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Hybrid MOF-COF structures for advanced gas separation membranes: a short review of synthesis, performance analysis and application potential

  • Maciej Szwast ORCID logo EMAIL logo and Daniel Polak
Published/Copyright: March 25, 2025
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Reviews in Chemical Engineering
From the journal Reviews in Chemical Engineering Volume 41 Issue 5

Abstract

This review examines the application potential of hybrid MOF-COF structures in fabricating advanced membranes for gas separation. MOF-COF membranes demonstrate exceptional gas separation performance, surpassing the Robeson upper bound for several gas mixtures, including H2/CH4, CO2/CH4, CO2/N2 and O2/N2. Key findings indicate that thin-film MOF-COF membranes exhibit remarkable selectivity and permeability, with some hybrids achieving permeance values exceeding 1,000,000 GPU and ideal separation factors over 30. Additionally, mixed matrix membranes (MMMs) containing MOF-COF hybrids show potential for combining mechanical robustness with high separation efficiency, despite challenges in achieving uniform dispersion. Future research should prioritize scaling up production methods, enhancing the mechanical stability of thin films, and improving polymer-hybrid compatibility in MMMs. Experimental validation of theoretical predictions is essential to address discrepancies and unlock the full potential of these materials. MOF-COF hybrids are poised to revolutionize gas separation technologies and offer promising directions for broader applications, including catalysis and energy storage.

Keywords: MOF; COF; hybrid; membranes; mixed matrix; gas separation

1 Introduction

Membrane processes are increasingly gaining a larger market share in gas mixture separation within various industries. These processes primarily utilize non-porous polymer membranes (Bakonyi et al. 2013; Bera et al. 2021; Szwast 2012). The development of polymer chemistry has made polymers readily accessible at affordable prices and easily processable (Xu et al. 2022; Zou et al. 2021). However, it has long been known that polymer membranes have inherent limitations that prevent achieving both high selectivity in separation and high product flux simultaneously (Robeson 1991, 2008). These limitations are primarily due to thermodynamic constraints associated with the properties of polymers (Freeman and Carolina 1999). In the literature, this limitation is often illustrated by the “Robeson upper bound,” depicted on a graph of ideal selectivity versus the permeability of one of the components in the gas mixture.

Scientific research has shown that achieving membranes with improved separation properties is possible by incorporating fillers into the polymer matrix, leading to the formation of heterogeneous membranes known as mixed matrix membranes (MMMs) (Mahajan et al. 2002; Mahajan and Koros 2000; Zimmerman et al. 1997). These fillers alter the gas transport mechanism through the membrane, enabling the surpassing of the Robeson upper bound. Much of the current research on the development of new membranes for gas separation focuses on finding membranes that can significantly exceed the Robeson upper bound. The most commonly used fillers in these membranes are inorganic particles, such as SiO2 nanoparticles (Polak and Szwast 2022; Sforça et al. 2001), carbon-based materials, including carbon nanotubes (Sung et al. 2004; Xie et al. 2005), graphene and graphene oxide (Pazani et al. 2022; Qiao et al. 2012), as well as zeolites (Polak and Szwast 2022; Zornoza et al. 2011). Another group of fillers consists of organic materials, such as porous aromatic frameworks (PAFs) (Cheng et al. 2018) and covalent-organic frameworks (COFs) (Zhang et al. 2022). Hybrid fillers, such as metal-organic polyhedra (MOP) (Dechnik et al. 2017) and metal-organic frameworks (MOFs) (Tanh Jeazet et al. 2012), are also being investigated. Among the fillers mentioned, MOF and COF particles are currently of particular interest.

MOFs (metal-organic frameworks) are particles in which metal ions are connected by linkers, which are rigid molecules with at least two functional groups that can interact with metal ions (Li et al. 1999). Carboxylate groups are an example of common linkers (Lu et al. 2014; Yuan et al. 2015). These particles can form two- or three-dimensional structures (Oh et al. 2019; Tang et al. 2021), with a remarkable diversity estimated at over 100,000 different possible metal ion-linker combinations (Freund et al. 2021). Importantly, these particles exhibit crystalline properties and are porous (Long and Yaghi 2012), with pore sizes that can reach even a few angstroms Å (10−10 m) (Chen et al. 2006). In view of the numerous potential applications of MOFs, the possibility of designing particles with specific pore sizes by selecting appropriate linkers is especially important. Currently, MOF particles have various applications, including the storage of gases, particularly fuel gases, i.e. hydrogen (Li et al. 2018; Wong-Foy et al. 2006) and methane (Alezi et al. 2015; Mason et al. 2014). One of the most critical applications of MOF particles, relevant to this article, is their use in gas separation processes (Qian et al. 2020; Zhang et al. 2016). This application is especially feasible due to the narrow pore size distribution in MOF structures. MOF particles can form standalone membranes for gas separation (Wang et al. 2020) or be dispersed as the filler phase in MMMs (Tien-Binh et al. 2016). Other applications of these particles are catalysis (e.g. biomass enrichment (Herbst and Janiak 2017), polymerization (Goetjen et al. 2020), CO2 conversion (Hou et al. 2019)), biomedical engineering (drug delivery (Wang et al. 2018), biomedical imaging (Wu et al. 2018)), construction of electronic components (Kung et al. 2019; Stavila et al. 2014), construction of electrochemical sensors (e.g. glucose detection (Shi et al. 2018), dopamine detection (Xu et al. 2019) and others (Golshadi et al. 2024)).

COFs (covalent-organic frameworks), on the other hand, are a type of porous polymeric particle with two- or three-dimensional structures. They are formed by chemical reactions between organic precursors, which are bonded by strong covalent bonds (Sun et al. 2023). The diversity of these porous structures is much smaller than that of MOF particles, with estimates of just below 600 (Freund et al. 2021). Porosity is the key property of COF particles, like MOFs, relevant to this article. The narrow pore size distribution and reproducibility of their synthesis are crucial for gas separation and storage applications. The pore sizes in these structures are typically around several angstroms Å (10−10 m) (Tilford et al. 2006). Currently, COF particles are employed in applications such as gas separation membranes (Li et al. 1999; Qu et al. 2022) and water purification (Azadi et al. 2024; Kandambeth et al. 2017; Mokhtari et al. 2022). Another broad application of COF particles is in energy storage and generation. COF particles are used in the production of batteries (Gerhardt et al. 2017; Liao et al. 2018), the construction of capacitors (Chen et al. 2014), and also in the construction of solar cells and fuel cells (Colson et al. 2011; Montoro et al. 2017). An important application of COF particles is also medical diagnostics, drug delivery (Dinari et al. 2020), and in particular immunosensors – here they are used to detect markers such as kidney injury molecule (KIM) or prostate-specific antigen (PSA) in samples (Boyacıoğlu et al. 2022; Zheng et al. 2021a).

In recent years, significant effort has been dedicated to the hybridization of MOF and COF particles (Peng et al. 2018). These MOF-COF hybrid particles exhibit interesting properties resulting from the synergy of their individual components. This study aims to explore the potential of MOF-COF hybrids in gas separation processes using membrane structures, specifically those incorporating these hybrids.

2 MOF-COF hybrids applications

The aim of this review article is specifically to highlight the applications of MOF-COF hybrid structures in the fabrication of membranes for gas separation. However, this application is less obvious when analyzing the literature on these hybrid compounds. Therefore, the applications of MOF-COF hybrids mentioned in the literature will be briefly discussed.

MOF-COF hybrids find widespread use in catalytic and photocatalytic reactions. For example, MOF-COF hybrids have been successfully applied in the catalysis of the Knoevenagel reaction (Rafiee 2021; Rahmati and Rafiee 2021), C–C coupling reaction of pyrimidine sulfonate and arylboronic acid (Yang et al. 2022a), as well as in electrocatalytic and non-electrocatalytic CO2 reduction (Diercks et al. 2018; Nam et al. 2020; Niu et al. 2022; Wang et al. 2022, 2023; Yang et al. 2022b, 2023; Zhou et al. 2022), species oxidation (Cai et al. 2019; Zhang et al. 2021b), O2 reduction (Guo et al. 2021), reactive oxygen species generation (Li et al. 2023b), and hydrogen production (Chen et al. 2020, 2022; Sun and Kim 2020; Xue et al. 2021; Zhang et al. 2018, 2021a).

In the literature, a lot of attention is devoted to the use of MOF-COF structures in energy storage, particularly in batteries. The use of these particles in battery production is made possible due to their large specific surface area and the well-defined geometry of the channels formed between the particle bonds (Chu et al. 2021). The energy storage systems produced in this way are characterized by voltages reaching up to 4 V and capacities of several hundred mAh/g (Hong et al. 2024; Sun et al. 2019; Zhao et al. 2020; Zhang et al. 2017; Zheng et al. 2021b). MOF-COF hybrids are also used to produce electrodes for batteries (Kong et al. 2022; Liu et al. 2021).

Another important application of hybrid MOF-COF particles is in the construction of specific sensors. These particles are used to build sensors capable of detecting ampicillin (Liu et al. 2019), tetracycline (Li et al. 2023a; Zhou et al. 2019), platelet-derived growth factor-BB (Li et al. 2021b), HIV-1 DNA (Xu et al. 2021) and even bacteria (Meng et al. 2023).

The discussed hybrid particles are also being increasingly applied in biotechnology. This is especially true in mimicking natural enzymes (Feng et al. 2022; Zhang et al. 2021c, 2024).

Due to their porous structure and highly developed specific surface area, MOF-COF particles are also used as adsorbents (Dinari and Jamshidian 2021; Firoozi et al. 2020; Zhong et al. 2021). These properties make MOF-COF hybrids promising materials for the production of membranes, including gas separation membranes, which will be discussed later.

As a summary of this chapter, Figure 1 shows the areas of application of MOF-COF hybrids.

Figure 1: Applications of MOF-COF hybrids.
Figure 1:

Applications of MOF-COF hybrids.

MOF-COF hybrids are emerging as versatile materials with applications in gas separation, catalysis, energy storage, sensing, and biomedical technologies. Their well-defined porosity and tunable chemical functionality enable precise molecular sieving, selective adsorption, and enhanced reactivity, making them attractive for both industrial and research applications.

3 MOF and COF manufacturing

This chapter offers a concise summary of the synthesis methods of MOF and COF particles. This information will serve as a foundation for presenting the synthesis methods of MOF-COF hybrids, which are the subject of this review paper.

MOF particles consist of a metal ion (inorganic) and an organic ligand, which are connected by a coordination bond (Ding et al. 2019). Practically all transition metals can be used to synthesize MOFs. Due to the diversity of coordination numbers and oxidation states, it is possible to design and fabricate particles with a wide variety of geometries, both two-dimensional and three-dimensional (Ghanbari et al. 2020). The ligands can include organic compounds such as carboxylates, imidazolates, porphyrin derivatives, phosphonates, and amines (Li et al. 2009; Mondloch et al. 2013; Yaghi et al. 2003).

MOF synthesis requires the input of external energy. The most conventional method for fabricating these particles is one in which thermal energy is supplied from traditional heat sources. The temperature range used for synthesis spans from room temperature to approximately 250 °C (Wang et al. 2014). As part of this approach, solvothermal and non-solvothermal methods are distinguished by the pressure ranges applied. Since certain types of MOFs are sensitive to prolonged exposure to high temperatures or pressures, and given the high energy costs of this method, alternative synthesis methods have been developed (Moharramnejad et al. 2023). One such alternative is the sonochemical method (Jodłowski et al. 2023). In this method, energy is supplied to the reaction through the phenomenon of acoustic cavitation caused by mechanical waves at frequencies as high as 10 MHz (Abdolalian et al. 2017). This method allows reactions to proceed at lower temperatures. An intermediate-temperature method is MOF synthesis using microwave electromagnetic waves (Thomas-Hillman et al. 2018). The energy transferred via electromagnetic radiation causes the metal ions and ligands to bond at moderate temperatures, around 100 °C (Blanita et al. 2016). This method yields MOF particles with properties similar to those obtained by conventional methods, though some differences in pore size have been observed (Choi et al. 2008). Another method for synthesizing MOF structures is the mechanochemical method, in which the reaction takes place using no solvent or only a minimal amount (Friić and Fábián 2009; Garay et al. 2007).

For the synthesis of COF particles, various methods such as solvothermal, interfacial, vapor-assisted conversion, synthesis under continuous flow conditions, solvent-assisted exfoliation, chemical exfoliation, mechanical delamination, and self-exfoliation are used (Wang et al. 2019). The solvothermal method is the simplest, in which COF powders precipitate from a reaction mixture onto a substrate under appropriate temperature conditions (Colson et al. 2011). The interfacial method produces thin COF films at the liquid/liquid or liquid/air phase boundary, naturally limiting the film thickness (Matsuoka et al. 2017). Vapor-assisted conversion is a relatively gentle method conducted at room temperature. In this method, a reaction mixture applied to a substrate in small droplets is evaporated in a desiccator, leaving behind a thin layer of COF particles (Medina et al. 2015). The synthesis under continuous flow conditions method is a variant of conventional synthesis but is conducted under dynamic flow conditions rather than statically, as in the solvothermal method (Bisbey et al. 2016).

The previously mentioned methods of producing thin COF films fall under the so-called “bottom-up strategy,” where COF particles are formed from a solution. The second group of methods is the “top-down strategy,” in which thin COF films are produced by separating them from larger structures (Rodríguez-San-Miguel et al. 2020). Solvent-assisted exfoliation and chemical exfoliation are methods in which the bonds between the layers of COF material (e.g. formed through condensation) are weakened by the action of organic solvents or other chemicals (Khayum et al. 2016; Peng et al. 2017). In the mechanical delamination method, similar effects are achieved by mechanically grinding the materials (Mu et al. 2017; Wang et al. 2017). The last method, self-exfoliation, involves the spontaneous exfoliation of COF layers due to internal stresses within the material (Haldar et al. 2018).

4 MOF-COF hybrid types and manufacturing

The synthesis of MOF-COF hybrids does not fundamentally rely on simply combining two pre-formed structures, namely MOFs and COFs, though this is not a strict rule. MOF-COF hybrids are synthesized via one of several methods more extensively discussed in the literature. Broadly, the literature categorizes MOF-COF hybrid synthesis methods as single component and multicomponent.

The first method in the single component group is the synthesis of C-MOF compounds, where COF linkers are coordinated to metal ions, which then connect via additional COF linkers to form a covalent-metal framework, namely C-MOF. Examples of such structures include those where copper ions are connected by linkers such as 1,3,5-tris(4-aminophenyl)benzene (Wei et al. 2021) or 2,3,6,7,10,11-hexahydroxytriphenylene (Liu et al. 2023). The second method within this group aims to produce a structure where COF linkers are incorporated into the porous MOF framework by interacting with MOF linkers, creating what is referred to as a COF-in-MOF structure (Li et al. 2021a). An example of this structure is a zeolitic imidazolate framework coupled with the ketoenamine-linked TpPa-1 (Biswal et al. 2013), which has also been used to fabricate and study membranes (Fan et al. 2021).

The second group of hybrids comprises the so-called multicomponent hybrids. This group includes structures such as COF-on-MOF, MOF-on-COF, and MOF + COF. The first method in this group, COF-on-MOF, involves using a pre-formed MOF compound as a substrate for the growth of a COF layer on its surface (Chen et al. 2021; Deng et al. 2022; Li et al. 2021a). One approach to such hybridization involves growing COF compounds on the surface of MOF structures that have been functionalized with aldehyde groups. For instance, the MOF-In2S3@FcDc-TAPT hybrid is produced by growing a COF structure on an NH2-MIL-68(In) substrate using 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and ferrocene-1,10-dicarbaldehyde (FcDc) (He et al. 2019). Another approach involves preparing MOF structures functionalized with amino groups, and then growing COF compounds that will covalently bind to the surface, forming hybrids. For instance, NH2-MIL-125@TAPB-PDA was prepared by growing a COF from terephthaldehyde and 1,3,5-tris(4-aminophenyl)benzene on pre-functionalized NH2-MIL-125 at high temperatures (120 °C) (Lu et al. 2020). The MOF-on-COF method, on the other hand, uses a pre-formed COF compound as a substrate for the growth of a MOF layer on its surface (Chen et al. 2021; Deng et al. 2022; Li et al. 2021a). An example of this hybridization is the synthesis of a structure formed by 1,4-phenylenediamine and 1,3,5-tribenzaldehyde (COF) and subsequent connection with Mn(NO3)2·4H2O (MOF) and trimesic acid in ethanol (Sun et al. 2019). The final type within the multicomponent hybrids is the MOF + COF structure, which fundamentally differs in its spatial structure from the MOF-on-COF and COF-on-MOF configurations. Unlike these two, it lacks a core-shell architecture. MOF + COF synthesis generally uses one of two approaches: post-synthetic modification or the one-pot strategy (Li et al. 2021a). In the first approach, a chosen MOF or COF structure is surface-modified to introduce functional groups capable of binding to a COF or MOF, respectively. In the second approach (one-pot), the MOF and COF compounds are reacted together in a single reaction system. For example, benzoic acid-functionalized CTF-1 nanosheets (COF) were combined with NH2-MIL-125(Ti) (MOF) through sonication in an inert atmosphere, followed by transferring the dispersion to a reaction system containing N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole, and N,N-diisopropylethylamine (Li et al. 2019).

Regardless of the synthesis method, MOF/COF hybrid materials exhibit stable properties that generally represent a synergistic combination of the constituent materials characteristics (Ma et al. 2022). Such hybrids find applications in catalysis, energy storage, gas separation, and chemical detection, as previously discussed.

The methods of synthesizing various MOF and COF compounds and their hybrids are summarized in Figure 2.

Figure 2: Methods of synthesizing various MOF and COF compounds and their hybrids. Various synthesis methods have been developed to tailor the structure and properties of MOFs, COFs, and their hybrids. This figure categorizes key fabrication approaches, including solvothermal, mechanochemical, and microwave-assisted methods, as well as hybridization techniques that integrate MOF and COF components into single materials with enhanced functionality.
Figure 2:

Methods of synthesizing various MOF and COF compounds and their hybrids. Various synthesis methods have been developed to tailor the structure and properties of MOFs, COFs, and their hybrids. This figure categorizes key fabrication approaches, including solvothermal, mechanochemical, and microwave-assisted methods, as well as hybridization techniques that integrate MOF and COF components into single materials with enhanced functionality.

Like any chemical structures, MOF-COF hybrids have their advantages and disadvantages. Table 1 summarizes these issues in relation to different aspects.

Table 1:

Advantages and disadvantages of hybrid MOF-COF structures.

Advantages Disadvantages
Structural properties High porosity and surface area enhance gas adsorption and separation efficiency Structural fragility, especially in thin-film configurations, increases risk of mechanical failure
Chemical versatility Tunable pore sizes and chemical functionalities achieved via MOF and COF selection Complex and resource-intensive synthesis
Mechanical properties Mixed matrix membranes improve robustness compared to pure MOF or COF membranes Agglomeration due to non-uniform dispersion in the polymer matrix reduces performance
Thermal stability Excellent thermal stability suitable for high-temperature applications Sensitivity of some components limits performance at extreme temperatures
Gas separation performance High selectivity and permeability, often exceeding the Robeson upper bound Reduced mechanical durability linked to high selectivity and permeability
Environmental impact Use of MOF-COF hybrids can enable more energy-efficient separation processes Limited knowledge on disposal and recyclability of hybrid materials

5 Gas separation membranes with MOF or COF

As mentioned in the introduction, two characteristic parameters that describe the properties of membranes used in gas separation are permeability, Equation (1), and selectivity, Equation (2) (Szwast 2012).

(1) P i = J i ∙ l ∆ p i
(2) α A / B = P A P B

where P i , P A , P B  – permeability of component i, A, B, respectively [mol m−2 m Pa−1 s−1],

J i  – molar flux of gaseous component i [mol m−2 s−1], l – membrane thickness [m],

Δp i  – transmembrane partial pressure of component i [Pa], αA/B – ideal separation factor for components A and B [−].

Due to the miniscule values of permeability expressed in SI units, it is common in the literature to use an alternative unit for permeability, according to the following conversion:

1 barrer = 3.35 × 10−16 mol m−2 m Pa−1 s−1.

It was also noted that polymer-based membranes have thermodynamic limitations that prevent the production of membranes with both high permeability and high selectivity – two parameters whose maximization is the goal in membrane manufacturing. This limitation is typically represented on plots of selectivity versus permeability as the Robeson upper bound. A potential approach to surpassing this limit is the creation of heterogeneous membranes of the mixed matrix type. Figure 1 compiles literature data for membranes produced as thin films made of MOF or COF materials, as well as mixed matrix membranes, in which MOF or COF particles are embedded within a polymer matrix.

Figure 3 demonstrates that it is indeed possible to exceed the Robeson upper bound by producing thin-film membranes from MOF or COF. However, it is also economically more viable and convenient for later membrane applications to surpass the Robeson upper bound by manufacturing heterogeneous membranes containing MOF or COF particles. In summary, porous structures such as MOFs and COFs have the potential to overcome the limitations characteristic of polymer membranes. In the next chapter, a similar analysis will be conducted in more detail for the less commonly described materials, specifically membranes produced with hybrid MOF-COF structures.

Figure 3: Selective/permeability properties of membranes made of MOF, COF or as a mixed matrix containing MOF or COF: (a) separation of H2/CH4, (b) separation of O2/N2, (c) separation of CO2/N2, (d) separation of CO2/CH4. Data from the selected papers. The figure presents a comparative analysis of membrane selectivity and permeability for different gas pairs, highlighting the ability of MOF and COF membranes to surpass the Robeson upper bound. The data illustrate the potential of these materials – both as thin films and in mixed-matrix membranes – to achieve superior gas separation efficiency compared to conventional polymer membranes.
Figure 3:

Selective/permeability properties of membranes made of MOF, COF or as a mixed matrix containing MOF or COF: (a) separation of H2/CH4, (b) separation of O2/N2, (c) separation of CO2/N2, (d) separation of CO2/CH4. Data from the selected papers. The figure presents a comparative analysis of membrane selectivity and permeability for different gas pairs, highlighting the ability of MOF and COF membranes to surpass the Robeson upper bound. The data illustrate the potential of these materials – both as thin films and in mixed-matrix membranes – to achieve superior gas separation efficiency compared to conventional polymer membranes.

6 Gas separation membranes with MOF-COF hybrids

In the previous chapter, literature reports confirming the suitability of MOF and COF structures for gas separation membranes were discussed. The potential of both structures is evident in the fabrication of both thin-film membranes and heterogeneous mixed-matrix polymer membranes. From the perspective of this review article, it is crucial to answer whether hybrid MOF-COF structures exhibit similar properties. Given sparse documentation on the hybridization of MOF-COF structures, especially their applicability, in the literature, the answer to this question is challenging. Some studies, based on experiences with other nanoporous structures, point to a significant potential for MOF/COF hybrid structures in gas separation, even suggesting their breakthrough potential in this application area (Duan et al. 2023).

Hybrid MOF/COF structures combine the unique features of metal-organic materials (MOFs) and organic materials (COFs) to achieve improved gas separation efficiency. The enhanced gas separation using these particles relies on molecular sieving. This is possible because both MOFs and COFs, as well as their hybrids, are porous materials with tunable pore sizes, where MOF structures offer precise control of pore dimensions through the coordination of metal centers and organic linkers, enabling selective diffusion of gas molecules, while COF structures provide stiffness and stability of the structure, which supports the formation of well-defined channels facilitating gas transport. For example, narrow pore size distributions in MOF/COF hybrids increase separation efficiency by allowing the passage of smaller gas molecules such as hydrogen (H2) while blocking larger ones such as carbon dioxide (CO2).

The first type of membranes made from MOF-COF hybrids are flat thin films formed from native structures, according to one of the previously described fabrication methods. These spatial structures have been studied for their properties in separating components from selected gas mixtures. To separate a mixture of two hydrocarbons, namely C3H6/C3H8, membranes were made from ZIF-8 + EBCOF (ethidium bromide COF) (Liu et al. 2022) and ZIF-8 + TpPa-SO3H (Triformylphloroglucinol with sulfonic acid functional groups) (Pu et al. 2023). In the first case, the material exhibited a permeance value of 125 GPU, while the second showed a permeance of 600 GPU measured for C3H6. Meanwhile, the ideal separation factors were 200 and 90, respectively. Analyzing these data alongside results for other membranes made from polymers, inorganic particles, hybrid materials, or mixed matrix membranes, it can be concluded that the properties of these MOF-COF membranes are far superior to those defined by the Robeson upper bound and outperform membranes made from MOF structures and zeolites. For separating an H2/CH4 mixture, membranes were made from ZIF-67-TpPa-155 (Pu et al. 2023) and ZIF-67-in-PBD (Qi et al. 2024). In the first case, a permeance of 3,800 GPU and an ideal separation factor of 37.8 were achieved, which surpasses the Robeson upper bound. In the second case, ZIF-67-in-PBD membranes achieved a permeance of 109 GPU and an ideal separation factor of 33.48. Particularly, the results for the second membrane are impressive and support the idea of a breakthrough potential for MOF-COF hybrid structures in gas separation. For the industrially important H2/CO2 mixture, MOF-COF membranes also showed results far surpassing the Robeson upper bound and exceeding the properties of membranes made from other materials (MOF only, COF only, zeolites, MMM). ZIF-67-TpPa-155 membranes (Qi et al. 2024) exhibited a permeance of 3,800 GPU and an ideal separation factor of 38.3, while [COF-300]-[Zn2(bdc)2(dabco)] membranes (Fu et al. 2016) displayed a permeance of 13,000 GPU and an ideal separation factor of 12.6. Although the selectivity of 12.6 is not impressive, it is still higher than most homogeneous polymer membranes. Excellent H2/CO2 separation results were also achieved for membranes made from the hybrid H2P-DHPh COF−UiO-66 (Das et al. 2020), which exhibited a permeance of 108,341.30 GPU and an ideal separation factor of 32.9, a result significantly better than that achieved by other membranes. Much higher permeance values, 1,059,354.60 GPU, with a slightly lower ideal separation factor of 24.2, were obtained for membranes made from [COF-300]-[UiO-66] (Das and Ben 2018). Such values indicate that MOF-COF hybrid membranes could indeed represent a breakthrough in gas mixture separation processes.

An important positive feature of the membranes discussed above is their high permeance. This is a measure relating to the unit surface area of the membrane, meaning that for a given industrial process, a smaller membrane surface will be required compared to other types of membranes. However, scaling up the production of these membranes will be necessary for larger industrial applications, requiring membranes with greater surface areas than those investigated in the studies analyzed. Scaling up the production of thin-film MOF-COF hybrid membranes presents a significant challenge. Thin films made from these structures are susceptible to mechanical damage (cracking, tearing or breaking) (Tan and Cheetham 2011), which can easily lead to defects, reducing the performance of such membranes or even eliminating them from use.

The combination of good separation properties of the particles and the mechanical strength of polymers is achieved in mixed-matrix membranes (Goh et al. 2011). A study focused on predicting the separation properties of mixed-matrix membranes containing MOF-COF hybrids is particularly interesting (Aydin et al. 2023). Using the Maxwell model (Pal 2008), permeability and selectivity calculations were made for mixed-matrix membranes for CO2/N2, CO2/CH4, H2/N2, H2/CH4, and H2/CO2 mixtures. Numerical studies were conducted for as many as 966,330 different configurations of MOF/COF/polymer/gases. The conclusions from these calculations can be summarized as follows: points on the Robeson plot describing MMM membranes containing COF structures are below the Robeson upper bound, points describing MMM membranes containing MOF structures are clearly above the Robeson upper bound, while points describing MMM membranes containing MOF-COF hybrids are just above the Robeson upper bound. These results could lead to abandoning research on mixed-matrix membranes containing MOF-COF hybrids in favor of membranes containing only MOF structures. However, the analysis of previously cited experimental data shown in Figure 1 for mixed-matrix membranes containing MOF and COF structures leads to the conclusion that the general conclusions drawn from numerical calculations are not entirely accurate. As shown in Figure 3, some MOF-containing membranes lie below the Robeson upper bound, and some COF-containing membranes lie above it. Discrepancies between the calculations and experiments arise from the assumption of an ideal filler distribution in the membrane matrix, which does not occur in practice. Given that the predictions from numerical calculations may not reflect the results obtained in experimental studies, research on mixed-matrix membranes containing MOF-COF hybrids should continue, as their process and operational properties may provide a viable alternative to current technical solutions.

So far, there have been few studies in the literature describing mixed-matrix membranes containing MOF-COF hybrids for gas separation. Searching in Web of Science, Scopus, and Google Scholar returns only two results. The first study involves a hybrid Cu(BDC-NH2)/TpPa dispersed in the polymer Pebax (Liang et al. 2024). For the CO2/CH4 gas mixture, a permeability of 815.9 barrer and an ideal separation factor of 20.3 were obtained, compared to a permeability of 472.9 barrer and selectivity of 18.4 for the Pebax membrane. A moderate improvement in separation properties was achieved compared to the homogeneous membrane, but there was no significant breakthrough. The point on the Robeson plot for this membrane lies below the Robeson upper bound. The second study concerns a mixed-matrix membrane in which the hybrid MOF-COF NH2-UiO-66@TpPa-1 was dispersed in a polysulfone matrix (Cheng et al. 2019). For the same CO2/CH4 mixture, a permeability of 7.1 barrer and an ideal separation factor of 46.7 were achieved, compared to a permeability of 6.68 barrer and selectivity of 27.83 for the polysulfone membrane (Suhail et al. 2023). This results in only a slight improvement in the separation properties of the membrane.

7 Summary

Research on new gas separation membranes aims to identify economically viable solutions that can achieve membrane properties surpassing the Robeson upper bound. The literature analysis conducted in this paper indicates that a promising research direction involves the use of nanoporous MOF and COF structures, as well as their hybrids. Both ultra-thin film membranes made solely from these materials and heterogeneous mixed matrix membranes (MMMs) often demonstrate much better process parameters than other membranes used for gas separation. A particularly interesting and underexplored research direction is the use of MOF-COF hybrids in membrane fabrication. Thin-film membranes produced from these hybrids exhibit documented properties that can be considered potentially groundbreaking for membrane-based gas separation technologies. Additionally, the mixed matrix membrane area incorporating MOF-COF hybrids remains largely unexplored but shows potential for applications of these hybrid fillers in heterogeneous membranes.

As a final summary of the considerations on the use of MOF-COF hybrids for gas separation, the information in Table 2 is summarized, which synthetically presents the issues considered in this work.

Table 2:

Selected issues related to the use of MOF-COF hybrids for gas separation.

Scaling-up Thin-film MOF-COF hybrid membranes face challenges in industrial implementation due to susceptibility to mechanical damage (e.g., cracking, tearing) during fabrication and operation. Scalable production methods for uniform, defect-free membranes are urgently required
Mechanical stability While thin-film MOF-COF membranes offer high separation efficiency, their mechanical fragility limits long-term industrial viability. Mixed matrix membranes (MMMs) incorporating MOF-COF hybrids in polymer matrices provide a synergistic solution, enhancing mechanical durability without compromising separation performance
Heterogeneity in MMMs Uniform dispersion of MOF-COF hybrids within polymer matrices is critical but remains technically challenging. Poor dispersion results in agglomeration, causing defects and reduced efficiency. Surface functionalization and advanced processing techniques are needed to improve distribution
Economic viability High synthesis costs and scaling difficulties hinder widespread adoption of MOF-COF hybrids. Developing cost-effective synthesis routes and recycling strategies is essential for industrial feasibility
Research gaps Limited experimental validation of MOF-COF hybrids in MMMs for gas separation constrains progress. Current studies often rely on theoretical models that overlook practical fabrication and operational conditions. Rigorous experimental testing is imperative to bridge this gap
Opportunities MOF-COF hybrids represent a breakthrough in separation technologies, particularly for demanding applications such as hydrogen purification (H2/CO2) and carbon capture (CO2/CH4). Modular design enables precise tailoring of pore sizes and functionalities, achieving exceptional selectivity and permeability. Integration with advanced fabrication methods (e.g., 3D printing, layer-by-layer assembly) could transform membrane manufacturing
Corresponding author: Maciej Szwast, Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warynskiego 1, Warsaw 00-661, Poland, E-mail:

Funding source: Politechnika Warszawska

Award Identifier / Grant number: IDUB

Acknowledgments

The authors thank Warsaw University of Technology for financial support of research and literature studies as part of the IDUB program.

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission. M.S.: conceptualization, writing, resources, editing, funding, project administration, supervision; D.P.: conceptualization, writing, resources.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The authors state no conflict of interest.

  6. Research funding: Warsaw University of Technology, IDUB program.

  7. Data availability: Not applicable.

Abbreviations

BDC

benzene dicarboxylate

COF

covalent organic framework

CTF

covalent triazine framework

FcDc

ferrocene-1,10-dicarbaldehyde

GPU

gas permeation unit

KIM

kidney injury molecule

MMMs

mixed matrix membranes

MOF

metal-organic framework

MOP

metal-organic polyhedra

NH2-MIL-

metal-organic framework functionalized with amino groups

PAF

porous aromatic framework

PEBAX

polyether block amide

PIM

polymers of intrinsic microporosity

PSA

prostate-specific antigen

TAPT

2,4,6-tris(4-aminophenyl)-1,3,5-triazine

TpPa

triformylphloroglucinol-phenyleneamine

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Received: 2024-12-12
Accepted: 2025-03-04
Published Online: 2025-03-25
Published in Print: 2025-07-28

© 2025 the author(s), published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/revce-2024-0088
Keywords for this article
MOF; COF; hybrid; membranes; mixed matrix; gas separation
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