可光助再生二氧化钛/层状双氢氧化物去除水体中有机染料

doi:10.11949/0438-1157.20191579

摘要/Abstract

摘要：

利用吸附-光催化技术去除水体中有机染料，是高效节能的方法之一。然而，碳基吸附剂在光催化降解污染物过程中，由于活性氧的攻击会发生自身的逐渐氧化。本研究中，采用尿素水解水热法制备二氧化钛/层状双氢氧化物（TiO₂/LDH）非碳基复合材料，不仅对水体中有机染料具有较高的吸附容量，也在光辐射后具有可重复的再生能力。对甲基橙的吸附量为527.5 mg/g，在4轮循环再生后仍具有88.6%的再生率；对亚甲基蓝的吸附量为208.3 mg/g，在4轮循环再生后仍具有94.7%的再生率。在吸附-光再生过程中，LDH基底自身具有强抗氧化能力和高吸附能力，同时提高了负载剂TiO₂的光吸收效率，为水中有机污染物去除和吸附-光催化复合材料设计优化提供了可行的策略。

关键词: 二氧化钛, 层状双氢氧化物, 复合材料, 吸附（作用）, 光催化, 再生

Abstract:

Removal of organic dyes in water by adsorption-photocatalysis technology is one of the efficient and energy-saving methods. However, in the process of photocatalytic degradation of pollutants by carbon-based sorbents, gradual oxidation of carbon-based adsorbents occurs due to active oxygen attack. In this study, titanium dioxide/layered double hydroxide (TiO₂/LDH) non-carbon-based composites are synthesized using the urea hydrolysis hydrothermal method. They not only have high adsorption capacity for organic dyes in water, but also are capable to regenerate themselves by light irradiation. Their adsorption capacity for methyl orange is 527.5 mg/g, which regenerate percentage is up to 88.6% after 4 cycles. In addition, their adsorption capacity for methylene blue is 208.3 mg/g, which regenerate percentage is up to 94.7% after 4 cycles. During the adsorption-photocatalytic regeneration process, the LDH substrate itself has strong oxidation resistance and high adsorption capacity. Moreover, LDH improves light absorption efficiency of the loading agent TiO₂. It provides a feasible strategy for the removal of organic pollutants in water and optimization of adsorption-photocatalytic composite materials.

Key words: titanium dioxide, layered double hydroxide, composites, adsorption, photocatalysis, regeneration

中图分类号:

X 703.1

胡京宇, 姚戎, 潘玉航, 朱超, 宋爽, 沈意. 可光助再生二氧化钛/层状双氢氧化物去除水体中有机染料[J]. 化工学报, 2020, 71(7): 3296-3303.

Jingyu HU, Rong YAO, Yuhang PAN, Chao ZHU, Shuang SONG, Yi SHEN. Photo-assisted regeneration of titanium dioxide/layered double hydroxide for removal of organic dyes in water[J]. CIESC Journal, 2020, 71(7): 3296-3303.

图/表 11

表1 TiO2/LDH中TiO2负载量实验数据

Table 1 Test on TiO2 loaded in TiO2/LDH

元素

项目

TiO₂/LDH

样品1

TiO₂/LDH

样品2

TiO₂/LDH

样品3

图1 LDH和TiO2/LDH的扫描透射电镜及TiO2/LDH元素映射图

Fig.1 Scanning electron microscopy (SEM) and mapping image of LDH and TiO2/LDH

图2 LDH和TiO2/LDH的X射线衍射谱图

Fig.2 X-Ray diffraction (XRD) patterns of LDH and TiO2/LDH

表2 LDH和TiO2/LDH材料的比表面积及孔隙性质

Table 2 Specific surface area and pore textural properties of LDH and TiO2/LDH

吸附剂	比表面积/(m²/g)	平均孔径/nm	孔体积/(cm³/g)
LDH	59.4	5.66	0.26
TiO₂/LDH	67.1	7.34	0.35

图3 LDH和TiO2/LDH对有机染料的Langmuir等温吸附拟合图

Fig.3 Adsorption isotherms of organic dyes onto LDH and TiO2/LDH fitted by Langmuir model

表3 LDH和TiO2/LDH对有机染料的Freundlich和Langmuir等温吸附参数

Table 3 Regression parameters of adsorption isotherms of organic dyes onto LDH and TiO2/LDH fitted by Freundlich and Langmuir models

污染物	吸附剂	Freundlich 模型			Langmuir 模型
污染物	吸附剂	K_f	N	R²	q_m/(mg/g)	K_L/(L/g)	R²
甲基橙	LDH	141.11867	0.29511	0.90351	462.34149	0.25171	0.96492
	TiO₂/LDH	163.77771	0.29323	0.90024	527.49174	0.2654	0.96388
亚甲基蓝	LDH	75.76239	0.2844	0.89484	166.92703	0.95467	0.95936
	TiO₂/LDH	94.99944	0.29356	0.92097	208.32481	1.07183	0.9804

图4 LDH和TiO2/LDH对有机染料的吸附动力学

Fig.4 Adsorption kinetics of organic dyes onto LDH and TiO2/LDH

表4 LDH和TiO2/LDH对有机染料的吸附动力学参数

Table 4 Adsorption kinetic parameters of organic dyes onto LDH and TiO2/LDH

污染物	吸附剂	拟一级动力学			拟二级动力学
污染物	吸附剂	q_e/(mg/g)	k₁/(1/s)	R²	q_e/(mg/g)	k₂/(g/(mg·s))	R²
甲基橙	LDH	178.46944	0.01407	0.97968	198.49873	0.01815	0.92925
	TiO₂/LDH	206.09581	0.02074	0.98208	225.49671	0.02831	0.92758
亚甲基蓝	LDH	69.2104	0.01416	0.98638	76.08457	0.01969	0.95594
	TiO₂/LDH	81.4685	0.01977	0.99344	89.16015	0.02729	0.95272

图5 LDH和TiO2/LDH对有机染料的再生动力学

Fig.5 Regenerated kinetics of LDH and TiO2/LDH for organic dyes in timeline of photocatalytic regeneration

表5 LDH和TiO2/LDH对有机染料的再生动力学参数

Table 5 Regenerated kinetic parameters of LDH and TiO2/LDH for organic dyes in timeline of photocatalytic regeneration

污染物	吸附剂	Recovery/%
污染物	吸附剂	0.5 h	1 h	1.5 h	2 h	3 h	4 h	5 h	7 h	10 h
甲基橙	LDH	0	0	0	0	0.4	1.0	1.3	1.9	2.2
甲基橙	TiO₂/LDH	22.52	42.36	59.95	73.60	84.89	93.05	93.95	93.95	93.94
亚甲基	LDH	0	0	0	0	0.3	0.8	1.0	1.6	3.0
亚甲基	TiO₂/LDH	29.48	49.55	68.41	81.26	90.29	95.69	96.87	96.85	96.85

图6 TiO2/LDH吸附有机染料的多轮循环吸附再生

Fig.6 Percentage of regenerated adsorption capacity of LDH and TiO2/LDH for organic dyes in cycles of photocatalytic regeneration

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