利用空位和缺陷工程协同效应提高Pebax膜的CO2分离

doi:10.11949/0438-1157.20250266

摘要/Abstract

摘要：

由于二维MoS₂纳米片表面孔隙率低、层间堆积传质路径长以及在聚合物中相容性差等问题，很难同时提高其混合基质膜的选择性和渗透速率。本工作首先通过离子印迹技术制备得富含空位和缺陷的MoS₂（P-MoS₂），并使用4-氨基-3-肼基-5-巯基-1,2,4-三唑（AHMT）对P-MoS₂改性制备杂化材料（AHMT-MoS₂）。然后将AHMT-MoS₂添加到聚醚嵌段聚酰胺（Pebax）中制备铸膜液，并涂覆在亲水改性的聚砜（mPSf）支撑体上制备混合基质复合膜（Pebax/AHMT-MoS₂）。采用傅里叶变换红外光谱（FTIR）、X-射线衍射（XRD）、扫描电镜（SEM）和N₂吸附-脱附表征材料和膜的化学结构、孔隙结构和形态结构。研究了材料的制备条件和测试条件对气体分离的影响。结果表明，Pebax/AHMT-MoS₂的CO₂渗透速率为818 GPU，CO₂/N₂选择性为56。这是因为通过离子印迹策略在MoS₂表面构建缺陷，增加了CO₂亲和位点；其表面孔和层间通道为CO₂提供了扩散通道。同时，氨基和肼基的引入，增强了CO₂的反应选择性，显著提高分离效果。优异的气体分离性能与低成本，使制备的混合基质复合膜在CO₂分离领域极具应用潜力。

关键词: 膜, 分离, 二氧化碳捕集, MoS₂改性, 离子印迹策略

Abstract:

In view of the low surface porosity of 2D MoS₂ nanosheets, the long interlayer stacking mass transfer path and the poor compatibility in polymers, it is difficult to simultaneously improve the selectivity and permeance of their mixed matrix membrane. In this paper, vacancy- and defect-rich MoS₂ (P- MoS₂) was first prepared by ion imprinting technology, and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (AHMT) was used to modify P- MoS₂ to prepare hybrid materials (AHMT- MoS₂). Then, AHMT-MoS₂ was added to polyether block polyamide (Pebax) to prepare cast film solution and then coated on polysulfone (mPSf) support to prepare mixed matrix composite membranes (Pebax/AHMT-MoS₂). Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and N₂ adsorption and desorption were used to characterize the chemical, morphological and pore structures of the materials and membranes. The effects of the preparation and testing conditions of the materials on gas separation were investigated. The results showed that Pebax/AHMT-MoS₂ exhibited CO₂permeance of 818 GPU and CO₂/N₂ selectivity of 56. This was attributed to the construction of the defects on the surface of MoS₂ by ion imprinting strategy, which increased the CO₂ affinity; its surface pores could provide diffusion channels for CO₂. In addition, introduction of amino and hydrazine groups enhances the reaction selectivity of CO₂ and significantly improves the separation. Due to excellent gas separation performance and low cost, it makes as-prepared mixed matrix composite membranes highly potential for the application in CO₂ separation.

Key words: membranes, separation, carbon dioxide capture, MoS₂ modification, ion imprinting strategy

中图分类号:

TQ 028.8

魏梦玥, 张新儒, 王永洪, 李晋平. 利用空位和缺陷工程协同效应提高Pebax膜的CO₂分离[J]. 化工学报, 2025, 76(12): 6439-6452.

Mengyue WEI, Xinru ZHANG, Yonghong WANG, Jinping LI. Boosting CO₂ separation of Pebax membranes with synergistic effect of vacancies and defects[J]. CIESC Journal, 2025, 76(12): 6439-6452.

图/表 15

图1 气体分离测试设备流程示意图

Fig.1 Schematic diagram of gas separation test equipment

图2 Pebax/AHMT-MoS2膜的制备示意图

Fig.2 Depicting preparation of Pebax/AHMT-MoS2

图3 Fe-MoS2、P-MoS2和AHMT-MoS2的SEM图

Fig.3 SEM images of Fe-MoS2, P-MoS2 and AHMT-MoS2

图4 MoS2、Fe-MoS2、P-MoS2和AHMT-MoS2的表征

Fig.4 Characterization of MoS2, Fe-MoS2, P-MoS2 and AHMT-MoS2

表1 材料的孔结构参数

Table 1 Porous structure parameters of materials

Sample

BET surface area/

(m²·g^-1)

Total pore volume/(cm³·g^-1)

Average pore diameter/nm

Fe-MoS₂

P-MoS₂

图5 纯Pebax膜和Pebax/AHMT-MoS2的表征

Fig.5 Characterizations of the pure Pebax membrane and Pebax/AHMT-MoS2

图6 纯Pebax膜和Pebax/AHMT-MoS2的横截面SEM图像

Fig.6 Cross-section SEM images of pure Pebax membrane and Pebax/AHMT-MoS2

图7 MoS2、Fe-MoS2、P-MoS2和AHMT-MoS2在Pebax铸膜液中的分散性光学照片

Fig.7 Optical photos of MoS2, Fe-MoS2, P-MoS2 and AHMT-MoS2 in Pebax cast solutions

图8 (a)不同Fe∶Mo物质的量比制备的Fe-MoS2;(b)不同Fe∶Mo物质的量比制备的P-MoS2;(c)不同AHMT:P-MoS2质量比制备的AHMT-MoS2和(d)AHMT-MoS2添加量对膜气体分离性能的影响

Fig.8 Effect of (a) Fe to Mo different molar ratios in Fe-MoS2, (b) Fe to Mo different molar ratios in P-MoS2, (c) AHMT to P-MoS2 different the mass ratio in AHMT-MoS2 and (d) AHMT-MoS2 loading on the gas separation performance of the membranes

图9 选择性层的湿膜厚度对纯Pebax膜和Pebax/AHMT-MoS2的CO2渗透速率(a)和CO2/N2选择性(b)的影响(1 bar=0.1 MPa）

Fig.9 Effect of the wet coating thickness of the selective layer on the CO2 permeance (a) and CO2/N2 selectivity (b) of pure Pebax membrane and Pebax/AHMT-MoS2

图10 进料气压力对纯Pebax膜和Pebax/AHMT-MoS2的CO2渗透速率(a)和CO2/N2选择性(b)的影响

Fig.10 Effect of the feed gas pressure on the CO2 permeance (a) and CO2/N2 selectivity (b) of the pure Pebax membrane and Pebax/AHMT-MoS2

图11 操作温度对纯Pebax膜和Pebax/AHMT-MoS2的CO2渗透速率(a)与CO2/N2选择性(b)的影响；(c)ln (CO2 permeability)和(d)ln (N2 permeability)与1000/T的Arrhenius谱图

Fig.11 Effect of the operating temperature on the CO2 permeance (a) and the CO2/N2 selectivity (b) of the pure Pebax membrane and Pebax/AHMT-MoS2; (c) Arrhenius plot of ln (CO2 permeability) vs 1000/T and (d) Arrhenius plot of ln (N2 permeability) vs 1000/T

图12 纯Pebax膜和Pebax/AHMT-MoS2在纯气和混合气测试条件下的气体分离性能

Fig.12 Gas separation performance of the pure Pebax membrane and Pebax/AHMT-MoS2 as determined by pure gas and mixed gas testing

图13 不同填料混合基质复合膜的气体分离性能(添加量为7%)

Fig.13 Gas separation performance of MMCMs with different fillers at the loading of 7%

图14 Pebax/AHMT-MoS2气体分离对比：(a)与已报道Pebax基质MMCMs的增量百分比对比和(c)上限对比图；(b)与已报道片层填料MMCMs的增量百分比对比和(d)上限对比

Fig.14 Comparison of Pebax/AHMT-MoS2 gas separation performance: (a) percentage incremental increase vs reported Pebax-based and (c) its upper bound plot; (b) percentage incremental increase vs reported lamellar fillers and (d) its upper bound plot

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利用空位和缺陷工程协同效应提高Pebax膜的CO₂分离

Boosting CO₂ separation of Pebax membranes with synergistic effect of vacancies and defects

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