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近年来,有害藻类大量繁殖导致的水体富营养化现象在世界各国频繁出现[1 − 3]. 水华爆发时,以蓝藻为代表的有害藻类大量消耗水中溶解氧,造成水中其它水生植物、动物死亡,最终影响水环境质量,破坏水生态环境平衡,对人类健康和社会经济造成严重危害[4]. 同时,藻类在死亡过程中释放出的藻毒素和有机质等物质对环境造成二次污染. 因此,控制有害藻华繁殖,防治水体富营养化成为水污染控制的重要议题. 在此背景下,国家和地方在水华频繁爆发的地区制定出台政策文件,旨在控制水体富营养的危害. 国家发展改革委于2021年发布的《关于加强长江经济带重要湖泊保护和治理的指导意见》(发改地区[2021]1617号)明确,到2025年,确保太湖、巢湖地区不发生大面积蓝藻水华导致水体黑臭现象,以确保供水水源安全.
目前,已有多种除藻以及控制水华爆发的技术手段. 传统的治理手段主要包括化学法、物理法和生物法[5]. 化学法采用向水中投加混凝剂、絮凝剂等化学药剂,如CuSO4、Cl2等[6]. 在此过程中可能生成二次污染物,对水体造成不利影响[7]. 物理法采用超声波[8 − 10]、人工捕捞、紫外辐照[11 − 13]等手段,往往成本高且治标不治本,效果无法长期维持. 生物法采用种植沉水植物,改善水生态群落结构的方法,见效缓慢且作用效果不稳定,无法广泛应用[14 − 16]. 鉴于目前已有的除藻手段存在各自的缺陷,寻求一种新型高效环境友好的除藻手段迫在眉睫. 光催化技术是利用自然界中存在的太阳能激发材料产生高活性的自由基等,从而达到去除水中污染物的目的. 之前的研究中,光催化技术已被广泛应用于去除重金属[17]、活性染料[18]、抗生素类药物[19]等污染物,均取得了良好效果[20]. 蓝藻作为一种特殊的水体污染物,在光催化材料的作用下可被完全灭活从而从水体中去除. 同时,对于藻类死亡过程中产生的藻毒素类物质具有良好的协同降解作用,最终达到促进水体自净、恢复水生态平衡的目的. 本文从光催化材料的概念出发,系统梳理了已有的可除藻的光催化材料种类,阐明了光催化除藻的机理,并分析影响材料发挥性能的主要因素,并探讨了溶藻过程中藻毒素等有害副产物的释放与去除,对于现有光催化材料抑藻过程中尚存的不足进行分析,以期为后续研究提供参考和支撑.
光催化抑藻材料的研究进展
Advances in photocatalytic materials for algae inhibition
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摘要: 水体富营养化引起有害藻华爆发,严重危害了全球人类健康和生态环境. 这一难题困扰了湖泊生态环境保护的研究者们几十年,但目前各项传统除藻手段仍存在一定不足,亟需在此基础上引入各种新技术. 光催化技术凭借高效清洁、环境友好、操作简单等优势,在控制水体富营养化和抑制有害蓝藻水华爆发方面具有一定的应用前景. 本文综述了近年来光催化材料去除有害藻华爆发的研究进展,阐明了光催化技术的抑藻机理,强调了除藻过程中藻毒素类污染物质的释放与去除问题,最后总结了光催化抑藻的关键限制性条件,指出了该技术在应用推广中要关注的因素,并对未来光催化材料强化水生态自净能力的研究方向进行展望.Abstract: The eutrophication induced by harmful algal blooms has seriously endangered human health and ecological environment worldwide. It is a challenge that has plagued researchers for decades in the research direction of lake ecology and environment restoration. In the context of the existing algae removal methods, photocatalytic technology, with its advantages of high efficiency, cleanliness, environmental friendliness, and simplicity of operation, has some prospects for application in controlling harmful algal blooms and eutrophication. Therefore, this study reviews the research progress of photocatalytic materials for removing harmful algae in recent years, clarifies the mechanism of algae inhibition by photocatalytic materials, and emphasizes the release and removal of toxic pollutants in the process of algae removal. Finally, we summarize the crucial limiting factors of photocatalytic materials for algae inhibition, point out the remaining shortcomings in the application and promotion of this technology. We hope this review provides an outlook on the future research of photocatalytic materials to enhance the self-purification ability of aquatic ecology.
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Key words:
- photocatalysis /
- nanomaterials /
- water eutrophication /
- algae removal.
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表 1 现有光催化材料除藻性能及特性研究
Table 1. Research on the performance and characteristics of photocatalytic materials for algae removal
材料名称
Photocatalyst去除藻种
Algae species光源类型
Light source添加量
Dosage时间
Inactivation time去除率
Inactivation efficiency活性基团
ROS是否可回收
Recyclability参考文献
ReferenceF-Ce-TiO2/EP450 铜绿微囊藻 可见光 4 g·L−1 9 h 98.1% ·OH、h+、·O2- 是 [24] Zn-Fe LDHs 铜绿微囊藻 可见光 0.3 g·L−1 2.5 h 80.6% — 否 [25] Sg-Bi2Mo3O12 铜绿微囊藻 可见光 1 g·L-1 4 h >84% ·O2− 否 [26] Cp-Bi2Mo3O12 铜绿微囊藻 可见光 1 g·L−1 4 h 52% ·O2− 否 [26] B-SiO2@TiO2 野外绿藻 可见光 5 g·L−1 8.5 h 100% — 是 [27] AP-EGC-CT5 铜绿微囊藻 可见光 2 g·L−1 2 h 98.5% h+ 否 [28] NPT-EGC450 铜绿微囊藻 可见光 2 g·L−1 9 h 98.15% h+ 是 [29] 0.2PDDA@NPT-EGC 铜绿微囊藻 可见光 2 g·L−1 9 h 92.6% h+ 是 [30] Ag/AgCl@ZIF-8 sponge sponge 铜绿微囊藻 可见光 — 6 h 99.9% ·O2− 是 [31] Ag/AgCl@ZIF-8 铜绿微囊藻 可见光 10 g·L−1 6 h 93.1% ·O2− 否 [32] Ag2CO3-GO 铜绿微囊藻 可见光 0.1 g·L−1 9 h 100% ·OH、·O2- 否 [33] Ag2CO3-N:GO coating-4 铜绿微囊藻 可见光 4 g·L−1 5 h 100% ·O2− 是 [34] SnO2- montmorillonite 铜绿微囊藻 紫外光 0.3 g·L−1 1 h 95% — 否 [35] Ag2O/g-C3N4 铜绿微囊藻 可见光 0.05 g·L−1 6 h
99.94% ·O2− 否 [36] N掺杂黑色TiO2-N2(500℃) 铜绿微囊藻 可见光 0.2 g·L−1 12 h 99.09% ·O2−、·OH 否 [37] rGO/BiOBr 铜绿微囊藻 可见光 — 3 h 99% ·O2−、h+ 是 [38] N-TiO2 拟柱孢藻/铜绿微囊藻 可见光 0.2 g·L−1 20 h/14 h 100%/100% — 否 [39] 漂浮g-C3N4 铜绿微囊藻 可见光 2 g·L−1 6 h
74.7% ·O2−、·OH 是 [40] ZnO纳米颗粒 铜绿微囊藻 可见光 35 g·L−1 2 h 98% — 否 [41] g-C3N4/TiO2 铜绿微囊藻 可见光 2 g·L−1 6 h 88.1% ·OH、h+ 是 [41] TiO2 铜绿微囊藻 紫外光 0.2 g·L−1 — 100% — 否 [42] Zn掺杂的Fe3O4 铜绿微囊藻 可见光 0.05 g·L−1 6 h 96% — 否 [43] Ca-Ag3PO4 微绿球藻
可见光 0.9 g·L−1 12 h 96% ·OH 否 [44] Ag2O/g-C3N4 水凝胶 铜绿微囊藻 可见光 1 g·L−1 5 h 98.6% ·O2−、·OH 是 [45] Ag/AgCl@LaFeO3 铜绿微囊藻 可见光 50 mg·L−1 2 h >90% ·O2−、·OH 否 [46] g-C3N4/Bi-TiO2 铜绿微囊藻 可见光 — 6 h 75.9% ·OH、h+ 是 [47] Ag2O@PG 铜绿微囊藻 可见光 0.2 g·L−1 5 h 99.1% ·O2−、h+、·OH 否 [48] g-C3N4-MoO3 铜绿微囊藻 可见光 0.3 g·L−1 3 h 97% ·O2−、·OH 否 [49] Ag/AgCl@g-C3N4@UIO-66 铜绿微囊藻 可见光 30 g·L−1 3 h 99.9% ·O2−、h+、·OH 否 [50] b-N-TiO2/C 铜绿微囊藻 可见光 0.2 g·L−1 12 h 92.7% ·O2−、·OH 否 [51] F- TiO2 铜绿微囊藻 太阳光 0.75 g·L−1 8 h 97.5% ·O2−、h+、·OH 否 [52] 硫酸剥离的g-C3N4 铜绿微囊藻 可见光 0.3 g·L−1 3.5 h 92% h+、·OH 否 [53] Ag2CrO4-g-C3N4-TiO2/mEP 铜绿微囊藻 可见光 2 g·L−1 8 h 81.88% ·O2−、h+、·OH 是 [54] AGUN自浮泡沫 铜绿微囊藻 可见光 1 g·L−1 3 h 98% ·O2−、h+、·OH 是 [55] 改性TiO2/Ag3PO4 拟柱孢藻 可见光 0.3 g·L−1 5 h 91.75% ·O2− 否 [56] TiO2/Ag3PO4 铜绿微囊藻 可见光 0.2 g·L−1 8 h 95.0% ·O2 否 [57] Bi2O3@Cu-MOF 米氏凯伦藻 可见光 60 g·L−1 4 h 96.35% ·O2−、·OH 否 [58] ZnFe2O4/Ag3PO4/g-C3N4 铜绿微囊藻 可见光 100 g·L−1 3 h 96.33% ·O2−、·OH 是 [59] g-C3N4@Bi2MoO6@AgI 铜绿微囊藻 可见光 — 5 h >95% ·O2− 是 [60] Ni@ZnO@ZnS 勃那特螺旋藻、
水华鱼腥藻可见光 0.6 g·L−1 10—35 min 100% — 是 [61] “—”无数据. -
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