漂浮型光催化材料的制备及其在水处理领域的应用研究进展

doi:10.16085/j.issn.1000-6613.2022-1273

摘要/Abstract

摘要：

漂浮型光催化材料以高效光催化剂为核心，以太阳光等绿色清洁能源为驱动力，克服了纳米光催化剂难以回收利用这一瓶颈问题，通过吸附、光催化等耦合作用高效原位降解水体中的污染物，是实现光催化高级氧化技术规模化应用最有前景的途径之一。本文从载体类型出发，概括总结了近年来漂浮型光催化材料的轻质特性构建策略、形貌结构和不同载体利弊；分析比较了典型光催化剂-载体复合材料制备方法的优缺点；分类阐述了漂浮型光催化剂在水处理领域的应用研究成果。通过归纳漂浮型光催化材料在实际应用中存在的问题，指出未来漂浮型光催化剂的研究开发应重点关注环境友好型载体和材料性能稳定性；同时可通过构建多功能复合材料或采取多工艺耦合的方式以推动高效光催化剂在水处理方面的规模化应用。

关键词: 漂浮, 光催化, 催化剂载体, 复合材料, 水污染

Abstract:

Photocatalysis with floating photocatalysts is one of the promising advanced oxidation technologies in water treatment field, which can overcome the recovery problem of nanoparticles. This method relies on the high-efficiency photocatalysts and could be driven by green energy such as sunlight. Pollutants can be efficiently in-situ degraded under the synergistic effects of adsorption and photocatalysis. In this paper, the lightweight construction strategies, morphological structures and pros and cons are summarized from the point of support styles. The advantages and disadvantages of typical composites preparation methods are analyzed and compared, and the applications of floating photocatalysts of different categories in the water treatment field are presented. By summarizing the problems of floating photocatalysts in practical applications, we point out that future research and development of floating photocatalysts should focus on the eco-friendly carriers and the stability of composites. Multifunctional floating photocatalysts as well as coupling technologies can be applied for promoting the large-scale application of high-efficiency photocatalysts in water treatment.

Key words: floating, photocatalysis, catalyst support, composites, water pollution

中图分类号:

张宁, 吴海滨, 李钰, 李剑锋, 程芳琴. 漂浮型光催化材料的制备及其在水处理领域的应用研究进展[J]. 化工进展, 2023, 42(5): 2475-2485.

ZHANG Ning, WU Haibin, LI Yu, LI Jianfeng, CHENG Fangqin. Recent advances in preparation and application of floating photocatalysts in water treatment[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2475-2485.

图/表 8

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载体	制备方法	参数（长度/粒径/密度）	反应条件（光源/污染物浓度）	降解效率	参考文献
TiO₂/硅藻土颗粒	煅烧法	2mm	150W 氙灯可见光滤光片	四环素：92%/150min	[4]
g-C₃N₄/膨胀玻璃珠	煅烧法	2~4mm	36W 荧光灯四组	微囊藻毒素-LR：100%/60min 柱状藻毒素：100%/100min	[13]
TiO₂-ZnO/轻质膨胀黏土	浸渍-焙烧	4~8mm	125W UV-C（398mW/cm²） NH₃·H₂O：400mg/L	NH₃·H₂O：95.2%/3h	[17]
TiO₂/泡沫玻璃	喷涂法	1~2mm	8W UV-A LED 柴油：688mg/L 自然太阳光亚甲基蓝：20μmol/L	柴油：60.6%/68h 亚甲基蓝：56.4%/6h	[24]
BiOI/SiO₂微球	浸渍-水热法	1.2μm	300W 氙灯（λ>400nm）柴油：1000mg/L 罗丹明B：10mg/L	柴油：86%/300min 罗丹明B：86.2%/15h（36W LED）	[28]
CeO₂/膨胀石墨	浸渍-焙烧法	片状石墨（80目）为基材	300W 氙灯（λ>400nm）苯酚：10mg/L	苯酚：吸附率38.8%/30min 降解率97.3%/2h	[30]
聚二甲基二烯丙基氯化铵- g-C₃N₄-膨胀石墨	浸渍改性	400~500μm	500W 氙灯（λ>420nm）	微囊藻毒素-LR：100%/2h	[31]
Ag/g-C₃N₄/还原氧化石墨烯气凝胶	水热法	块状	300W 氙灯（λ>420nm）罗丹明6G：10mg/L	罗丹明6G：降解率93%/4h 矿化率70.5%/4h	[33]

载体	制备方法	参数（长度/粒径/密度）	反应条件（光源/污染物浓度）	降解效率	参考文献
TiO₂/硅藻土颗粒	煅烧法	2mm	150W 氙灯可见光滤光片	四环素：92%/150min	[4]
g-C₃N₄/膨胀玻璃珠	煅烧法	2~4mm	36W 荧光灯四组	微囊藻毒素-LR：100%/60min 柱状藻毒素：100%/100min	[13]
TiO₂-ZnO/轻质膨胀黏土	浸渍-焙烧	4~8mm	125W UV-C（398mW/cm²） NH₃·H₂O：400mg/L	NH₃·H₂O：95.2%/3h	[17]
TiO₂/泡沫玻璃	喷涂法	1~2mm	8W UV-A LED 柴油：688mg/L 自然太阳光亚甲基蓝：20μmol/L	柴油：60.6%/68h 亚甲基蓝：56.4%/6h	[24]
BiOI/SiO₂微球	浸渍-水热法	1.2μm	300W 氙灯（λ>400nm）柴油：1000mg/L 罗丹明B：10mg/L	柴油：86%/300min 罗丹明B：86.2%/15h（36W LED）	[28]
CeO₂/膨胀石墨	浸渍-焙烧法	片状石墨（80目）为基材	300W 氙灯（λ>400nm）苯酚：10mg/L	苯酚：吸附率38.8%/30min 降解率97.3%/2h	[30]
聚二甲基二烯丙基氯化铵- g-C₃N₄-膨胀石墨	浸渍改性	400~500μm	500W 氙灯（λ>420nm）	微囊藻毒素-LR：100%/2h	[31]
Ag/g-C₃N₄/还原氧化石墨烯气凝胶	水热法	块状	300W 氙灯（λ>420nm）罗丹明6G：10mg/L	罗丹明6G：降解率93%/4h 矿化率70.5%/4h	[33]

载体	制备方法	参数（长度/粒径/密度）	反应条件（光源/污染物浓度）	降解率	参考文献
还原氧化石墨烯/BiOBr/丝瓜海绵	水热法	d=5.5cm 圆柱状	300W氙灯（80mW/cm²）（λ>420nm）	铜绿微囊藻：90%/3h 总有机碳（TOC）：74%	[34]
表面改性-TiO₂/棕榈树干	浸渍法	块状	自然阳光刚果红：10mg/L 苯酚：10mg/L 4-硝基苯酚：10mg/L 2.4-二硝基苯酚：10mg/L 甲苯胺：10mg/L	刚果红：98.2%/210min 苯酚：58.4%/210min 4-硝基苯酚：83.0%/210min 2.4-二硝基苯酚：70.7%/210min 甲苯胺：61.6%/210min	[35]
Fe⁰/低密度聚乙烯	低温热附着法	4mm 0.9~2.0g/cm³	85W商用荧光灯丽春红4R：50~150mg/L	丽春红4R：100%/15min （50mg/L时）	[44]
Ag/AgCl@ZIF-8/改性聚氨酯海绵	涂层法	4.5cm×4.5cm×0.5cm	500W卤灯（λ>420nm）	铜绿微囊藻：98.5%/4h	[46]
ZnO-C₃N₄/聚对苯二甲酸乙二醇酯	超声浸渍法	—	150W卤钨灯苯：8400mg/L	苯：99.7%/1.5h	[47]
聚醚酰亚胺/g-C₃N₄	黏结法	块状	11W近自然光甲基橙：4mg/L	甲基橙：80%/68h	[49]
聚二甲基硅氧烷/聚多巴胺/普鲁士蓝	模板法	2~3mm	70mW/cm² 亚甲基蓝：5mg/L	亚甲基蓝：/1.5~2h	[50]
介孔黑色 TiO₂泡沫	冷冻干燥-筑造成型-表面氢化	d=1.0cm h=0.2~0.3cm	300W 氙灯 100mW/cm² 催化剂：2.5g/L 污染物：1mg/L	十六烷：99%/15h（TOC）罗丹明B：100%/3h（TOC）	[51]
Ag₂O/g-C₃N₄水凝胶	原位合成法	31.86g 5cm	500W钨灯 4.78×10⁶个细胞/mL 催化剂：1g/L	铜绿微囊藻：98.6%/5h	[52]
g-C₃N₄-纳米纤维素	溶剂浇铸法	h=0.3mm (40±3)kg/m³	LED 罗丹明B：5mg/L	95%/6h	[59]
生物质-TiO₂-气凝胶	凝胶法-浇筑法	丸状棒状	300W 氙灯（50W/m²）可见光（>420nm） Cr⁶⁺：10μg/g	Cr⁶⁺：100%/90min	[53]
TiO_2-有机硅复合气凝胶	原位缩聚法	d=4cm h=0.3cm	4W/40W/250W 紫外灯（300nm＜λ＜380nm）罗丹明B：20mg/L 双酚A：20mg/L	罗丹明B 4W：100%/11h 40W：100%/5h 250W：100%/150min 双酚A 4W：TOC，87%/25h	[54]
TiO₂-NaOB/海藻酸钙	离子凝胶法	3.0~4.9mm	10组3W UV LED 柠檬黄：50mg/L 亚甲基蓝：50mg/L	柠檬黄：降解率95%/3h 矿化率34.4%/3h 亚甲基蓝：降解率99%/3h 矿化率53.6%/3h	[56]
聚砜/海藻酸盐/TiO₂	相转变	1~6mm	15WUV 亚甲基蓝：3.2mg/L 双氯芬酸：20mg/L 三氯生20mg/L	100%/50min 100%/40min 100%/120min	[58]

载体	制备方法	参数（长度/粒径/密度）	反应条件（光源/污染物浓度）	降解率	参考文献
还原氧化石墨烯/BiOBr/丝瓜海绵	水热法	d=5.5cm 圆柱状	300W氙灯（80mW/cm²）（λ>420nm）	铜绿微囊藻：90%/3h 总有机碳（TOC）：74%	[34]
表面改性-TiO₂/棕榈树干	浸渍法	块状	自然阳光刚果红：10mg/L 苯酚：10mg/L 4-硝基苯酚：10mg/L 2.4-二硝基苯酚：10mg/L 甲苯胺：10mg/L	刚果红：98.2%/210min 苯酚：58.4%/210min 4-硝基苯酚：83.0%/210min 2.4-二硝基苯酚：70.7%/210min 甲苯胺：61.6%/210min	[35]
Fe⁰/低密度聚乙烯	低温热附着法	4mm 0.9~2.0g/cm³	85W商用荧光灯丽春红4R：50~150mg/L	丽春红4R：100%/15min （50mg/L时）	[44]
Ag/AgCl@ZIF-8/改性聚氨酯海绵	涂层法	4.5cm×4.5cm×0.5cm	500W卤灯（λ>420nm）	铜绿微囊藻：98.5%/4h	[46]
ZnO-C₃N₄/聚对苯二甲酸乙二醇酯	超声浸渍法	—	150W卤钨灯苯：8400mg/L	苯：99.7%/1.5h	[47]
聚醚酰亚胺/g-C₃N₄	黏结法	块状	11W近自然光甲基橙：4mg/L	甲基橙：80%/68h	[49]
聚二甲基硅氧烷/聚多巴胺/普鲁士蓝	模板法	2~3mm	70mW/cm² 亚甲基蓝：5mg/L	亚甲基蓝：/1.5~2h	[50]
介孔黑色 TiO₂泡沫	冷冻干燥-筑造成型-表面氢化	d=1.0cm h=0.2~0.3cm	300W 氙灯 100mW/cm² 催化剂：2.5g/L 污染物：1mg/L	十六烷：99%/15h（TOC）罗丹明B：100%/3h（TOC）	[51]
Ag₂O/g-C₃N₄水凝胶	原位合成法	31.86g 5cm	500W钨灯 4.78×10⁶个细胞/mL 催化剂：1g/L	铜绿微囊藻：98.6%/5h	[52]
g-C₃N₄-纳米纤维素	溶剂浇铸法	h=0.3mm (40±3)kg/m³	LED 罗丹明B：5mg/L	95%/6h	[59]
生物质-TiO₂-气凝胶	凝胶法-浇筑法	丸状棒状	300W 氙灯（50W/m²）可见光（>420nm） Cr⁶⁺：10μg/g	Cr⁶⁺：100%/90min	[53]
TiO_2-有机硅复合气凝胶	原位缩聚法	d=4cm h=0.3cm	4W/40W/250W 紫外灯（300nm＜λ＜380nm）罗丹明B：20mg/L 双酚A：20mg/L	罗丹明B 4W：100%/11h 40W：100%/5h 250W：100%/150min 双酚A 4W：TOC，87%/25h	[54]
TiO₂-NaOB/海藻酸钙	离子凝胶法	3.0~4.9mm	10组3W UV LED 柠檬黄：50mg/L 亚甲基蓝：50mg/L	柠檬黄：降解率95%/3h 矿化率34.4%/3h 亚甲基蓝：降解率99%/3h 矿化率53.6%/3h	[56]
聚砜/海藻酸盐/TiO₂	相转变	1~6mm	15WUV 亚甲基蓝：3.2mg/L 双氯芬酸：20mg/L 三氯生20mg/L	100%/50min 100%/40min 100%/120min	[58]

制备方法	优点	缺点
表面涂层法	适用基材范围广，方法简便易操作，无需昂贵的实验室设备	制备时间长，易造成催化剂浪费，质量难控
溶胶凝胶法	沉积催化剂的纯度、均匀性、较低的温度、材料的形貌（形状、分布、尺寸）易控、可多层涂层，易在大的表面上获得涂层均匀的多组分氧化物膜，无需复杂设备	后期需煅烧适合耐高温基材，制备时间长，溶剂多有毒性，实验室研究，若用于放大生产尚需进一步研究
喷雾热解法	经济有效，沉积层均匀、精细，制备的材料比表面积高，活性强，无需昂贵仪器设备和试剂	易从基材上脱落、浸出和溶解
溶剂浇铸法	成本合理，反应可控，制备时间短	光催化剂活性降低