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化学进展 2021, Vol. 33 Issue (10): 1874-1886 DOI: 10.7536/PC200902 前一篇   后一篇

• 综述 •

多孔液体在气体捕集与分离领域的应用

王德超, 辛洋洋, 李晓倩, 姚东东*(), 郑亚萍*()   

  1. 西北工业大学化学与化工学院 西安 710129
  • 收稿日期:2020-09-03 修回日期:2020-11-05 出版日期:2021-10-20 发布日期:2020-12-21
  • 通讯作者: 姚东东, 郑亚萍
  • 基金资助:
    西北工业大学博士论文创新基金(CX201963); 国家自然科学基金(21905228); 航空基金(2018ZF53065)
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Porous liquids and Their Applications in Gas Capture and Separation

Dechao Wang, Yangyang Xin, Xiaoqian Li, Dongdong Yao(), Yaping Zheng()   

  1. School of Chemistry and Chemical Engineering, Northwestern Polytechnical University,Xi'an 710129, China
  • Received:2020-09-03 Revised:2020-11-05 Online:2021-10-20 Published:2020-12-21
  • Contact: Dongdong Yao, Yaping Zheng
  • Supported by:
    Innovation Foundation for Doctor Dissertation of NWPU(CX201963); National Natural Science Foundation of China(21905228); Aeronautical Science Foundation of China(2018ZF53065)

多孔液体是指具有永久性孔隙的液体材料,其将多孔固体的有序规整孔道和液体的流动性等诸多优点相结合,在气体捕集与分离领域表现出巨大的应用潜力,成为新的研究热点。本文首先简单阐述了多孔液体的概念及分类,并总结了多孔液体形成的必要条件;然后分别详细综述了三类多孔液体的合成进展,并阐述了多孔液体在气体捕集与分离方面的应用,着重介绍了近五年的研究进展;最后对其现存的挑战及未来展望进行了总结。

关键词： 多孔液体, 多孔空腔, 位阻溶剂, 气体捕集, 分离

Porous liquids(PLs), an emerging class of liquid materials with permanent porosity and good fluidity, have shown great potential in gas capture and separation. As a result, PLs used as gas capture materials have become a new research hot spot. In the present paper, the concept of PLs is firstly introduced in a nutshell. Then, the composition characteristics and the necessary conditions for constructing PLs are analyzed. Next, the synthesis progress of these three types of PLs are reviewed in detail, and their gas capture and separation performance are analyzed, especially after 2015. Lastly, the existing challenges of porous liquids and their outlooks of synthetic methods and applications in gas capture are outlined and presented.

Contents

1 Introduction

2 The classification of porous liquids and characteristics of composition

3 The synthesis progress of porous liquids and gas capture

3.1 The Type 1 porous liquids

3.2 The Type 2 porous liquids

3.3 The Type 3 porous liquids

4 Conclusion and outlook

Key words: porous liquids, porous cavities, steric solvents, gas capture, separation
()
图1 多孔液体相关文章的发表情况
Fig. 1 Publication of articles associated with porous liquids
图2 多孔液体的分类 (根据组成成分分类[30])
Fig. 2 Three classes of porous liquids based on the component properties(Reproduced from Ref.[30] with permission from Wiley)
图4 (a) 气体渗透量(i) PEGS, (ii) HS- liquid, (iii) SS-liquid, (iv) CS-liquid, (v) CS/Ni-liquid[30];(b)支撑多孔液膜的气体分离示意图[30];(c) HCS-liquid 、PEGS、SCS-liquid 和PILs-PEGS 的CO2的吸脱附等温线(10 bar, 298 K)[54];(d)多孔液体PS-OS@SiNR的吸附与脱附等温线[69];(e) 有机高分子长链改性中空硅壳纳米棒制备各向异性的多孔液体[69];(f) 静电辅助空心二氧化硅制备多孔液体[70]
Fig. 4 (a) Gas permeability obtained on (i) PEGS, (ii) HS- liquid, (iii) SS-liquid, (iv) CS-liquid, and (v) CS/Ni-liquid;(Reproduced from Ref. [30] with permission from Wiley)(b) Schematic representation of gas separation in membrane supported HS-liquid;(Reproduced from Ref. [30] with permission from Wiley)(c) CO2 adsorption-desorption isotherms of HCS-liquid, PEGS, SCS-liquid and PILs-PEGS composite collected below 10 bar at 298 K, respectively;(Reproduced from Ref. [54] with permission from Wiley)(d) The adsorption(closed symbols) and desorption(open symbols) cycles in solvent-free PS-OS@SiNR show hysteresis;(Reproduced from Ref. [69] with permission from the Royal Society of Chemistry)(e) Schematic showing the three-step procedure for the fabrication of the anisotropic porous liquid from SiNRs.(Reproduced from Ref. [69] with permission from the Royal Society of Chemistry)(f) Synthesis and schematic structures of hollow silica and porous liquid.(Reproduced from Ref. [70] with permission from the Chemical Industry Press)
图3 (a) 多孔有机笼的合成[51];(b) 上:阴离子有机笼的合成步骤与化学结构,中:15-冠-5和二环己烷并18-冠-6的化学结构,下:阴离子的共价有机笼多孔液体的合成[53];(c) 两步法合成空心SiO2多孔液体[30];(d) 静电辅助多孔液体的制备示意图[54];(e) 空心SiO2多孔液体的合成[55]
Fig. 3 (a) Synthesis of dodecaalkyl iminospherand cages.(Reproduced from Ref. [51] with permission from the Royal Society of Chemistry)(b) Top: Synthetic procedure and chemical structure of anionic covalent cage(ACC). Middle: Chemical structures of 15-crown-5 and dicyclohexano-18-crown-6. Bottom: Schematic representation of synthetic procedures for the crown ether-ACC porous liquids.(Reproduced from Ref. [53] with permission from the American Chemical Society)(c) Two-step synthetic strategy for porous liquids fabrication. HS=hollow silica, OS=organosilane.(Reproduced from Ref. [30] with permission from Wiley)(d) Synthesis strategy for HCS-liquid.(Reproduced from Ref. [20] with permission from Wiley)(e) Synthesis of hollow silica porous liquids.(Reproduced from Ref. [55] with permission from Wiley)
图5 (a) 多孔液体的制备:a1:冠醚的合成;a2:吸附量对比[24];(b) b1:CC3-R, CC13与33 :133-R乱序笼结构的对比;b2:CC33133笼的计算模型,展示出内在空腔结构;b3:多孔液体的计算模型及未被占据的多孔空腔;b4:CH4吸附量的对比[80];(c) c1:所选择的14种位阻溶剂;c2:Xe的吸附行为;c3:5种高溶解性的位阻溶剂[81];(d) d1:具有乱序笼的CC33 :13-R(左)和 CC15-R(右);d2:N2的吸附脱附曲线;d3:不同气体在多孔液体PLs上的吸附量对比;d4:气体在液体与POC中的对比[82];(e) e1:MOP多孔液体的合成步骤;e2:可接触的自由体积;e3:气体渗透量对比[29]
Fig. 5 (a) a: Preparation of porous liquid. a1: Synthesis of the crown-ether cage. a2: The comparation of sorption capacity;(adapted from Ref. [24])(b) b1: Comparison of the ‘parent' CC3-R and CC13 cage structures with the scrambled 33 :133-R mixture, b2: Schematic representation of the scrambled CC33133 cage used in the computational modeling showing the guest-accessible intrinsic cavity, b3: molecular simulation of the scrambled porous liquid showing the available free space in the cages(purple spheres); PCP solvent molecules shown as pale blue spheres; cage molecules omitted for clarity; b3: Comparison of the calculated CH4 uptake(mmol/mL) observed in PCP ;(Reproduced from Ref. [80] with permission from the Royal Society of Chemistry)(c) c1: The 14 bulky solvents screened for both cage solubility and size-exclusion from the cage cavity, c2: Comparison of the amount of Xenon evolved at different concentrations and using different release mechanisms; c3: The five highly solubilising candidate solvents, all displaced small volumes of gas from the known porous liquid.(Reproduced from Ref. [81] with permission from the Royal Society of Chemistry)(d) d1: Structures of the trans-33133 component of the scrambled cage mixture CC33 :133-R(magenta, left) and CC15-R(teal, right) with the average window diameters calculated using the pywindow package, d2: N2 adsorption(filled) and desorption(empty) isotherms for CC33 :133-R and CC15-R, d3: Uptake by volumetric gas evolution for CH4, CO2, Xe, and N2 for CC33 :133-R(magenta) and CC15-R(teal) PLs, d4: Comparison of gas uptake in the liquid and solid state for each POC;(Reproduced from Ref. [82] with permission from the Royal Society of Chemistry)(e) e1: Schematic preparation process of porous liquid. e2: Accessible void space displayed by accessible Voronoi node for CO2 in 15-crown-5 system. e3: Permeance of H2, CO2 and N2 in 15-crown-5/GO and PLs-5 wt%/GO at 60 ℃.(Reproduced from Ref. [29] with permission from Willey)
图6 (a) 金属有机骨架多孔液体表面改性、设计和溶剂设计图[20];(b) b1:多孔液体沸石(H-ZSM-5-liquid/[P6,6,6,14][Br])制备示意图;b2 沸石内部空腔[40];(c) ZIF-8多孔液体的合成[95];(d) d1:多孔液体的照片;d2: 水蒸气的等温吸附线[20];(e) 多孔沸石液体的吸附量对比[40];(f) ZIF-8多孔液体的CO2吸附-脱附等温线[95]
Fig. 6 (a) Schematic illustration of surface engineering, filler design, and solvent design for the construction of MOF-based porous liquids.(Reproduced from Ref. [20] with permission from the American Chemical Society)(b) b1: Depiction of the preparation strategy for the porous liquid zeolites(H-ZSM-5-liquid/[P6,6,6,14][Br]); b2: internal cavity of zeolite.(Reproduced from Ref. [40] with permission from the Royal Society of Chemistry),(c): Schematic illustration of the formation of ZIF-8 porous liquid.(Reproduced from Ref. [95] with permission from the American Chemical Society),(d) d1: Photos of tilting a vial of PL, d2: Water vapor sorption isotherms at 298 K of PLs after 3 months storage(Reproduced from Ref. [20] with permission from the American Chemical Society),(e): CO2 adsorption-desorption isotherms of H-ZSM-5 NPs, [P6,6,6,14][Br] and H-ZSM-5-liquid/[P6,6,6,14][Br] collected at 298 K, respectively.(Reproduced from Ref. [40] with permission from The Royal Society of Chemistry),(f): CO2 adsorption-desorption isotherms of ZIF-8 porous liquids at ambient temperature.(Reproduced from Ref. [95] with permission from the American Chemical Society)
图7 (a) 多孔液体UiO-66-liquid/[M2070][IPA]构筑原理及气体吸附示意图[41];(b) ZIF-8多孔液体路线[96];(c) CO2 在离子液体[M2070][IPA]及多孔液体UIO-66-liquid/[M2070][IPA]的吸附脱附等温线[41];(d) CO2在离子液体[Bpy][NTf2]及ZIF-8多孔液体的穿透曲线[96]
Fig. 7 (a) Fabrication based on a similar compatibility principle of the MOF-based porous liquid UIO-66-liquid/[M2070][IPA] and the illustration for adsorption of gas molecules.(Reproduced from Ref. [41] with permission from the Royal Society of Chemistry)(b) Synthesis strategy for ZIF-liquid.(Reproduced from Ref. [96] with permission from the American Chemical Society)(c) CO2 adsorption-desorption isotherms of [M2070][IPA] and UIO-66-liquid/[M2070][IPA] at 298 K, respectively.(Reproduced from Ref. [41] with permission from the Royal Society of Chemistry)(d) CO2 adsorption in [Bpy][NTf2](1 mL) and ZIF-8(20 mg) in [Bpy][NTf2](1 mL) at 298 K.(Reproduced from Ref.[96] with permission from the American Chemical Society)
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