三维多金属氧酸盐/石墨烯气凝胶作为高效可回收的油水分离吸收剂

WANG Sen; WANG Xiao; SHI Xiao-yu; MENG Cai-xia; SUN Cheng-lin; WU Zhong-Shuai

doi:10.1016/S1872-5805(21)60013-6

三维多金属氧酸盐/石墨烯气凝胶作为高效可回收的油水分离吸收剂

doi: 10.1016/S1872-5805(21)60013-6

王森^1,,
王潇^{1, 3},
师晓宇^{1, 3},
孟彩霞¹,
孙承林^2, ,,
吴忠帅^{1, 2, ,}

1.
中国科学院大连化学物理研究所催化基础国家重点实验室，辽宁大连 116023
2.
中国科学院大连化学物理研究所洁净能源国家实验室，辽宁大连 116023
3.
中国科学院大学，北京， 100049

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中图分类号: TB33
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出版历程
- 收稿日期: 2021-01-13
- 修回日期: 2021-01-20
- 刊出日期: 2021-02-01

A three-dimensional polyoxometalate/graphene aerogel as a highly efficient and recyclable absorbent for oil/water separation

WANG Sen^1
,,
WANG Xiao^{1, 3},
SHI Xiao-yu^{1, 3},
MENG Cai-xia¹,
SUN Cheng-lin^{2
, ,},
WU Zhong-Shuai^{1, 2
, ,}

1.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China
2.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China
3.
University of Chinese Academy of Sciences, Beijing, 100049, China

Funds: This work was financially supported by the National Key R@D Program of China (Nos. 2016YFB0100100, 2016YFA0200200), the National Natural Science Foundation of China (Nos. 51872283, 22075279, 21805273, 22005297, 22005298), the Liao Ning Revitalization Talents Program (No. XLYC1807153), the Natural Science Foundation of Liaoning Province, Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science (No. 20180510038), Dalian Innovation Support Plan for High Level Talents (No. 2019RT09), Dalian National Laboratory For Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS (Nos. DNL180310, DNL180308, DNL201912, and DNL201915), DICP (Nos. DICP ZZBS201708, DICP ZZBS201802, DICP I2020032), and China Postdoctoral Science Foundation (Nos. 2019M661141, 2020M680995)

More Information

Author Bio:
WANG Sen, Ph. D. E-mail: senwang@dicp.ac.cn

Corresponding author: SUN Cheng-lin, Professor. E-mail: clsun@dicp.ac.cn; WU Zhong-Shuai, Professor. E-mail: wuzs@dicp.ac.cn

摘要

摘要: 三维石墨烯气凝胶具有可调控的孔结构、大的比表面积、优异的压缩性、弹性和润湿性，是一种高效的油水分离吸附剂。然而，三维石墨烯气凝胶的制备方法通常包括高温过程，导致高成本、能耗高和耗时长。本文以磷钼酸为交联剂和促进剂，水合肼为还原剂，在室温条件下同时将氧化石墨烯还原与自组装，制备出三维多孔的多金属氧酸盐复合石墨烯气凝胶（POM-GA），并证明其是一种高效、可回收的油水分离吸收剂。研究表明，POM-GA具有三维连通的多孔结构、大的比表面积、优异的压缩性、弹性和润湿性，对不同的有机溶剂具有良好的吸附能力（100~210 g g⁻¹），可快速去除水中的各种有机污染物，优于先前报道的大多数高温合成的石墨烯基宏观组装体。经10次吸附-挤压和吸附-挤压-燃烧循环后，POM-GA的吸油量保持率分别达到96%和90%。因此，三维POM-GA具有广泛的适用性和优异的耐用性，在高效油水分离方面具有良好的应用前景。
- 石墨烯 /
- 三维 /
- 石墨烯气凝胶 /
- 油水分离
Abstract: Three-dimensional (3D) graphene aerogels (GAs) with a tunable pore structure, a highly accessible surface area, and exceptional compressibility, elasticity and wettability have been explored as promising absorbents for efficient oil/water separation. However, the strategies for assembling 3D GAs usually involve a high-temperature process, resulting in high cost. We report the synthesis of a 3D porous polyoxometalate (POM)-hybridized GA (POM-GA) as a highly efficient and recyclable absorbent for oil/water separation. The material was fabricated at room temperature by the self-assembly and reduction of graphene oxide using POM as a functional cross-linker and hydrazine hydrate as a reductant. It had a 3D interconnected macroporous structure, a large specific surface area, and exceptional compressibility, elasticity and wettability, and had excellent absorption capacities of 100－210 g g⁻¹ for the rapid removal of various organic pollutants from water, outperforming most of the previously reported graphene-based macro-assemblies synthesized at high temperatures. Moreover, the absorbed oils can be readily removed by squeezing or first squeezing and then burning the remaining organic from the 3D POM-GA. The oil-absorption capacity retention rates of the 3D POM-GA are 96 and 90% after 10 absorbing-squeezing and absorbing-squeezing-burning cycles, respectively. The material therefore has great potential for efficient oil/water separation with wide applicability and excellent durability.
- Graphene /
- Three-dimensional /
- Graphene aerogels /
- Oil/water separation

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Figure 1. Schematic illustration of the room-temperature assembly of 3D POM-GA.

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Figure 2. Morphological and structural characterization of 3D POM-GA: (a,b) Photographs of POM-GAs (a) held by a tweezer and (b) supported on a flower, (c) SEM image, (d) nitrogen adsorption and desorption isotherms and the pore size distribution (inset), (e) TGA curve of POM-GA, (f) XRD patterns and (g) Raman spectra of POM-GA and GO.

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Figure 3. The wettability and mechanical compressibility of 3D POM-GA: (a) photograph of 3D POM-GA under the water, (b) photograph of water and methylbenzene droplets on the surface of 3D POM-GA, (c,d) contact angles of 3D POM-GA with (c) water, and (d) methylbenzene and (e) reversible mechanical compressibility and elasticity of 3D POM-GA.

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Figure 4. Absorption performance of 3D POM-GA: (a,b) removal of (a) methylbenzene on the water surface and (b) dichloromethane from the water bottom by 3D POM-GA, (c) adsorption capacities for various organic liquids and (d) a comparison of 3D POM-GA with various 3D porous absorbents for absorption of organic solvents.

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Figure 5. Recyclability of 3D POM-GA: (a) recycling organic solvents from POM-GA by squeezing, and (b) recovery of 3D POM-GA via combustion, and (c,d) absorption capacity of POM-GA versus (c) absorbing-squeezing cycles, and (d) absorbing-squeezing-burning cycles.

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资源附件(6)

Video S3 removal dichloromethane from water bottom.mp4
支撑材料.pdf
Video S4 Recycle oil from the POM-GFs by squeezing_Trim.mp4
Video S5 recovery POM-GFs via combustion_Trim_Trim.mp4
Video S2 removal methylbenzene on the water surface_Trim.mp4
Video S1 reversible compressibility_Trim.mp4