双功能气凝胶吸附-降解协同处理染料废水

doi:10.6023/A23010009

摘要/Abstract

针对吸附法处理染料废水易产生二次污染和基于过一硫酸氢盐(PMS)的高级氧化技术降解有机污染物易受水体复杂成分影响的问题, 设计构筑具有吸附和活化PMS功能的铁掺杂纤维素纳米纤维/还原氧化石墨烯气凝胶(CNFs/RGO/Fe)用于吸附-降解协同处理染料废水. CNFs/RGO/Fe对阳离子染料具有良好的选择性吸附功能, 其对亚甲基蓝(MB)、罗丹明B (RhB)和结晶紫(CV)的最大吸附容量分别高达655.1 mg/g、696.5 mg/g和962.1 mg/g, 吸附过程符合准二级动力学模型和Langmuir等温模型. 将吸附染料的CNFs/RGO/Fe置于PMS溶液中, 可以促进PMS活化产生大量•OH, 实现对吸附质的降解和气凝胶的再生. 经5次吸附-降解循环后, CNFs/RGO/Fe对染料去除率仍保持在75%以上, 表现出良好的重复使用性. 本研究有望为去除复杂水体中有机污染物提供新思路.

关键词: 吸附, 降解, 气凝胶, 高级氧化技术, 染料废水

Dye wastewater with high toxicity and poor biodegradability poses a considerable threat to human health and the ecosystem. Although the adsorption effectively removes organic pollutants from wastewater, the pollutants are merely transferred from liquid phase to solid adsorbents. Destroying the adsorbed pollutants and regenerating adsorbents require additional treatments, which may cause secondary harm to the environment. In addition to the removal of organic pollutants by adsorption, the pollutants can be oxidatively degraded by oxidative radicals that are generated in peroxymonosulfate (PMS)-based advanced oxidation technology. However, the degradation efficiency of organic pollutants treated by advanced oxidation technology may be affected by complex components of dye wastewater. Herein, Fe-doped cellulose nanofiber/reduced graphene oxide aerogel (CNFs/RGO/Fe) was prepared and served as both adsorbent and catalyst in advanced oxidation process for dyes wastewater treatment. The morphology and chemical composition of the composite aerogel were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). It was proved that CNFs/RGO/Fe possessed layered porous structures, which are beneficial for the transport, diffusion, and adsorption of pollutants. The uniform loading of Fe⁰ and Fe₃O₄ particles on the aerogel skeleton contributed to the efficient activation of PMS. The results of the adsorption experiment showed that the CNFs/RGO/Fe exhibited excellent selective adsorption for cationic dyes. The maximum adsorption capacity of methylene blue (MB), rhodamine B (RhB), and crystal violet (CV) on CNFs/RGO/Fe were 655.1 mg/g, 696.5 mg/g, and 962.1 mg/g, respectively. The pseudo-second-order kinetic model and Langmuir isothermal model fitted well with the adsorption process of CNFs/RGO/Fe for cationic dyes. After adsorption, the CNFs/RGO/Fe was immersed in PMS solution separately to study the degradation performance for the adsorbate. The results showed that CNFs/RGO/Fe could promote the activation of PMS to generate a large amount of •OH, leading to the degradation of adsorbate and the regeneration of adsorbent. In addition, the synergistic adsorption-degradation process established by CNFs/RGO/Fe achieved over 75% removal of dyes even after 5 cycles, indicating CNFs/RGO/Fe had good repeatability. The study on the synergistic treatment of dye wastewater by adsorption-degradation is expected to provide a new perspective for the removal of organic pollutants in complex water.

Key words: adsorption, degradation, aerogel, advanced oxidation technology, dye wastewater

引用此文

王文涛, 赖欣婷, 闫士全, 朱雷, 姚玉元, 丁黎明. 双功能气凝胶吸附-降解协同处理染料废水[J]. 化学学报, 2023, 81(3): 222-230.

Wentao Wang, Xinting Lai, Shiquan Yan, Lei Zhu, Yuyuan Yao, Liming Ding. Synergistic Treatment of Dye Wastewater by the Adsorption-Degradation of a Bifunctional Aerogel[J]. Acta Chimica Sinica, 2023, 81(3): 222-230.

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图/表 7

图1. CNFs/RGO/Fe气凝胶的(a) 数码照片; (b, c) SEM图和(d~f) 元素映射图

Figure 1. (a) Digital photo, (b, c) SEM images and (d~f) element mappings of CNFs/RGO/Fe aerogel

图2. (a) CNFs、RGO和CNFs/RGO/Fe气凝胶的压缩应力-应变曲线; CNFs/RGO/Fe气凝胶的(b) XRD谱图; (c) XPS全谱图和(d) Fe 2p高分辨XPS谱图

Figure 2. (a) Compression stress-strain curves of the CNFs, RGO and CNFs/RGO/Fe aerogels, (b) XRD patterns, (c) XPS full spectrum and (d) the high-resolution Fe 2p of CNFs/RGO/Fe aerogel

图3. (a) 不同吸附剂对MB的吸附(Cadsorbent=1 g/L, CMB=200 mg/L); (b) 吸附剂浓度和(c) 温度对CNFs/RGO/Fe吸附MB的影响; (d) 确定热力学参数的lg(Qe/Ce)与1/T的关系; (e) 初始pH值对CNFs/RGO/Fe吸附MB的影响; (f) CNFs/RGO/Fe对不同染料的吸附(Cdye=200 mg/L)

Figure 3. (a) The adsorption of MB by different adsorbents (Cadsorbent=1 g/L, CMB=200 mg/L); (b) effects of adsorbent dosage and (c) temperature on adsorption of MB by CNFs/RGO/Fe; (d) the relationship between lg(Qe/Ce) and 1/T of determining thermodynamic parameters; (e) effect of initial pH on adsorption of MB by CNFs/RGO/Fe; (f) the adsorption of different dyes by CNFs/RGO/Fe (Cdye=200 mg/L)

图4. (a) MB, (b) RhB和(c) CV吸附的准一级和准二级动力学模型拟合; (d) MB, (e) RhB和(f) CV吸附的Langmuir和Freundlich等温模型拟合

Figure 4. Fits of pseudo-first-order and pseudo-second-order kinetic models for the adsorption of (a) MB, (b) RhB and (c) CV; fits of Langmuir and Freundlich isotherm models for the adsorption of (d) MB, (e) RhB and (f) CV

图5. PMS浓度对(a) 解吸至溶液中MB降解和(b) CNFs/RGO/Fe再生效率的影响(CCNFs/RGO/Fe=1 g/L, CMB=100 mg/L); (c) CNFs/RGO/Fe对MB、RhB和CV的循环吸附(CCNFs/RGO/Fe=1 g/L, CMB=100 mg/L, CPMS=1.5 g/L); (d) 循环降解过程PMS溶液中MB、RhB和CV的残留浓度

Figure 5. Effect of PMS dosage on (a) degradation of MB in desorption to solution and (b) regeneration efficiency of CNFs/RGO/Fe (CCNFs/RGO/Fe=1 g/L, CMB=100 mg/L); (c) the cyclic adsorption of CNFs/RGO/Fe for MB, RhB, and CV (CCNFs/RGO/Fe=1 g/L, CMB=100 mg/L, CPMS=1.5 g/L); (d) residual content of MB, RhB and CV in PMS solution during cyclic degradation

图6. (a) MB、CNFs/RGO/Fe吸附MB前后及PMS处理后的FTIR谱图; (b) RhB、CNFs/RGO/Fe吸附RhB前后及PMS处理后的FTIR谱图; (c) CV、CNFs/RGO/Fe吸附CV前后及PMS处理后的FTIR谱图; (d) CNFs/RGO/Fe活化PMS产生?OH的DMPO自旋捕获EPR谱图

Figure 6. (a) FTIR spectra of MB, CNFs/RGO/Fe before and after adsorption of MB and after PMS treatment; (b) FTIR spectra of RhB, CNFs/RGO/Fe before and after adsorption of RhB and after PMS treatment; (c) FTIR spectra of CV, CNFs/RGO/Fe before and after adsorption of CV and after PMS treatment; (d) EPR spectra of DMPO-?OH in PMS activation by CNFs/RGO/Fe

图7. CNFs/RGO/Fe对模拟染料废水中MB的循环吸附(CCNFs/RGO/Fe=1 g/L, CMB=100 mg/L, CPMS=1.5 g/L)

Figure 7. The cyclic adsorption of CNFs/RGO/Fe for MB in simulated dye wastewater (CCNFs/RGO/Fe=1 g/L, CMB=100 mg/L, CPMS=1.5 g/L)

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