚浓度20mg·L^-1条件下，苯酚在120min实现完全氧化 AND-1000表现出优异的可重复使用性，第3次回收催化剂在相同反应时间仍可达到89.0%的苯酚去除效率	[36]
石墨化纳米金刚石 G-ND	在600~1200℃的温度下对NDs进行退火	苯酚、苯胺、雷尼替丁、双酚-A、对乙酰氨基酚、磺胺甲基唑、卡马西平、苯甲酸	非自由基机制	污染物浓度0.01mmol·L^-1，催化剂量为0.1g·L^-1，PDS投加量为1mmol·L^-1条件下，10min内苯酚实现完全去除 G-ND在PDS活化方面优于石墨、石墨烯、富勒烯和碳纳米管 G-ND/PDS显示出对酚类化合物和一些药物的选择性反应性，对乙酰氨基酚、苯胺、双酚A、磺胺甲唑的化合物显示出相对较高的降解效率，而苯甲酸对降解有一定的抵抗力	[42]
废麦芽根生物炭	900℃热解	磺胺甲唑（SMX）	自由基机制非自由基机制	在600mg·L^-1 PDS和500mg·L^-1 BC存在下，250μg·L^-1 SMX在30min后完全去除与纯水的运行相比，瓶装水和二级处理废水的实验表明水基质对降解的影响很小或没有影响	[77]
木基生物炭	400~700℃的不同温度热解	氯贝特酸（CA）	自由基机制非自由基机制	在10mmol·L^-1 PDS和0.5g·L^-1 BC700的条件下，60min实现了97.8%的CA去除 BC700/PDS工艺去除的CA远远高于均相的Fe²⁺/PDS和UV/PDS工艺在pH从4.0至9.0时显示出略微的下降，在pH=11.0时，CA去除率显著下降至22.8%	[78]

催化剂	催化剂来源	目标污染物	反应机制	催化活性评价	参考文献
活性炭	商业购买	对氯苯胺（PCA）	非自由基机制	在0.5mmol·L^-1 PCA，2.5mmol·L^-1 PDS，5g·L^-1 AC和 pH=7.0的条件下，120min内PDS/AC系统的PCA降解效率为98.03%，TOC去除率约41% 在30min内实现PCA快速脱氯，并且在初始pH 3～9时PCA去除无明显影响	[52]
煤质活性炭、木质活性炭、椰壳活性炭	商业购买	偶氮染料橙黄G	非自由基机制	3个体系对染料的去除率在120min内均可达到97%以上活性炭/过硫酸盐体系对1～100mmol·L^-1氯化钠有很强的耐受作用，适用于高盐废水中有机污染物的去除	[53]
表面改性活性炭ACNH	硝酸氧化联合高温处理	苯酚	非自由基机制	苯酚浓度80mg·L^-1，活性炭投加量0.4g·L^-1，PDS与苯酚摩尔比3∶1，初始pH=6.6，ACNH/PS体系反应2h苯酚的降解率达到100% 改性后苯酚的降解速率是未改性的5倍，ACNH的pH适用范围宽	[54]
原始石墨烯、氧化石墨烯、纳米石墨粉末	商业购买	对羟基苯甲酸酯（PP）	自由基机制	在pH=9,PP浓度1mg·L^-1，催化剂量500mg·L^-1，PDS投加量20mg·L^-1，原始石墨烯，纳米石墨粉末在20min内PP降解率超过95%，GO在20min内PP降解约为70%	[28]
还原氧化石墨烯rGO-900	改良Hummers法	苯酚、2,4-二氯苯酚、邻苯二酚、1,4-二羟基苯、亚甲基蓝	自由基机制	催化剂投加量0.2g·L^-1，6.5mmol·L^-1 PDS，苯酚浓度20μg·g^-1，30min内可使苯酚完全降解。催化活性：rGO-900>CMK-8>SWCNT>g-C₃N₄>C₆₀ 对其他有机污染物（2,4-二氯苯酚，邻苯二酚和 1,4-二羟基苯，亚甲基蓝）均表现出极大的催化氧化效率	[35]
多壁碳纳米管	商业购买	2,4-二氯苯酚、邻苯二甲酸二甲酯、双酚A、邻苯二甲酸二乙酯、己烯雌酚	非自由基机制	催化剂量0.1g·L^-1，PDS和2,4-DCP量为0.031mmol·L^-1，在30min时PDS/CNTs系统中2,4-DCP的降解率高达95.9%，实现了40%的矿化对酚类化合物产生选择性降解，BPA、DES、苯酚和 2,4-DCP 30min内得到有效降解	[45]
单壁碳纳米管SWCNT多壁碳纳米管MWCNT	商业购买	苯酚、对乙酰氨基酚、三氯苯酚、磺胺甲唑、普萘洛尔、卡马西平、 4-氯苯酚、双酚A、苯甲酸、硝基苯、糠醇	非自由基机制	催化剂量0.1g·L^-1，PDS量为1mmol·L^-1，苯酚为0.1mmol·L^-1，MWCNT/PDS和SWCNT/PDS系统在20min内完全降解苯酚，其他碳材料，如活性炭和石墨，在PDS存在下对苯酚的降解无效酚类化合物和某些药物（即卡马西平、普萘洛尔、磺胺甲唑和对乙酰氨基酚）在CNT/PDS系统中可实现有效降解，硝基苯、苯甲酸和糠醇的化合物对降解具有抗性	[39]
中孔炭CMK-3和CMK-8	二氧化硅作为硬模板合成	苯酚	自由基机制非自由基机制	在催化剂投加量0.2g·L^-1，苯酚浓度为20mg·L^-1，PDS投加量为6.5mmol·L^-1条件下，CMK-3和CMK-8在20min和45min内实现了完全的苯酚氧化，分别具有0.209min^-1和0.104min^-1的高速率常数中孔炭比均相Ag⁺/PS和Fe²⁺/PS具有更好的去除苯酚的性能	[26]
中孔炭CMK-3	浸渍法	2,4-二氯苯酚	自由基机制非自由基机制	2,4-DCP浓度为200mg·L^-1，催化剂用量和PDS用量的分别为0.2μg·L^-1和2μg·L^-1条件下，20min内去除率为90% 与其他碳基催化剂相比，如碳纳米管、立方有序介孔碳（CMK-8）、活性炭、还原氧化石墨烯（rGO），CMK-3稳定性更好且与纳米金刚石（AND）相似，具有更好的可重复使用性	[33]
退火纳米金刚石（ANDs）	N₂下于600~1000℃退火	苯酚	自由基机制	在催化剂量为0.2g·L^-1，PDS投加量为6.5mmol·L^-1，苯酚浓度20mg·L^-1条件下，苯酚在120min实现完全氧化 AND-1000表现出优异的可重复使用性，第3次回收催化剂在相同反应时间仍可达到89.0%的苯酚去除效率	[36]
石墨化纳米金刚石 G-ND	在600~1200℃的温度下对NDs进行退火	苯酚、苯胺、雷尼替丁、双酚-A、对乙酰氨基酚、磺胺甲基唑、卡马西平、苯甲酸	非自由基机制	污染物浓度0.01mmol·L^-1，催化剂量为0.1g·L^-1，PDS投加量为1mmol·L^-1条件下，10min内苯酚实现完全去除 G-ND在PDS活化方面优于石墨、石墨烯、富勒烯和碳纳米管 G-ND/PDS显示出对酚类化合物和一些药物的选择性反应性，对乙酰氨基酚、苯胺、双酚A、磺胺甲唑的化合物显示出相对较高的降解效率，而苯甲酸对降解有一定的抵抗力	[42]
废麦芽根生物炭	900℃热解	磺胺甲唑（SMX）	自由基机制非自由基机制	在600mg·L^-1 PDS和500mg·L^-1 BC存在下，250μg·L^-1 SMX在30min后完全去除与纯水的运行相比，瓶装水和二级处理废水的实验表明水基质对降解的影响很小或没有影响	[77]
木基生物炭	400~700℃的不同温度热解	氯贝特酸（CA）	自由基机制非自由基机制	在10mmol·L^-1 PDS和0.5g·L^-1 BC700的条件下，60min实现了97.8%的CA去除 BC700/PDS工艺去除的CA远远高于均相的Fe²⁺/PDS和UV/PDS工艺在pH从4.0至9.0时显示出略微的下降，在pH=11.0时，CA去除率显著下降至22.8%	[78]

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