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碳纳米管复合纤维素水凝胶的界面光热净水性能研究

王雪 孙洋 赵冠宇 王旭珍 邱介山

王雪, 孙洋, 赵冠宇, 王旭珍, 邱介山. 碳纳米管复合纤维素水凝胶的界面光热净水性能研究. 新型炭材料. doi: 10.1016/S1872-5805(22)60621-8
引用本文: 王雪, 孙洋, 赵冠宇, 王旭珍, 邱介山. 碳纳米管复合纤维素水凝胶的界面光热净水性能研究. 新型炭材料. doi: 10.1016/S1872-5805(22)60621-8
WANG Xue, SUN Yang, ZHAO Guan-yu, WANG Xu-zhen, QIU Jie-shan. Study on carbon nanotube-cellulose hydrogel composites to interfacial solar-thermal water purification. New Carbon Mater.. doi: 10.1016/S1872-5805(22)60621-8
Citation: WANG Xue, SUN Yang, ZHAO Guan-yu, WANG Xu-zhen, QIU Jie-shan. Study on carbon nanotube-cellulose hydrogel composites to interfacial solar-thermal water purification. New Carbon Mater.. doi: 10.1016/S1872-5805(22)60621-8

碳纳米管复合纤维素水凝胶的界面光热净水性能研究

doi: 10.1016/S1872-5805(22)60621-8
基金项目: 国家自然科学基金项目(22179017)资助
详细信息
    作者简介:

    王雪:王 雪,硕士研究生. E-mail:17865572197@163.com

    通讯作者:

    王旭珍,博士,教授. E-mail:xzwang@dlut.edu.cn

  • 中图分类号: TQ352.9

Study on carbon nanotube-cellulose hydrogel composites to interfacial solar-thermal water purification

Funds: National Natural Science Foundation of China (No.22179017)
More Information
  • 摘要: 基于低温溶剂法从大宗农林废弃物玉米芯中提取的纤维素,耦合具有优异吸光性能的碳纳米管(CNTs),构筑复合纤维素水凝胶(CNTs-CH),利用纤维素凝胶的高保水性、可降解性,以及碳纳米管的高效光热转换能力、优良的力学性能和生物相容性,将其用于太阳能驱动界面水蒸发净化领域。考察了吸光材料CNTs的不同添加量对CNTs-CH复合水凝胶的太阳能吸收率、机械性能及界面光热水蒸发效率的影响。最优条件下,CNTs添加量仅需0.2 wt.%,此CNTs-CH复合纤维素水凝胶的平均蒸发速率可达到~1.52 kg m−2 h−1,太阳能-蒸汽转换效率约92%;在海水中连续蒸发8 h,蒸发速率可保持在1.37 kg m−2 h−1左右,且无积盐现象,净化水质远高于WHO和EPA对饮用水的标准,说明CNTs-CH抗盐性能较强。此外,CNTs-CH水凝胶在强酸/碱性水溶液体系、染料废水和重金属离子污染水体中的蒸发速率可维持在1.30-1.40 kg m−2 h−1,太阳能-蒸汽效率可达到80-86%,对污染物及盐分截留率高达99.9%,蒸发效果稳定,说明CNTs-CH光热蒸发器在海水淡化和工业废水净化回用领域有广阔的应用前景。
  • 1  界面太阳能水蒸发速率测试装置图

    1.  Schematic diagram of device for testing water evaporation rate by interfacial solar driven.

    图  1  纤维素水凝胶的制备、外观及FTIR表征。(a) CNTs-CH复合纤维素水凝胶的制备流程图. (b) CNTs-CH脱模后的宏观照片. (c) 商品纤维素、自制纤维素与纤维素水凝胶(CH)的红外谱图. (d) 纤维素水凝胶(CH)、复合纤维素水凝胶(CNTs-CH)的承重图(插图为:承重后样品复原图)

    Figure  1.  Preparation, appearance and FTIR characterization of cellulose hydrogels. (a) Flow chart of preparation of CNTs-CH composite cellulose hydrogel. (b) Digital photos of CNTs-CH after demolding. (c) Infrared spectra of commercial cellulose, homemade cellulose and cellulose hydrogel (CH). (d) Load-bearing diagrams of cellulose hydrogel (CH) and composite cellulose hydrogel (CNTs-CH) (the inset is the recovery diagram of the sample after load-bearing).

    图  2  纤维素水凝胶的微观结构电镜图像及其DSC曲线。(a) CH、(b) 0.02%CNTs-CH、(c) 0.2%CNTs-CH和(d) 1.0%CNTs-CH水凝胶溶胀、冻干后在200 μm标尺下的SEM图像. (e, f) 代表样品0.2%CNTs-CH在30 μm和20 μm标尺下的局部放大SEM图像(e中插图显示其网络结构交联处的局部放大图). (g)、(h)分别为0.2%CNTs-CH的TEM和HRTEM图像. (i) 0.2%CNTs-CH水凝胶溶胀平衡后的DSC曲线

    Figure  2.  Electron microscopic images and DSC curve of cellulose hydrogels. (a-d) SEM images of (a)CH, (b)0.02%CNTs-CH, (c)0.2%CNTs-CH, (d)1.0%CNTs-CH hydrogels swollen and freeze-dried at 200 μm size, respectively. (e,f) Local enlarged SEM images of typical 0.2%CNTs-CH at 30 μm and 20 μm size (the inset shows the local enlarged view of the crosslinking of its network structure). (g) TEM and (h) HRTEM image of 0.2%CNTs-CH. (i) DSC curve of 0.2%CNTs-CH hydrogel after swelling equilibrium.

    图  3  CNTs-CH水凝胶的太阳能吸收及光热转换性能。(a, b) CH、0.02%CNTs-CH、0.2%CNTs-CH、1.0%CNTs-CH的紫外/可见/近红外反射光谱(a)和吸收光谱(b),b图中背底为太阳能全光谱. (c)在一个标准太阳照射下,不同水凝胶蒸发器表面温度随时间的变化. (d)红外热成像仪记录的0.2%CNTs-CH水凝胶表面温度随时间的变化

    Figure  3.  Solar energy absorption and photo-thermal conversion properties of CNTs-CH hydrogels. UV/Vis/NIR reflectance spectra (a) and absorption spectra (b) of CH, 0.02%CNTs-CH, 0.2%CNTs-CH, 1.0%CNTs-CH, the background in b is solar energy full spectrum. (c) Change of surface temperature over different hydrogel evaporators with time under a standard solar irradiation. (d) Change of surface temperature over 0.2%CNTs-CH hydrogel recorded by infrared thermal imager with time.

    图  4  CNTs-CH水凝胶在一个标准太阳光下的水蒸发性能及其与文献对比。(a, b) CH、0.02%CNTs-CH、0.2%CNTs-CH、1.0%CNTs-CH各自在蒸发时水蒸汽的质量变化(a)及其蒸发速率折线图(b). (c) 0.2%CNTs-CH与其他文章报道的蒸发器蒸发性能对比图. (d) 0.2%CNTs-CH在10天里的蒸发速率图(插图分别为第1天和第10天太阳能蒸发时水蒸气的质量变化)

    Figure  4.  Water evaporation performance of CNTs-CH hydrogel under a standard sunlight and a comparison with the previous literature. (a) The mass change of water vapor during evaporation and (b) its evaporation rate line graph of CH, 0.02%CNTs-CH, 0.2%CNTs-CH, and 1.0%CNTs-CH, respectively. (c) Comparison of evaporation performance of 0.2%CNTs-CH with others previously reported. (d) Evaporation rates of 0.2%CNTs-CH in 10 days (insets show the mass change of water vapor during solar evaporation on day 1 and day 10, respectively).

    图  5  0.2%CNTs-CH对盐水的界面光热蒸发性能(光照强度:1kW m−2)。 (a)含NaCl为3.5、5.0、10、20 wt.%的模拟盐水与纯水对照的水蒸发速率及太阳能-蒸汽效率. (b)采集的黄海海水蒸发脱盐前后四种主要离子Na+、Mg2+、K+、Ca2+的浓度,并与WHO和EPA所设标准进行比较. (c)在黄海海水中连续8小时的蒸发速率图(插图为固体盐颗粒溶解实验)

    Figure  5.  Interfacial photo-thermal evaporation performance of 0.2% CNTs-CH to brine (light intensity: 1kW m−2). (a) Water evaporation rate and solar steam efficiency of simulated brine with NaCl mass percentage of 3.5, 5.0, 10 and 20 wt.% compared with pure water. (b) The concentrations of the four primary ions (Na+, Mg2+, K+, and Ca2+) before and after evaporative desalination of the seawater collected from Yellow Sea, and compared with the standards set by WHO and EPA. (c) Evaporation rate plot in the Yellow Sea seawater for continuous 8 hours (inset is the dissolution experiment of solid salt particle).

    图  6  0.2%CNTs-CH对模拟工业废水的蒸发性能(光照强度:1kW m−2)。(a)酸性体系(0.1、0.3、1.0、3.0 M HNO3溶液)和 (b)碱性体系(0.1、0.3、1.0、3.0 M NaOH溶液)中的水蒸发速率及其太阳能-蒸汽效率. (c)染料废水10 % RhB溶液蒸发前后的宏观照片及其紫外-可见吸收光谱. (d)重金属溶液(含Cr6+、Cd2+、Cu2+、Zn2+)蒸发前后的重金属离子浓度变化

    Figure  6.  Evaporation performance of 0.2% CNTs-CH on simulated industrial wastewater (light intensity: 1kW m−2). (a, b) Water evaporation rates and their solar-steam efficiency in (a) acidic systems (0.1, 0.3, 1.0, 3.0 M HNO3 solutions) and (b) alkaline systems (0.1, 0.3, 1.0, 3.0 M NaOH solutions). (c) Digital photo and UV-Vis absorption spectra of 10% RhB dye wastewater before and after evaporation. (d) Change of heavy metal ion concentration before and after evaporation of heavy metal solution (including Cr6+, Cd2+, Cu2+, Zn2+).

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