三维碳纳米管/硅藻土基多孔陶瓷复合材料的制备及其光热水蒸发性能

李梦涵; 魏娜; 徐瑞琪; 杨泽钰; 崔洪芝

三维碳纳米管/硅藻土基多孔陶瓷复合材料的制备及其光热水蒸发性能

李梦涵¹,
魏娜^1, ,,
徐瑞琪²,
杨泽钰¹,
崔洪芝^{1, 2}

1.
山东科技大学材料科学与工程学院, 青岛 266590
2.
中国海洋大学材料科学与工程学院, 青岛 266100

基金项目: 国家自然科学基金项目(52002228, 51772176, 51971121)

详细信息

通讯作者:
魏娜，博士，讲师，硕士生导师，研究方向为太阳能海水淡化　E-mail: weina@sdust.edu.cn

中图分类号: TB34
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- 被引次数: 0
出版历程
- 收稿日期: 2022-09-28
- 修回日期: 2022-11-01
- 录用日期: 2022-11-12
- 网络出版日期: 2022-11-24
- 刊出日期: 2023-08-15

Preparation of carbon nanotubes/diatomite based porous ceramic composites and its photothermal evaporation performance

LI Menghan¹,
WEI Na^{1
, ,},
XU Ruiqi²,
YANG Zeyu¹,
CUI Hongzhi^{1, 2}

1.
College of Materials Science and Engineering, Shandong University of Science and Technology, qingdao 266590, China
2.
College of Materials Science and Engineering, Ocean University of China, qingdao 266590, China

Funds: National Natural Science Foundation of China (52002228, 51772176, 51971121)

摘要

摘要: 目的界面型光蒸汽转化技术为从海水和废水中提取淡水提供了一种高效、可持续的策略，以有效应对水资源短缺危机。本文通过高温烧结法制备硅藻土基多孔陶瓷，并在多孔陶瓷表面涂覆一层海藻酸钠(SA)/多壁碳纳米管(CNTs)薄膜以提高光吸收能力，探究其海水淡化和污水处理性能。方法三维光热蒸发器由于热损失和光反射的减少以及蒸发面积和吸光面积的扩大，表现出了优异的蒸发性能。本文采用注浆成型工艺，利用高温烧结法制备三维硅藻土基多孔陶瓷，通过添加不同含量的造孔剂(CaCO)来调控大孔结构，以提高其蒸汽通量。高的光吸收率是提高能量转换效率的关键，为了进一步提高其吸光及光热转换能力，在硅藻土基多孔陶瓷表面涂覆一层海藻酸钠/多壁碳纳米管薄膜，改变海藻酸钠与多壁碳纳米管的比例，探究三维碳纳米管/硅藻土基多孔陶瓷复合材料的光热海水淡化和污水处理效果。结果硅藻土基多孔陶瓷在没有添加CaCO时，主要成分为无定型的SiO相，而随着造孔剂CaCO含量的掺入，逐渐生成了CaSiO，随着CaCO含量的进一步增加，CaSiO与周围过量的CaO进一步发生反应生成CaSiO。硅藻土颗粒存在被液相包覆的迹象，且样品表面均存在微米级的孔形貌，证明了在烧结过程中，硅藻土发生了晶相转变，存在CaCO的分解、CO的逸出及CaSiO的生成等多种化学反应。随着CaCO含量的增加，样品的孔隙率逐渐升高。SC-5样品孔隙率可达73.2%，且具有超亲水性。所制备的SC-5/CNTs-45复合材料可以实现89.1%的光吸收率。蒸发速率以及光热转换效率分别可达2.07 kg·m·h和95.6%。淡化前后海水中Na、K、Ca和Mg的浓度由9075.66、441.03、345.55和1188.21 mg·L分别下降到4.39、1.27、1.17和0.50 mg·L，离子截留率分别可达99.95%、99.71%、99.66%、99.96%，净化后水体主要离子浓度均达到了世界卫生组织对饮用水的离子浓度标准。用SC-5/CNTs-45净化罗丹明B有机溶液，净化后的罗丹明B溶液失去了特征吸收峰，证明SC-5/CNTs-45样品对罗丹明B有机染料溶液具有良好的净化效果。结论以硅藻土为主要原料，CaCO作为造孔剂，采用高温烧结法，成功制备出具有不同孔结构的硅藻土基多孔陶瓷。所制备的硅藻土基多孔陶瓷主要物相为SiO及CaSiO，具有超亲水性，随着造孔剂含量的增加，孔隙率逐渐增大。将多壁碳纳米管和海藻酸钠凝胶的混合物均匀涂覆在多孔陶瓷的表面形成一层薄膜，结合多孔结构的多重散射特性及碳纳米管高效的光热性能，样品光吸收率最高可达89.1%，在一个光强下蒸发速率可达2.07 kg·m·h，光热转换效率为95.9%，对海水中几种主要离子具有超过99%的离子截留率，且对有机染料具有优良的净化作用，表现出了显著的海水淡化效果和污水处理能力，且具有良好的循环稳定性。
- 硅藻土 /
- 多孔陶瓷 /
- 碳纳米管 /
- 海水淡化 /
- 污水处理 /
- 光热水蒸发
Abstract: Interface solar steam generation technology provides an efficient and sustainable strategy for extracting fresh water from seawater and wastewater, which can effectively solve the current water crisis. In present work, diatomite based porous ceramics were prepared by grouting molding process by using natural diatomite as the main raw material and CaCO₃ as the pore forming agent. Then, carbon nanotube / diatomite based porous ceramic composites were prepared successfully by surface modification of the diatomite based porous ceramics coating with the multi walled carbon nanotubes and sodium alginate mixed gel. Characterizations confirm that the diatomite based porous ceramics have a three-dimensional connected porous structure, and the pore size is mainly 10-30 µm. When the mass fraction of CaCO₃ is 50%, the porosity can reach 73.2%. Owing to the multiple scattering effect and hydrophilicity of the porous structure and the excellent photothermal conversion ability of carbon nanotubes, the evaporator show excellent properties. Under one solar intensity, the evaporation rate and energy conversion efficiency of the evaporator are up to 2.07 kg·m⁻²·h⁻¹ and 95.6%, respectively and maintains good cycle stability. Additionally, the ion rejection rate of seawater and wastewater for the evaporator can achieve nearly 100%. It shows broad application potential in the field of seawater desalination.
- diatomite /
- porous ceramics /
- carbon nanotubes /
- seawater desalination /
- wastewater purification /
- photothermal evaporation

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图 1 三维碳纳米管/硅藻土基多孔陶瓷复合材料的制备流程图

Figure 1. Schematic illustration of the fabrication process of 3 D diatomite based porous ceramic/carbon nanotubes composites

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图 2 硅藻土基多孔陶瓷(SC)的XRD图谱

Figure 2. XRD pattern of diatomite based porous ceramics (SC)

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图 3 硅藻土粉末及SC-5样品的形貌图

Figure 3. (a) Optical photographs of diatomite powder, (b, c) SEM images of diatomite raw material, (d)-(f) SEM image of SC-5

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图 4 SC-5的TG和DTG曲线

Figure 4. TG and DTG curves of SC-5

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图 5 所制备样品(a)孔隙率; (b)孔径分布; (c)质量损失曲线; (d)蒸发速率和蒸发效率图

Figure 5. Samples prepared (a) Porosity; (b) Pore size distribution; (c) Mass change curves; (d) Evaporation rates and efficiency

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图 6 多壁碳纳米管及SC-5/CNTs-45形貌图(a-c); SC-5/CNTs和SC-5的紫外-可见-近红外光谱(d-f)

Figure 6. SEM images of samples prepared (a) Multi-walled carbon nanotubes; (b) SC-5/CNTs-45 surface; (c) SC-5/CNTs-45 section; UV–Vis-NIR spectrum of the samples (d) Reflection (R); (e) Transmission (T); (f) Absorption (A)

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图 7 (a)纯海水、SC-5与SC-5/CNTs-45的表面温度曲线; (b)SC-5/CNTs-45表面与内部的温度曲线; (c)SC-5与SC-5/CNTs-45的温度热像图

Figure 7. (a) Surface temperature curves of pure seawater, SC-5 and SC-5/CNTs-45, (b) Surface and internal temperature curves of SC-5/CNTs-45, (c) Surface temperature images of SC-5 and SC-5/CNTs-45

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图 8 (a)不同比例复合材料的质量损失曲线; SC-5/CNTs-45水蒸发性能(b)不同光强的质量损失曲线; (c)不同海水浓度速率图; (d)循环测试图; (e)淡化前后海水主要离子浓度; (f)净化罗丹明b前后紫外-可见吸收光谱

Figure 8. (a) Mass change curve of composites with different proportions; The Evaporation performance of SC-5/CNTs-45 (b) Mass change curve under different solar intensities; (c) The evaporation rates under different salinity concentrations; (d) The cyclic curve; (e) Seawater concentration of main ions before and after purification; (f) UV-Vis absorption spectra before and after purification of RhB

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表 1 本工作与相关研究在一个光强下性能对比

Table 1. Comparison the performance of this work with related studies under one solar intensity

Sample	Evaporation rate/(kg·m⁻²·h⁻¹)	Evaporation efficiency/%
Our work	2.07	95.9
Cotton-CNT fabric^[7]	1.59	89.6
Graphene oxide/CNTs^[8]	1.58	87.5
All-carbon nanotube hybrid films^[34]	1.37	87.4
Cellulose/Carbon Nanotubes Membrane^[35]	1.60	89
CNT@Dialdehyde microcrystalline cellulose membrane^[36]	1.58	90.86
Porous Ni mesh/CNTs^[37]	2.13	94.3
Hydroxyapatite nanowires/CNT photothermal paper^[38]	1.31	83.2

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