State-of-the-art membrane based CO2 separation using mixed matrix membranes (MMMs): An overview on current status and future directions

Membrane processes have evolved as a competitive approach in CO2 separations compared with absorption and adsorption processes, due to their inherent attributes such as energy-saving and continuous operation. High permeability membrane materials are crucial to efficient membrane processes. Among existing membrane materials for CO2 separations, polymer-based materials have some intrinsic advantages such as good processability, low price and a readily available variety of materials. In recent years, enormous research effort has been devoted to the use of membrane technology for CO2 separations from diverse sources such as flue gas (mainly N2), natural gas (mainly CH4) and syngas (mainly H2). Polymer-based membrane materials occupy the vast majority of all the membrane materials. For large-scale CO2 separations, polymer-based membrane materials with high CO2 permeability and good CO2/gas selectivity are required. In 2012, we published a Perspective review in Energy & Environmental Science on high permeability polymeric membrane materials for CO2 separations. Since then, more rapid progress has been made and the research focus has changed significantly. This review summarises the advances since 2012 on high permeability polymer-based membrane materials for CO2 separations. The major features of this review are reflected in the following three aspects: (1) we cover polymer-based membrane materials instead of purely polymeric membrane materials, which encompass both polymeric membranes and polymer–inorganic hybrid membranes. (2) CO2 facilitated transport membrane materials are presented. (3) Biomimetism and bioinspired membrane concepts are incorporated. A number of representative examples of recent advances in high permeability polymer-based membrane materials is highlighted with some critical analysis, followed by a brief perspective on future research and development directions.

Advances in high permeability polymer-based membrane materials for CO2 separations

Mixed matrix membranes (MMMs) for gas separation applications have enhanced selectivity when compared with the pure polymer matrix, but are commonly reported with low intrinsic permeability, which has major cost implications for implementation of membrane technologies in large-scale carbon capture projects. High-permeability polymers rarely generate sufficient selectivity for energy-efficient CO2 capture. Here we report substantial selectivity enhancements within high-permeability polymers as a result of the efficient dispersion of amine-functionalized, nanosized metal–organic framework (MOF) additives. The enhancement effects under optimal mixing conditions occur with minimal loss in overall permeability. Nanosizing of the MOF enhances its dispersion within the polymer matrix to minimize non-selective microvoid formation around the particles. Amination of such MOFs increases their interaction with thepolymer matrix, resulting in a measured rigidification and enhanced selectivity of the overall composite. The optimal MOF MMM performance was verified in three different polymer systems, and also over pressure and temperature ranges suitable for carbon capture. Mixed matrix membranes can separate CO2 from flue gas mixtures but increasing selectivity without sacrificing permeability remains challenging. Selectivity can be increased with little loss in permeability by using nanoparticulate, amine-functionalized metal–organic framework fillers.

Enhanced selectivity in mixed matrix membranes for CO2 capture through efficient dispersion of amine-functionalized MOF nanoparticles

Here we report a solution-processing strategy to stabilize the perovskite-based heterostructure. Strong Pb–Cl and Pb–O bonds formed between a [CH(NH2)2]x[CH3NH3]1−xPb1+yI3 film with a Pb-rich surface and a chlorinated graphene oxide layer. The constructed heterostructure can selectively extract photogenerated charge carriers and impede the loss of decomposed components from soft perovskites, thereby reducing damage to the organic charge-transporting semiconductors. Perovskite solar cells with an aperture area of 1.02 square centimeters maintained 90% of their initial efficiency of 21% after operation at the maximum power point under AM1.5G solar light (100 milliwatts per square centimeter) at 60°C for 1000 hours. The stabilized output efficiency of the aged device was further certified by an accredited test center.

Stabilizing heterostructures of soft perovskite semiconductors

Hundreds of polymers have been evaluated as membrane materials for gas separations, but fewer than 10 have made it into current commercial applications, mainly due to the effects of physical aging and plasticization. Efforts to overcome these two problems are a significant focus in gas separation membrane research, in conjunction with improving membrane separation performance to surpass the Robeson upper bounds of selectivity versus permeability for commercially important gas pairs. While there has been extensive research, ranging from manipulating the chemistry of existing polymers (e.g., thermally rearranged or cross-linked polyimides) to synthesizing new polymers such as polymers of intrinsic microporosity (PIMs), there have been three major oversights that this review addresses: (1) the need to compare the approaches to achieving the best performance in order to identify their effectiveness in improving gas transport properties and in mitigating aging, (2) a common standardized aging protocol that all...

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Gas Permeation Properties, Physical Aging, and Its Mitigation in High Free Volume Glassy Polymers

The purpose of this work is the structural analysis of graphene oxide (GO) and by means of a new structural model to answer the questions arising from the Lerf–Klinowski and the Lee structural models. Surface functional groups of GO layers and the oxidative debris (OD) stacked on them were investigated after OD was extracted. Analysis was performed successfully using Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-Vis), X-ray photoemission spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, solid-state nuclear magnetic resonance spectroscopy (SSNMR), standardized Boehm potentiometric titration analysis, elemental analysis, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The analysis showed that graphene oxide layers, as well as oxidative debris contain different functional groups such as phenolic –OH, ketone, lactone, carboxyl, quinone and epoxy. Based on these results, a new structural model for GO layers is proposed, which covers all spectroscopic data and explains the presence of the other oxygen functionalities besides carboxyl, phenolic –OH and epoxy groups.

https://www.mdpi.com/2079-4991/9/8/1180/pdf

Structural Characterization of Graphene Oxide: Surface Functional Groups and Fractionated Oxidative Debris

PEBAX® with PEG functionalized POSS as nanocomposite membranes for CO2 separation

Enhanced gas permeability by fabricating mixed matrix membranes of functionalized multiwalled carbon nanotubes and polymers of intrinsic microporosity (PIM)

The present work reports on the gas transport behavior of mixed matrix membranes (MMM) which were prepared from multi-walled carbon nanotubes (MWCNTs) and dispersed within polymers of intrinsic microporosity (PIM-1) matrix. The MWCNTs were chemically functionalized with poly(ethylene glycol) (PEG) for a better dispersion in the polymer matrix. MMM-incorporating functionalized MWCNTs (f-MWCNTs) were fabricated by dip-coating method using microporous polyacrylonitrile membrane as a support and were characterized for gas separation performance. Gas permeation measurements show that MMM incorporated with pristine or functionalized MWCNTs exhibited improved gas separation performance compared to pure PIM-1. The f-MWCNTs MMM show better performance in terms of permeance and selectivity in comparison to pristine MWCNTs. The gas permeances of the derived MMM are increased to approximately 50% without sacrificing the selectivity at 2 wt.% of f-MWCNTs' loading. The PEG groups on the MWCNTs have strong interaction with CO2 which increases the solubility of polar gas and limit the solubility of nonpolar gas, which is advantageous for CO2/N2 selectivity. The addition of f-MWCNTs inside the polymer matrix also improved the long-term gas transport stability of MMM in comparison with PIM-1. The high permeance, selectivity, and long term stability of the fabricated MMM suggest that the reported approach can be utilized in practical gas separation technology.

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Muntazim Munir Khan

Papers

Structural Characterization of Graphene Oxide: Surface Functional Groups and Fractionated Oxidative Debris

PEBAX® with PEG functionalized POSS as nanocomposite membranes for CO2 separation

Enhanced gas permeability by fabricating mixed matrix membranes of functionalized multiwalled carbon nanotubes and polymers of intrinsic microporosity (PIM)

Functionalized carbon nanotubes mixed matrix membranes of polymers of intrinsic microporosity for gas separation.

Cross-linking of Polymer of Intrinsic Microporosity (PIM-1) via nitrene reaction and its effect on gas transport property