二维材料膜在气体分离领域的最新研究进展

doi:10.3866/PKU.WHXB201810059

物理化学学报 >> 2019, Vol. 35 >> Issue (10): 1090-1098.doi: 10.3866/PKU.WHXB201810059

所属专题：二维材料及器件

二维材料膜在气体分离领域的最新研究进展

程龙,刘公平,金万勤*()

材料化学工程国家重点实验室，南京工业大学化工学院，南京 210009

收稿日期:2018-10-26 发布日期:2018-11-28
通讯作者: 金万勤 E-mail:wqjin@njtech.edu.cn
作者简介:JIN Wanqin is a professor of chemical engineering at Nanjing Tech University. He received his PhD degree from Nanjing University of Technology in 1999. He was a research associate at the Institute of Materials Research & Engineering of Singapore (2001), an Alexander von Humboldt Research Fellow (2001-2013), and visiting professors at Arizona State University (2007) and Hiroshima University (2011, JSPS invitation fellowship). His current research focuses on membrane materials and processes
基金资助:
国家自然科学基金(21490585);国家自然科学基金(21476107);国家自然科学基金(21776125);国家自然科学基金(51861135203);教育部创新团队项目(IRT17R54)

Recent Progress in Two-dimensional-material Membranes for Gas Separation

Long CHENG,Gongping LIU,Wanqin JIN*()

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, P. R. China

Received:2018-10-26 Published:2018-11-28
Contact: Wanqin JIN E-mail:wqjin@njtech.edu.cn
Supported by:
the National Natural Science Foundation of China(21490585);the National Natural Science Foundation of China(21476107);the National Natural Science Foundation of China(21776125);the National Natural Science Foundation of China(51861135203);the Innovative Research Team Program of the Ministry of Education of China(IRT17R54)

摘要/Abstract

摘要：

以石墨烯代表的二维材料已经成为新型高性能膜的纳米构建单元。原子级厚度的纳米片有利于制备超薄膜，极大提升膜的通量；与此同时，可实现在亚纳米级别精度下操纵传输通道实现精确的分子筛分，在气体分离领域有着广阔的前景。本文简要综述了二维材料膜在气体分离领域的最新突破性研究，重点介绍了如何实现亚纳米级别的二维通道，结构完整的二维纳米片的剥离方法及气体传输特性可调节的层间通道，并分析了二维材料膜发展面临的挑战和机遇。

关键词: 二维材料, 气体分离膜, 亚纳米通道, 超薄膜, 可调节的气体传输

Abstract:

Two-dimensional (2D) materials, led by graphene, have emerged as nano-building blocks to develop high-performance membranes. The atom-level thickness of nanosheets makes a membrane as thin as possible, thereby minimizing the transport resistance and maximizing the permeation flux. Meanwhile, the sieving channels can be precisely manipulated within sub-nanometer size for molecular separation, such as gas separation. For instance, graphene oxide (GO) channels with an interlayer height of about 0.4 nm assembled by external forces exhibited excellent H₂/CO₂ sieving performance compared to commercial membranes. Cross-linking was also employed to fabricate ultrathin (< 20 nm) GO-facilitated transport membranes for efficient CO₂ capture. A borate-crosslinked membrane exhibited a high CO₂ permeance of 650 GPU (gas permeation unit), and a CO₂/CH₄ selectivity of 75, which is currently the best performance reported for GO-based composite membranes. The CO₂-facilitated transport membrane with piperazine as the carrier also exhibited excellent separation performance under simulated flue gas conditions with CO₂ permeance of 1020 GPU and CO₂/N₂ selectivity as high as 680. In addition, metal-organic frameworks (MOFs) with layered structures, if successfully exfoliated, can serve as diverse sources for MOF nanosheets that can be fabricated into high-performance membranes. It is challenging to maintain the structural and morphological integrity of nanosheets. Poly[Zn₂(benzimidazole)₄] (Zn₂(bim)₄) was firstly exfoliated into 1-nm-thick nanosheets and assembled into ultrathin membranes possessing both high permeance and excellent molecular sieving properties for H₂/CO₂ separation. Interestingly, reversed thermo-switchable molecular sieving was also demonstrated in membranes composed of 2D MOF nanosheets. Besides, researchers employed layered double hydroxides (LDHs) to prepare molecular-sieving membranes via in situ growth, and the as-prepared membranes showed a remarkable selectivity of ~80 for H₂-CH₄ mixture. They concluded that the amount of CO₂ in the precursor solution contributed to LDH membranes with various preferred orientations and thicknesses. Apart from these 2D materials, MXenes also show great potential in selective gas permeation. Lamellar stacked MXene membranes with aligned and regular sub-nanometer channels exhibited excellent gas separation performance. Moreover, our ultrathin (20 nm) MXene nanofilms showed outstanding molecular sieving property for the preferential transport of H₂, with H₂ permeance as high as 1584 GPU and H₂/CO₂ selectivity of 27. The originally H₂-selective MXene membranes could be transformed into membranes selectively permeating CO₂ by chemical tuning of the MXene nanochannels. This paper briefly reviews the latest groundbreaking studies in 2D-material membranes for gas separation, with a focus on sub-nanometer 2D channels, exfoliation of 2D nanosheets with structural integrity, and tunable gas transport property. Challenges, in terms of the mass production of 2D nanosheets, scale-up of lab-level membranes and a thorough understanding of the transport mechanism, and the potential of 2D-material membranes for wide implementation are briefly discussed.

10.3866/PKU.WHXB201809013.F009

Key words: Two-dimensional material, Gas separation membrane, Sub-nanometer channel, Ultrathin membrane, Tunable gas transport

程龙,刘公平,金万勤. 二维材料膜在气体分离领域的最新研究进展[J]. 物理化学学报, 2019, 35(10), 1090-1098. doi: 10.3866/PKU.WHXB201810059

Long CHENG,Gongping LIU,Wanqin JIN. Recent Progress in Two-dimensional-material Membranes for Gas Separation[J]. Acta Physico-Chimica Sinica 2019, 35(10), 1090-1098. doi: 10.3866/PKU.WHXB201810059

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201810059

https://www.whxb.pku.edu.cn/CN/Y2019/V35/I10/1090

图/表 5

Fig 1

Fig 2

Fig 3

Fig 4

Table 1

Comparison of gas separation performance of 2D-material membranes."

2D-material membranes	Preparation method	Membrane thickness	Feed condition ^a	Permeate rate/ permeance/permeability^b	Selectivity^b	Permeate rate/ permeance/permeability^c	Selectivity^c	Ref.
Porous graphene	Simulation All-H	Monolayer	H2/CH4	1 × 10^-20 mol-s^-1-Pa^-1	10²³			4
	passivation	graphene
Porous graphene	Simulation N and	Monolayer	CO₂/CH₄	10⁶ GPU	3.99			5b
	methyl passivation	graphene
Porous graphene	Simulation N and	Monolayer	CO₂/CH₄	4.4 × 10^-4 mol·m^-2-s^-1-Pa^-1	11.8			5a
	H passivation	graphene
Porous graphene	Ultraviolet-induced	Bilayer	H₂/CH₄	4.5 × 10^-23 mol-s^-1-Pa^-1	10⁴			6
	oxidative etching	graphene
Porous graphene	Focused ion	Bilayer	H₂/CO₂	5.0 × 10^-3 mol·m^-2-s^-1-Pa^-1	4.6			7
	beam perforation	graphene
Few-layered GO/PES	Spinning coating	3-7 nm	CO₂/N₂	120 GPU	55			8a
	Thermal reduced	Not available	H₂/CO₂(140 ℃)	1000 GPU	40
GO/AAO	Vacuum filtration	9 nm	H₂/CO₂			10^-7 mol·m^-2-s^-1-Pa^-1	3400	8b
			H₂/N₂				900
GO/a-Al₂O₃	External force	1	H₂/CO₂	840-1200 Barrer	29-33	783 Barrer	17.2	9
	driven assembly
			H₂/C₃H₈		260	648 Barrer	230.8
GO/PES	Borate crosslinking	8 nm	CO₂/CH₄	650 GPU	75	665 GPU	79	13
			CO₂/N₂		57		60
GO/PES hollow fiber	Vacuum filtration	9 nm	CO₂/N₂	49 GPU	50	35 GPU	34	14
			(15% : 85%)
	Piperazine crosslinking	16 nm	CO₂/N₂			1020 GPU	680
			(15% :85%, 80 ℃)
Zn₂(bim)₄/α-Al₂O₃	Hot-drop coating	Several nanometers	H₂/CO₂			2280 ± 490 GPU	230 ± 39	15
MAMS-1/AAO	Hot-drop coating	40 nm	H₂/CO₂			553 ± 228 GPU	235 ± 14	16
NiAl-CO₃ LDH/	In situ growth	5	H₂/CH₄(180 ℃)			4.6 × 10^-8 mol·m^-2-s^-1-Pa^-1	78.7	19
γ-Al₂O₃ modified
α-Al₂O₃
ZnAl-NO₃ LDH/	In situ growth	2.5	H₂/CH₄(180 ℃)			3.7 × 10^-8 mol·m^-2-s^-1-Pa^-1	13.7	19
γ-AkO₃ modified
α-Al₂O₃
Freestanding MXene	Vacuum filtration	2	H₂/CO₂	2402 Barrer	238.4	2226 Barrer	166.6	21
MXene/AAO	Vacuum filtration	20 nm	H₂/CO₂	1584 GPU	27	1200 GPU	20	22
	Borate/PEI crosslinking	20 nm	CO₂/CH₄	350 GPU	15.3	245 GPU	11.5

Table 1

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二维材料膜在气体分离领域的最新研究进展

Recent Progress in Two-dimensional-material Membranes for Gas Separation

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