Biochar-based membranes for CO₂ separation and capture: from conventional membrane materials to sustainable alternatives

Abstract

Rapid urbanisation has led to global warming and releasing of CO₂ into the atmosphere which is the primary anthropogenic greenhouse gas, accounting for almost 65% of the radiative forcing that contributes for global warming. With many innovations to mitigate this ongoing climate threat, capturing CO₂ from the atmosphere utilizing membranes-based methods are being focused on in contemporary studies. Membrane separation of CO₂ has higher efficiency, lower energy demand, cost effectiveness and scalability. The present work evaluates the existing membrane-based techniques for CO₂ capture including Polymeric membranes, Inorganic membranes, Mixed Matrix membranes (MMM), Metal organic frameworks (MOFs) based membranes, Nano material infused membrane, Carbon based membranes and biochar-based membranes. Although polymeric membranes have received widespread acceptance for carbon capture (CC), emerging hybrid membranes with multiple carbon capture mechanism, superior mechanical strength and surface chemistry are being extensively studied in recent times. Sustainable and green carbonaceous membranes such as activated carbon and biochar-based membranes formulated from a range of bio-waste is another avenue of recent research that adheres to the circular economy framework. However, there are very few works on biowaste derived biochar membranes for CC, though they show promising efficiency.

1 Introduction

Carbon Dioxide (CO₂) is one of the most important greenhouse gases (GHG) released due to anthropogenic activity and it accounts for about 65% of the entire radiative forcing contributing to global warming (Mehmood et al., 2022). Scientists have projected that the increase of global average temperature from 1.5 °C to 4.5 °C by the end of this century (IPCC, 2021) has resulted due to increase in carbon emission in the last decade. Concentration of CO₂ in the atmosphere has increased rapidly from a pre-industrial (∼280 ppm) era to over 421 ppm by 2024 (Tans et al., 2024). Studies has also reported an increase in concentrations of other greenhouse gases like CH₄ (13%) and NO₂ (9%) (WMO, 2023). Several paleoclimate data suggest that, the current rate of CO₂ increase is unprecedented over the past 800000 years. Atmospheric CO₂ is now 50% higher than it was before the Industrial Revolution (Letcher, 2020). This increase in has mainly resulted due to burning of fossil fuels in thermal power plants, transportation, deforestation and agricultural activities (Nunes, 2023). As per a report by the International Energy Agency, the increase of CO₂ emissions has contributed to one-fourth of the total emissions worldwide in 2021 (Dai and Deng, 2024). The rapid growth of consumeristic mindset has also played an important role in increasing global emission of GHGs (Li et al., 2023).

1.1 The threat of carbon dioxide to the environment

The increase in CO₂ levels have resulted in several adverse impacts including climate change, sea level rise, alterations in the timing and distribution of rain and disturbance of coastal, marine ecosystems (Masson-Delmotte et al., 2021). There has also been an increased frequency of extreme weather events such as hurricanes, droughts, wildfires, and heatwaves due to CO₂ induced climate alterations. Ocean acidification due to increased absorption of CO₂ by seawater is another concern, which in turn is causing detrimental effect on coral reefs and other marine ecology. The oceans have absorbed a significant amount of atmospheric CO₂, resulting in a decline of pH by approximately 0.1 units causing nearly a 30% increase in ocean acidity (Pratiwi et al., 2024).

The socioeconomic impacts of the increase of GHGs, especially CO₂ are also alarming. Several studies project that climate change has the potential to reduce global GDP by 5%–20%, and impact food security of developing nations (Kotz et al., 2024). The Intergovernmental Panel on Climate Change (IPCC) reports that there will be a long-lasting effect on people and ecosystems if the CO₂ concentration increased in the present rate (IPCC, 2023). According to the recently released Sixth Assessment Report (AR6) of the IPCC, climate change is the most serious threat with visible impacts across every region of the world (IPCC, 2021; IPCC, 2022). The World Health Organization (WHO) reports that approximately 250,000 additional deaths per year can occur within 2030–2050 in connection with climate change (World Health Organization, 2021). Recent studies show that, global mean sea levels have increased by 11.1 cm between 1993 and 2023. This severely intensifies the risks of submergence and flooding of coastal areas, saltwater intrusion, human rehabilitation, biodiversity and habitat loss (Hamlington et al., 2024). Global biodiversity loss is another serious consequence of climate change due to increase of GHGs. World Wildlife Fund reports have projected approximately 73% decline in monitored wildlife diversity between 1970 and 2020, threatening overall ecosystem stability, which can lead to species extinction (Deinet et al., 2024).

There is an urgent need to solve the crisis of rising levels of CO₂ for mitigating climate change. Use of renewable energy like solar, wind, hydrothermal and geothermal energy are one way in which this crisis can be addressed (Owusu and Asumadu-Sarkodie, 2016). However, despite their growing adoption and advancements, the intermittent nature and limited scalability of renewable energy systems pose challenges to their widespread implementation as the sole solution. To bridge this energy transition gap, Carbon Capture and Storage (CCS) technology has gained considerable attention as a complementary approach to reduce CO₂ emissions from fossil fuel-based power plants (Kazlou et al., 2024).

2 Framework of CO₂ capture techniques

To arrest the annual temperature, rise to <2 °C due to extensive GHG emission, a net zero emission goal was adapted (Mollahosseini et al., 2025). To achieve net zero emission goals as per SDG 13 (Climate Action), a 75% decrease in release of GHG by 2050 is required (Hou R. et al., 2025). With the increasing demand and crisis of energy worldwide, carbon capture (CC) techniques are being widely studied. Reducing emissions globally using CC techniques in various industries, especially fossil fuel-based ones, is the most effective pathway for sustainable development (Dai and Deng, 2024).

CO₂ separation and capture are conventionally done via three main pathways in power generating sectors which include pre-combustion capture, post combustion capture and use of oxy-fuel (Obi et al., 2025).

2.1 Pre-combustion CC techniques

In pre combustion method, the CO₂ is removed prior to combustion process by converting the fossil fuel to syngas which is a mixture of hydrogen and carbon monoxide (CO) (Hua et al., 2023). Gasification or reforming of the fossil fuel is done to achieve this syngas. Through a further water-shift reaction, the CO is converted to CO₂ and then separated from the hydrogen which is used for the combustion process in an Integrated Gasification Combined Cycle (IGCC) system (Ibigbami et al., 2024). Pre-combustion is advantageous as has a more robust configuration along with lower energy requirement for the separation process. High concentration of CO₂ and pressure (∼2–7 MPa) in the syngas helps in driving the separation process (Raganati and Ammendola, 2024). However, the major disadvantage of the process is the complicated steps involved in syngas production and the process is not cost effective (Obi et al., 2025).

2.2 Post-combustion CC techniques

Post combustion CC techniques are more widely used and involves removal of CO₂ after the fossil fuel burning is done. Various downstream steps are required for the removal of impurities such as dust, NO_x, SO₂ etc., from the flue gas (Wu et al., 2020). The flue gas usually goes via steps as denitrification and desulfurization before CC (Hong, 2022). Post combustion processes are usually more versatile and do not interfere with the energy production steps and has higher scalability (Raganati and Ammendola, 2024). The disadvantages of this process lie in the fact that the high volume of gas is released at atmospheric pressure that has lower driving pressure for any CC process (Obi et al., 2025). Due to the low driving force in post combustion flue gas, separation process has to be robust. Conventionally aqueous monoethanolamine are utilized to absorb the CO₂ (Zhang et al., 2024). This step is followed by desorption of CO₂ and recycling of the solution (Allangawi et al., 2023).

2.3 Oxy-fuel combustion

The other alternative to post and pre combustion CC method is oxy-fuel combustion. In this process the combustion is conducted in high oxygen atmosphere to produce a flue gas high in CO₂ and water vapour. This flue gas is then subjected to CC technologies and its advantage lies in the high concentration of CO₂ (∼98%) and low concentration of NO_X making the process cleaner and highly efficient (Adamu et al., 2020). This process also facilitates use of a variety of fuels and the flue gas emitted is also low in dust, SO₂ and other air pollutants (Obi et al., 2025). Although oxy-fuel combustion is a highly efficient process, its major drawback is its high cost and energy requirement. Production of pure oxygen for the fuel gas remains of the most energy intensive steps (Li et al., 2022). Presently, cryogenic distillation is widely used as the primary method for production of pure oxygen for oxy-fuel combustion (Chen et al., 2019).

The presence of concentrated CO₂ in the flue gas leads to corrosion of system, adding to extra cost of maintenance (Obi et al., 2025).

Figure 1 illustrates the three main carbon capture methods used in industries such as power plants.

FIGURE 1

3 Methods for CO₂ separation

CO₂ separation at different stages is now, by far the most important step for achieving reduced emission. Choice of the right separation and capture method is important for achieving the goal. While selecting the separation process special emphasis is given to the composition, source, temperature and pressure of the flue gas (Hekmatmehr et al., 2024). The medium for CO₂ capture is also vital in this process. The efficiency of the separation technique depends on the selectivity and stability of the separating media (Dziejarski et al., 2023).

Various mechanisms are used to separate CO₂ during post-combustion, precombustion and oxy-fuel combustion (Al Mesfer et al., 2024). These methods include adsorption, absorption, cryogenic and membrane separation. In some instances, a combination of these methods is used (Mukherjee et al., 2022). Finalization of the process and mechanism dependent on the raw material used and the operational process. The comparison of various CO₂ separation mechanism highlighted in Table 1 associated with pre- and post-combustion CO₂ separation systems.

TABLE 1

Technology	Mechanism	Advantages	Drawbacks	CO2 capture Efficiency (%)	Energy demand (MJ/kg CO2)	Maturity (TRL)
Absorption	Physical, chemical absorption of CO2 using a liquid solvent followed by regeneration by heating or pressure reduction	• High CO2 capturing efficiency • Wide use in industries • Tested operation reliability	− High energy requirement for solvent regeneration − Solvent degradation and corrosion issues − High operational and maintenance cost − Large equipment size	80–99	4.0–5.0	9
Adsorption	Physical or chemical adsorption of CO2 onto a solid sorbent with regeneration by temperature or pressure swing	• Less energy requirement • Suitable for compact systems • Easy operation and maintenance	− Limited adsorption capacity performance affected by moisture and impurities − Sorbent degradation over repeated cycles − Scale-up challenges for industrial application	80–98	2.0–4.5	7–9
Cryogenic separation	Separation of CO2 by cooling and liquefaction at very low temperatures, mainly for high CO2 concentration streams	• Generate liquid CO2 for commercial use • Simple operational process • High purity CO2 recovery	− High energy consumption expensive cooling system − Less suitable for low CO2 concentration − High operational cost	90–99	>9.0	9
Membrane separation	Selective transport of CO2 through a membrane driven by pressure difference across the membrane	• Lower space requirement • Reduced ecological footprint • Lower maintenance cost • Compatible with existing systems	− Lower selectivity − Membrane degradation − Multi-stage operation often required	80–90	6.0–6.5	6

Advantages and drawbacks of various CO₂ separation methods.

3.1 Absorption

The most commercially applicable and useful technique is absorption, mainly used in thermal power plants and chemical manufacturing industries due to its simple operational process, comparatively lower energy requirement and versatility (Raganati and Ammendola, 2024). Carbon capture using absorption used both physical and chemical process. Principle of physical process uses Henry’s law for absorption at low temperature and high-pressure situation (Ochedi et al., 2020). In case of chemical absorption, CO₂ forms a weak bond with the solvents to produce an intermediate molecule, and this CO₂ can be subsequently released through heating. The most widely used solvents for this process are amine and carbonate solutions (Shah et al., 2020). Selection and screening of solvent is the most important criteria for efficiency of separation of carbon through absorption method. Various physical solvents like propylene carbonate, rectisol, Selexol etc., and chemical solvents such as Monoethanolamine (MEA), Diethanolamine (DEA), Methyl diethanolamine (MDEA) are used for this method (Khan et al., 2025). Mixture of solvents are also used in absorption-based CO₂ capture to increase the efficiency of various different solvents which enhances the overall performance of the process. Studies shows that amine-based solvents like MEA have gained almost 80%–99% CO₂ separation capabilities although a massive amount of thermal energy (around 3–5 GJ t^-1 CO₂) is required to regenerate the solvents (Du et al., 2024). Though absorption is a technique that is widely accepted and matured, it requires huge capita, energy and space for installation (Rahimalimamaghani et al., 2023a).

3.2 Adsorption

Removal of CO₂ through adsorption is another promising approach in recent times due to its less energy requirement, flexibility and compatibility with various process systems (Raganati and Ammendola, 2024). Solid and liquid adsorbents namely, activated carbon or porous carbon-based material (Creamer et al., 2016), metal-organic frameworks (MOFs) (Lin et al., 2021), zeolites (Tao et al., 2024), solid amine-based materials (Hack et al., 2022) and porous liquids are most effective for separation of CO₂ (Fan et al., 2025). The adsorption efficiency, selectivity, and regeneration ability of adsorbents depends on various factors, such as composition and structure of adsorbent, surface area, pore size distribution, surface chemistry of materials and external conditions like temperature, pressure, moisture content etc (Saenz et al., 2023). The adsorption mechanism can be divided into two main types namely, physisorption and chemisorption. Physical adsorption or Physisorption is the reversible process in which Van der Waals interaction occurs between CO₂ and the adsorbent. Chemisorption occurs when any chemical bonds developed between CO₂ and the adsorbent. Chemisorption is highly selective toward the adsorbent and needs high energy to regenerate the solvent (Gunawardene et al., 2022). The basic adsorbent properties that influencing CO₂ adsorption are shown in Figure 2.

FIGURE 2

Carbon-based porous adsorbent materials like carbon nanotubes (CNTs) and graphene have been found to be highly efficient in capturing CO₂ (Pan et al., 2023). CNTs are linear nanomaterials developed by cylindrical structures of rolled graphene layers consisting of either a single or multiple layers, while graphene consists of carbon atoms with a two-dimensional honeycomb lattice arrangement through sp² hybridization (Qin et al., 2019). As compared to other carbon-based porous adsorbent materials, CNTs and graphene provide excellent uniformity in their structure along with faster diffusion of CO₂, but their use in various applications is limited due to their expensive fabrication process (Ren et al., 2017).

MOF based adsorbents consist of a central metal ion linked with organic ligands forming a three-dimensional complex pours network (Mahajan and Lahtinen, 2022). These materials are noteworthy due to their large surface area, tuneable porous structure, versatility, stability and low density making them perfect for separation of CO₂ (Singh et al., 2020). Composite MOF based adsorbent such as water stable titanium bisphosphate, MIL-91(Ti) added with graphene oxide (GO) as additive can increase the efficiency of CO₂ capture (Muschi et al., 2021). Various mechanisms are used for CO₂ adsorption based on material composition like electrostatic interaction, Van Der Waals interactions, weak chemical bonding etc (Elhenawy et al., 2020). Among the various known metal–organic frameworks (MOFs), MOF-74 analogues have raised significant attention because of their excellent CO₂ adsorption capacity (Suh et al., 2017). This high performance is mainly due to the presence of open metal sites within their hexagonal channels aligned along the c-axis (Wang et al., 2024). Extensive research has been conducted on these materials to regulate CO₂ adsorption properties and to achieve selective CO₂ capture, even under humid or wet operating conditions (Das et al., 2025).

Zeolites used as an adsorbent consist of microporous aluminosilicates structure based on a frame work of TO₄ tetrahedra (T = Si or Al) (Perez et al., 2022). Based on the Si/Al ratio, zeolites can be divided into three types such as low-silica zeolites, intermediate-silica zeolites, and high-silica zeolites. If an aluminium atom can be introduced in the structure, it induces a negative charge on the framework, and this can be compensated by positively charged cations. Increasing the quantity of aluminium in the system or cation introduction can increase the CO₂ capture capacity of the zeolites (Dias et al., 2025).

Amine based adsorbent are widely used for CO₂ capturing from flue gas due to their excellent performance (Chen et al., 2025a). Amine molecules can be grafted onto a porous structure through impregnation, covalent grafting etc. It is called solid amine, which are used as an efficient adsorbent. CO₂ and solid amine produce ammonium carbamate in anhydrous condition and in presence of moisture they form ammonium carbonate and bicarbonate (Lin et al., 2023).

Organic polymers consisting of microporous cavity are also used effectively for adsorption of CO₂ due to large surface areas, adjustable pore sizes and abundant functional groups with strong affinity towards CO₂ (Song et al., 2022). Inorganic salts, oxides of metals and natural minerals incorporated on solid surfaces are also used as adsorbents. This type of adsorbents interacts via acid base reaction with CO₂ (Khdary et al., 2022). Recently wood biochar has been established as an efficient adsorbent in capturing CO₂ owing to its high carbon content (82.14%–84.70%) and relatively less ash content (3.28%–4.61%). Studies shows that, wood biochar is more effective than polyethyleneimine impregnated silicon carbide fibres and TiO₂. The efficiency of CO₂ absorption is highly dependent on the porosity, alkalinity and surface area of wood biochar (Wahby et al., 2026).

3.3 Cryogenic process

Cryogenic process is another viable way for separation of CO₂ from flue gas. This process can reduce almost 95%–99% of CO₂ from thermal power plant emission along with other impurities like SO_X and NO_X (Wanison et al., 2025). Liquefied natural gas is used to supply cryogenic colling effects and capture CO₂ (Font-Palma et al., 2021). This technique is used in oxyfuel combustion technology and also during post combustion separation of CO₂ from exhaust gas. Mechanisms like compression, separation, expansion and cooling are used in this process, which can efficiently separate up to 99.17% CO₂ from the gas mixture (Shen et al., 2022). Cryogenic carbon capture operates at very low temperature (up to −500 °C), which condense or solidify the gas streams and selectively separates CO₂ with lower energy consumption (Asgharian et al., 2023). Two types of cryogenic capture methods are widely used, namely, cryogenic distillation and cryogenic desublimation. Cryogenic distillation method liquefies the gas stream at low temperature and separate CO₂ and in cryogenic desublimation process CO₂ is solidified (dry ice) by freezing and is then isolated from other flue gases (Aneesh and Sam., 2023). The general method of cryogenic process is illustrated in Figure 3. Cryogenic capture works using physical separation techniques based on the principle of phase equilibria, specifically boiling points for vapor–liquid (V-L) separation, and sublimation temperature for vapor–liquid (V-S) separation of gases. Recently there are significant advancements in this field, focusing on improving efficiency, scalability, and integration with existing CC technologies (Luberti al., 2024).

FIGURE 3

3.4 Membranes

Membrane-based CO₂ separation has raised considerable attention as cost effective and simple solution toward industrial decarbonisation (Park et al., 2025). Membrane separation emerged in the 1980s, when it was used for natural gas purification in industrial process as an alternative to amine-based solvents (Gkotsis et al., 2023). This technology uses selective membranes to isolate CO₂ from other gases present in flue gas streams. The schematic mechanism of CO₂ separation using membranes is shown in Figure 4. Various parameters are involved that affect the efficiency of membrane separation, such as concentration of CO₂, temperature of the exhaust gas, gas pressure, composition of permeate gases etc (Xu et al., 2018). Several types of membranes are used for the separation of CO₂ distinguished by its structure and composition and underlying separation mechanism. Mainly three types of membranes are widely used namely, polymeric membranes, inorganic membranes and mixed-matrix membranes (MMMs) (Christensen et al., 2025). Recently carbon-based membranes have received growing attention for higher efficiency in CO₂ removal (Li et al., 2026). Membrane separation technique offers greater advantage than absorption and adsorption process in several ways. This process does not need any chemical reactions or energy invasive solvent regeneration, which eases the operational process and reduces the overall ecological footprint (Merkel et al., 2010).

FIGURE 4

4 CO₂ separation using membrane techniques

The formation of membranes for CO₂ capture and sequestration is an essential technological advancement in the global front to mitigate climate change (Mollahosseini et al., 2025). Membranes were initially used as an alternative to amine solvents as absorbents for CO₂ capture (Gkotsis et al., 2023). However, due to its versatile and eco-friendly nature, membranes are being used more increasingly (Lei et al., 2025). This technique does not produce any secondary pollutant during the separation process as compared to the more conventional absorption using solvents (Seong et al., 2020). Moreover, it has been seen that specially designed membranes are highly selective and efficient in CO₂ separation (Odunlami et al., 2022). Membranes are also preferred over other separation techniques due to their easy operational method, cost effectiveness and lower energy requirements (Gkotsis et al., 2023). Membrane technology provides added advantage of high scalability, easy installation in isolated areas and no added reagent requirement (Aninwede and Kratky, 2025). It has also been found that when CO₂ concentration becomes >20% in the feed, the partial pressure increases the selectivity of membranes leading to greater CO₂ separation (Park et al., 2025).

4.1 Mechanism of CO₂ separation using membrane

4.1.1 Solution diffusion mechanism

CO₂ separation usually occurs in membranes via solution diffusion transfer. In the solution diffusion removal, CO₂ is separated in three main steps. The process initiates with the CO₂ dissolution onto the surface of the membrane from the feed flux. This is followed by the diffusion of CO₂ through the membrane and the final step being desorption and removal of the gas from the permeate end. The driving force for the CO₂ separation in this process is the pressure difference between the feed and permeate phase which is achieved by compression and vacuum. In the solution diffusion transfer, solubility and diffusivity are related. Gases with higher solubility can easily diffuse through a membrane from the feed to the permeate side. The difference between the two being that solubility is the quantity of gas dissolved in membrane material and diffusivity the prompt movement of the gas across the membrane (Fajrina et al., 2023). Solubility is determined by the gas’s interaction rate with the membrane material while diffusivity is determined by the kinetic size of the membrane chambers and the gas molecules (Aninwede and Kratky, 2025).

The permeability (Pm) of gas for this model is a product of diffusion coefficient D (m²/s) and solubility coefficient (S) of the gas on the membrane. It can be expressed as shown in Equation 1:where the solubility coefficient can be expressed as in Equation 2where ΔC (mol/m³) is the concentration of the gas dissolved from the flux and ΔP (Pa) is the pressure difference across the membrane.

The flux across the membrane is calculated using Fick’s law shown in Equation 3where F_c is the flux of gas c (mol/m²/s), Pm_c is the permeability of the membrane for gas c, t (m) is the thickness of the membrane. P_f is the pressure in the feed and P_p is the pressure (Pa) of the permeate. X_c and Y_c are the high- and low-pressure mole fraction (mol/mol).

More conventionally CO₂ permeability is expressed in terms of permeance via the unit GPU. GPU can be calculated using Equation 4.

Membrane selectivity is another crucial parameter in CO₂ separation. The feed flux contains multiple gases and the comparative permeation of one gas in comparison to the other through the membrane is known as separation factor (α).

α is calculated using the Equation 5where Y_b and Y_c are mole fraction of gas b and c in permeate respectively and X_b and X_c are mole fraction of gas b and c in the feed.

Membranes for CO₂ adsorption and separation are two techniques that have been investigated in various literature. The difference being that in the first case there is an adsorbent, usually liquid, embedded in the membrane matrix that captures the CO₂ based on mass transfer, whereas in the latter, separation is done via selectively allowing CO₂ to pass through the membrane matrix (Park et al., 2025).

4.1.2 Facilitated transport mechanism

In facilitated transport mechanism, the membranes are incorporated with carrier components, which are chemical compounds capable of binding with CO₂ and transporting it across the membrane. CO₂ enters the membrane and reacts quickly with the carrier component and the complex diffuses through the membrane. These carriers, usually basic, do not bond with lighter gases, making them highly selective and also formation of reversible bonds with acidic CO₂ makes them easily regeneratable (Kamio et al., 2023). CO₂-carrier complex flow through the membrane driven by transmembrane partial pressure variations, supressing the unreacted lighter gases (Kadirkhan et al., 2022). The partial pressure difference in the feed and permeate side of the membrane allows the carriers to release the bonded CO₂, making the carrier free to react with CO₂ from the feed (Tong and Ho, 2017). Amines have been widely used as carriers for CO₂ facilitated transport membranes as they form reversible CO₂ bond utilizing the zwitterion mechanism (Liang et al., 2025). Lighter gases are transported only via solution diffusion process, whereas CO₂ is transported both by the carrier complex and physical diffusion, making facilitated transport membranes faster and more efficient in CO₂ separation. Another advantage of facilitated transport membrane is that selectivity-permeability trade off or Robeson’s upper bond does not govern the separation process (Tong and Ho, 2017).

The CO₂ flux across the facilitated transport membrane can be calculated using Equation 6.where N_x is the steady state flux of CO₂, Diffusion coefficients of the CO₂-carrier complex and CO₂ are represented by D_XC and D_X respectively. C_XC,P and C_XC,F stand for the CO₂-carrier complex concentration in the feed and permeate side of the membrane respectively. C_X,F and C_X,P are the concentration of dissolved CO₂ in the feed and permeate interface respectively.

Facilitated transport mechanism is highly effective at lower concentration of CO₂ due to the presence of unsaturated carriers making them suitable for low pressure feed of flue gas like in coal-based power plants. Carriers can be mobile or fixed and are selected based on the membrane composition.

4.1.3 Membrane contactor

Another widely used CO₂ separation mechanism is the use of membrane contactor. The steps involved in the process include the movement of feed gas mixture onto the membrane interstitial space driven by transmembrane concentration variation. CO₂ diffuses through the membrane and reach the gas-liquid interphase wherein the CO₂ reacts with the liquid phase adsorbent (Li et al., 2020). There are mainly two types of membrane contactor, inert and catalytic. Inert contactor acts as a barrier without chemically reacting with the gas, whereas in catalytic contactor there is coating of catalytic material that facilitates the separation process. In CO₂ capture, membrane contactors employ hydrophobic membranes to enable efficient mass transfer between the gas stream and the liquid absorbent while preventing direct contact between them (Hafeez et al., 2021). Unlike the conventional separation mechanisms, the driving force for membrane contactors is concentration gradient and a very small drop in pressure is sufficient to keep the gas-liquid phase mobility at membrane pores (Petukhov et al., 2022). Gas-liquid membrane contactors offer several advantages such as scalability, a large contact area in a compact space allowing efficient transfer of CO₂ from the gas phase to the liquid absorbent. The gas and liquid flow can be controlled independently without flooding or weeping of membrane (Kianfar, 2023).

4.1.4 Molecular sieve mechanism

Molecular sieving is another a CO₂ separation mechanism where the feed gases are separated based on molecular size. In membranes various fillers are added that contain tiny pores that act like molecular sieves (Katare et al., 2023). The pore size of these fillers is slightly larger than the kinetic diameter of CO₂ but smaller than other feed gas molecules, thus allowing CO₂ to pass through the pores blocking the other gases. This results high selectivity in these membranes. Since the kinetic diameters of CO₂ and gases such as N₂ and CH₄ differ by only a small amount, the pore size of the filler must be carefully controlled to achieve effective separation. Therefore, microporous materials such commonly used as fillers in carbon sieve membranes because they have uniform molecular-sized pores that provide high CO₂ selectivity and improve membrane performance.

When evaluating membrane efficiency for CO₂ separation, permeability and selectivity are the two most important factor to consider. The performance of a membrane depends on how fast and specifically it can separate CO₂ from other flue gases. The cost of the membrane process is also determined by these two properties. The process economics is a trade-off amid energy cost governed by the membrane selectivity and capital cost, owing to the surface area of the membrane, that is governed by permeability. Increasing the selectivity of a membrane usually leads to a decrease in the volume of gas that permeates through the membrane, leading to a loss in energy. Enhancing permeability leads to a reduction of effective area of the membrane that adds in capital cost required for a proper feed flow rate (Kamio et al., 2023). This trade-off relation was given by Robeson in 1991 in the form of a plot which represents the logarithmic relationship between the selectivity of a gas pair and the permeability of the faster-permeating gas. The performance of a membrane in separating CO₂ is accessed through this empirical relation which preferably should be in the Robeson upper limit (Gkotsis et al., 2023). Membranes in the Robeson upper boundary usually exhibit high permeability and low selectivity (Tong and Sekizkardes, 2021). Highly selective membrane generally has a low specific energy, whereas moderately selective membranes with high permeability have lesser area requirement and are economically favoured (Asadi and Kazempoor, 2021). Efforts have been made over the years to formulate membrane materials capable of exceeding the Robeson limitation. The Robson’s plot was first developed in 1991 which the selectivity-permeability of all polymeric membranes were plotted against an empirical line. Accordingly, depending on the selectivity-permeability performance, membranes are placed either above or below the line. The upper right-hand corner in known as the commercially interesting zone where high performing membranes are usually placed. In 2008, based on new data available, the Robeson’s plot was redone and published. Figure 5 shows the Robeson’s trade off from 1991 to 2008. Most of the data presented in the 2008 Robeson’s plot was based on polymeric membranes (Jana and Modi, 2024). The plot is used to evaluate newly formulated membrane matrix as it provides the best permeability-selectivity combination of binary pairs of gases at any point.

FIGURE 5

Membrane efficiency is adversely affected due to pore clogging and membrane fouling over time, thus anti-fouling properties of membrane material should also be evaluated. The fouling of membranes is time dependent and other parameters that effect process productivity is temperature, cross membrane pressure and humidity (Kim, 2022).

4.2 Types of membranes used for CO₂ separation

Various types of membrane have been developed for the separation of CO₂ from industrial flux. These membranes can be widely classified as organic and inorganic membranes (Raganati and Ammendola, 2024). Organic membranes are mostly polymeric membranes whereas inorganic membranes include membranes fabricated with zeolite, ceramic, silica and metal-organic framework (Lin, 2025).

4.2.1 Polymeric membrane

Polymeric membranes are thin, selective membranes designed for post combustion capture of CO₂ (Koçak et al., 2026). These membranes showed high permeability and selectivity for CO₂ (Troy and Wagner, 2011). They are most widely used due to their low cost and mechanical flexibility. Adjustable pore size and high porosity of microporous polymers and molecular sieves are now gaining considerable attention (Lee and Bae, 2024). Common polymers include polyimides, polysulfones, and cellulose acetate (Gkotsis et al., 2023). Polymeric membranes are thought to be the most promising membranes matrix as they provide various advantages such as a porous surface that allows high CO₂ permeability, low cost of material, lightweight and easy to integrate into existing plants, low temperature operation, highly processable, and require relatively little energy, which lowers operating costs and environmental impact (Aninwede and Kratky, 2025; Khaki et al., 2021).

A variety of polymeric materials have been studied for CO₂ capture and separation, including polyimide (PI), polysulfone (PSF), cellulose acetate (CA), polyetherimide (PEI), and polymers of intrinsic microporosity (PIMs) (Jana and Modi, 2024). It was established that membranes with high gas permeability shows lower selectivity, whereas highly selective membranes often resulted in reduction of permeability, limiting their overall separation efficiency (Robeson, 1991; Goswami and Ingole, 2026). Glassy polymers have attracted considerable attention due to their excellent thermal and mechanical stability and strong affinity towards CO₂ (Fan et al., 2024). Despite these advantages, most polymeric membranes face an inherent trade-off between permeability and selectivity (Li et al., 2026).

4.2.2 Inorganic membrane

Inorganic membranes are composed of materials such as zeolite, ceramics silica etc. Compared to polymer membranes, porous inorganic membrane (PIM) offers better permeabilities often at the expense of lower separation factors, giving smaller layouts and reduced investment costs also unlike adsorbents, PIMs can operate continuously and handle higher flow rates, which adds value to their industrial application (Pera-Titus, 2014). Inorganic membranes require higher operating temperatures than polymeric membranes (Iulianelli et al., 2011), however they show higher stability at high temperatures and are chemical resistant with higher mechanical durability making them an attractive option in highly corrosive environment (Lin, 2025). Inorganic membranes can be utilized in various forms such as thin film membranes or self-supporting ceramic, glass or steel structure (Raganati and Ammendola, 2024).

The need for resistant membranes has driven formulation of inorganic membranes for industries that have harsh process conditions such as pharmaceuticals, waste water treatment and chemical industries. Inorganic membranes also show higher gas permeability as compared to organic membranes (Grekou et al., 2022).

4.2.2.1 Zeolite membrane

Zeolite membrane, because of its unique space-oriented pore arrangement has been studied for CO₂ capture. Zeolite membranes have narrow pore structure, strong electrostatic field, and high screening ability making them highly selective for CO₂ adsorption (Fan et al., 2024). Zeolite having pore diameters in the range of 0.3–1.0 nm has high CO₂ capture capacity through the molecular sieving effect (Sharma et al., 2021). CO₂ molecules are also strongly drawn to the electric field produced by the structural cations inside the zeolite framework because of their high quadrupole moment (Sharma et al., 2021). Ability of zeolite in CO₂ adsorption rises with increased pore volume and surface area, which improve molecular sieving, and the higher sodium content, fortifies the electric field (Salem et al., 2025). Though zeolite membranes have good efficiency, they are susceptible to thermal degradation when steam is present in the filtration chamber. Another drawback is that perfect zeolite membranes with enhanced selectivity are hard to produce at low costs (Rahimalimamaghani et al., 2023b).

4.2.2.2 Silica based membrane

Silica matrix incorporated with functional group is used to facilitate CC via post-synthesis grafting and in-situ condensation (Karimi et al., 2020). In Mesoporous silica membrane the CO₂ is chemisorbed onto the membrane active layer pore followed by diffusion throughout the membrane and finally desorption to the permeate side of the membrane, leaving behind the other gasses. With no intrinsic mechanical strength, ceramic, polymers and various microporous support are needed to help the mesoporous silica membrane to act as a path for transport process (Kim et al., 2015).

4.2.2.3 Ceramic membranes

Ceramic membranes are inorganic porous membranes fabricated from carbon nanotubules (CNTs), aluminium oxide (Al₂O₃) and titanium oxide. They have the advantage of enhanced durability and are stable under high pressure and temperature (Gkotsis et al., 2023). Ceramic membranes are mostly microporous and rely on surface properties, pore size and process parameters for the separation of CO₂ (Kamio et al., 2023). Al₂O₃ based ceramic membranes have been modified to enhance the separating efficiency of the membrane. Fu et al. (2023a) reported a modified hydrophobic Al₂O₃ based ceramic membranes that showed higher CO₂ capture by improving mass transfer. Fly-ash ceramic membranes can also be modified to superhydrophobic state via incorporation of silane grafts and fluoroalkylsilane which results in highly robust ceramic membrane with enhanced pore structure (Xue et al., 2025). The emerging technology of gas-liquid membrane CO₂ separation uses both membrane technology and absorption in which a liquid absorbent is infused in a membrane. Ceramic membranes provide excellent backbone for the gas liquid contact method. MEA absorbent used with ceramic membrane has shown a CO₂ removal efficiency of ∼95% with high mass transfer rate (Fu et al., 2023b).

4.2.3 Mixed matrix membranes (MMM)

Mixed matrix membranes (MMMs) have surfaced as one of the most innovative approaches for CO₂ capture (Hu et al., 2022). This method is very useful due to combination of flexibility and ease of processing of materials having strong adsorption efficiency with inorganic and hybrid materials (Ali et al., 2024). This type of membranes consists of inorganic particle inside a polymer structure, which increases strength and gas separation efficiency (Chua and Poon, 2024). MMM have various advantages over other membranes due to combination of CO₂ separation techniques of two or more filler materials (Wang et al., 2022). Most emerging membranes are using MMM for enhanced efficiency of the process. MMMs combined with microporous MOF or nanomaterials has potential in the near future to be developed for CO₂ capture and separation in real world applications (Chen et al., 2023). MMMs have been classified according to the filter types, polymer types, membrane structure and mechanism used and are shown in Figure 6. MOF-MMM are most widely used for separation of CO₂. Recent studies show improved efficiency and affinity toward CO₂ capture and higher selectivity toward CO₂/N₂ and CO₂/CH₄ (Ahsan et al., 2025). Kim et al. (2026) developed a MMM with 2D ZIF-8 nanosheets incorporated into poly (ether-blockamide) (Pebax) 1657 and Pebax 2533. The Pebax 1657 fabricated MMM showed enhances CO₂ permeability (∼350 Barrer) and also high CO₂/N₂ selectivity reaching up to 90 (Kim et al., 2026). Another study shows the growth of MOF on the zeolite surface including CaA@ZIF-8 core–shell structure to develop MMMs for CO₂ separation. This MMMs shows exceptional CO₂ permeability of 1142 Barrer with CO₂/CH₄ selectivity of 43.3 (Choi et al., 2024). Boutsika et al. (2025) studied CO₂ capture performance of Pebax MH1657-based MMMs integrating 5–20 wt% of Zr-based MOF, UiO-66, UiO-67, and also UiO-66 analogue with extended linker (UiO-66_A) or cluster (UiO-66_F) vacancies. Study result show that, combining the UiO nanoparticles increased CO₂ permeability to145 Barrer for the 20 wt% UiO-66_F MMM. Selectivity of CO₂/CH₄ and CO₂/H₂ also significantly increase with increasing MOF including UiO-66_F up to 25 and 18, respectively. MMM composed of SBA-15 and MOF-199 infused in PEBA polymer matrix has also shown high permeability for CO₂ of 67.11 Barrer and CO₂/N₂ selectivity of 3.48 while the CO₂/CH₄, and CO₂/H₂ selectivity were 38.36 and 17.12 respectively. The study also showed that in mixture of CO₂/CH₄, the permeability of CO₂ increased with increasing CO₂ concentrations (Dalakoti et al., 2025).

FIGURE 6

Dai et al. (2023) developed a MMM consisting of triphenyltriazine-based β-ketoenamine-linked covalent organic framework (TpTta-COF) into the polymer PIM-1. The homogeneous distributed covalent organic framework (COF) created interconnected pathways with enhanced CO₂ affinity and selectivity. This membrane consisting of PIM-1/TpTta-COF-6 exhibited remarkable stability and CO₂ permeability with elevation of CO₂/N₂ selectivity. Another study shows that CO₂ separation can be efficiently carried out by means of self-supporting or thin film MMM composed of 2D Ti₃C₂Tx MXene nanosheets and Pebax-1657. In particular, high CO₂/N₂ and CO₂/H₂ separation efficiency was observed. This was due to hydrogen bonding interaction of MXene with Pebax forming highly organized nanochannels facilitating CO₂ transportation (Shamsabadi et al., 2019).

He et al. (2026) developed a Pebax-based ultrathin MMM Combining with ZIF-8@COF composite porous nanosheets. The synthesis of ultrasmall ZIF-8 particles (∼4 nm) was obtained by direct growth on COF nanosheets to produce an ultrathin composite filler layer (∼11 nm in thickness). This combination of two materials gives the benefits of COFs high aspect ratio and good interface compatibility and CO₂ sorption capacity of ZIF-8. This ultrathin MMMs was capable of CO₂ separation with permeance value of 1365 GPU with CO₂/N₂ selectivity of 38.4.

Recent study involves the synthesis of hybrid matrices involving 3D and 2D indium MOF, MIL-68(In)-NH₂ and In(aip)₂ incorporated in polysulfone matrix. This synthesized MMMs were tested with biogas mixture (CO₂: CH₄ of 60: 40 vol%) and found to be effective CO₂ separator with permeability of 144 Barrer and 79.2 Barrer. The 15 wt% MIL-68(In)–NH₂/PSF membrane and 10 wt% In(aip)₂/PSF membrane exhibited remarkable CO₂/CH₄ selectivity (19.8 and 24.4, respectively). Various types of newly synthesized MMMs for selective separation of CO₂ from flue gas can show a new pathway for remediation of air pollution (Jonnalagedda and Kuncharam, 2025).

5 Limitations of membranes for CO₂ capture

Membranes are efficient separators for CO₂; however, they face various limitations when run in over a period of time. Membrane reusability declines due to factors such as aging, plasticization and interfacial defects.

5.1 Plasticization

Plasticization is a major challenge faced at high pressure CO₂ separation. In this phenomenon various components known as plasticizers gets integrated into the membrane matrix, reducing the selectivity and increasing the permeability. This effect is especially evident for polymeric membranes and is one of the biggest challenges faced. High pressure increases this effect as polymeric chain mobility increases resulting in high permeability and loss of molecular sieving mechanism (Kadirkhan et al., 2022). It has been observed that components such as CO₂, aromatic hydrocarbons and H₂S can integrate themselves within the polymer chain resulting in polymer swelling and increase in free volume (Jana and Modi, 2024). Plasticization also effects other membrane parameters such as glass transition temperature (Tg), structure and thickness. Plasticizers are seen to reduce Tg that further increases plasticization effect as the polymer chains become susceptible to CO₂ integration (Alcalde et al., 2024). Free volume of the polymeric membrane also rises with decrease in Tg as more plasticizers are introduced from the feed stream. The plasticization effect is often irreversible, causing loss of membrane functionality. Membranes which are made of thin polymers are at higher risk of plasticization as there is higher chain mobility present (Jana and Modi, 2024). Thus, resistance to plasticization under high pressure is an important criterion to understand while developing new membrane material.

5.2 Physical ageing

Physical ageing of membranes, especially amorphous or glassy polymer, is another important issue faced with gas separating membranes. Over time, polymeric membranes such as glassy polymers tend to undergo compaction and form denser polymeric matrix. Plasticization may increase permeability initially, however with compaction and physical ageing, the permeability decreases considerably (Kadirkhan et al., 2022). In glassy polymers, the chains are usually in non-equilibrium state, and they tend to achieve equilibrium at a temperature below Tg. This leads to densification of polymer chains, decreasing free volume. Physical ageing is mostly reversible and properties of the membrane can be restored by heating the membrane above its Tg. Thin film membranes are more affected by physical ageing than thick membranes (Jana and Modi, 2024). This is due to the fact that they have higher surface mobility and surface diffusion of free volume.

5.3 Interfacial defects

Interfacial defects are a major challenge in MMMs where these defects forms in the interphase region of the inorganic fillers and polymer chains. Polymer chains may face rigidification or dilution based on the interaction of the inorganic fillers with the polymer matrix (Klaysom and Shahid, 2019). Rigidification of polymer chains often lead to varying degree of pore blockage with respect to the bulk, decreasing permeability and increasing selectivity. On the other hand, dilution causes formation of nonselective void spaces along the inorganic fillers that increase permeability and decrease selectivity compared to polymer matrix (Ghasemi et al., 2025). Presence of interfacial defects impacts the membrane separation process negatively and also the prediction of the separation process using the transport theories becomes difficult. Various modified and computational models are required to predict the MMM performance dure to the presence of these interfacial defects.

The advantages and disadvantages of various membranes for CO₂ separation are elaborated in Table 2.

6 Emerging hybrid membranes for CO₂ separation

The need for more cost effective and high-performance membrane has led to formulation of various hybrid membranes that explore multiple aspects of CO₂ separation. Although polymeric membranes and MMMs are the most accepted membranes, they suffer from drawbacks such as plasticization, physical ageing, rigidity and dilution. Emerging membranes are being formulated to address all the drawbacks of classical membranes while also focusing on their sustainability. These membranes including incorporation of adsorbents/absorbents into membrane matrix. Various nanomaterials have also been explored as fillers in MMM. Recently, the demand for environment friendly and cost-efficient technologies are being focused with special importance given to circular economy.

6.1 Metal organic frameworks (MOFs) based membrane

Metal organic frameworks (MOFs) based membrane separation of CO₂ from flue gas is a sustainable method compared to conventional approaches (Hasan et al., 2025). MOF membranes act as a porous separator composed of metal ions linked with organic ligands to form an ordered crystalline structure (Deng et al., 2021). A MOF membrane is made up of a continuous layer of MOF material that is created on a porous substrate to give mechanical strength and minimal resistance to gas or liquid permeation (Lin, 2015). This type of membrane is more efficient due to their well-defined adjustable pore size, which allows selective separation, high surface area, and high porosity (Kang and Lee, 2023). MOF membrane works on the principle of selective permeation, various gases separated through membrane depending on their varying size and shape and interaction types with the membrane (Zhang Y. et al., 2025). This process is widely used in industrial processes like separation of CO₂/N₂ during post combustion, CO₂/H₂ during pre-combustion and CO₂/CH₄ during separation of natural gas (Zhao et al., 2013).

MOF based membrane cane be broadly classified into two categories namely, continuous MOF-based membranes and MOF-based mixed matrix membranes. MOF membranes can also be classified depending on their structural characteristics such as MOF thin film, continuous MOF membrane, Molecular sieve MOF membrane, Hollow fibre MOF membrane, ionic liquid (IL)/MOF membranes, MOF-COF (covalent organic framework) hybrid membranes, and MOF glass membranes (Demir et al., 2022).

Recent studies on MOF-based membranes have demonstrated substantial progress in the capture of CO₂. Song et al. (2023) reported that amine based ZIF-8 nanocrystals combined with polymeric membrane increase the efficiency of CO₂/N₂ separation with CO₂ permeance up to 778 GPU. Another research by Adegoke et al. (2024) shows high efficiency of CO₂ separation using UiO-66 based MOF membrane during post combustion. Contemporary studies on ionic liquid incorporated in ZIF-69 membrane shows high CO₂/N₂ selectivity, compared to other conventional MOF membranes (Veziri et al., 2024). Pazanialenjareghi et al (2026) developed a nanofilm based MOF membrane (UiO-66-Br) that significantly increased the selective separation of CO₂ with permeance value ∼1900 GPU with selectivity value of 37. Pazanialenjareghi et al. (2026) also synthesized NH₂-ZIF thin film membrane with an exceptional enhancement of CO₂ permeance to 156% (up to 778 GPU) and improved CO₂/N₂ selectivity by 55% (up to 34).

6.2 Nano material infused membrane

Nano composite membrane for separation of CO₂ is a new genre of membranes which are economically feasible and have infused functionalization nanofillers with different geometric and chemical feature which enhances the properties to get a high-performance membrane (Wong et al., 2022). Metal oxide nanoparticles like Alumina when mixed with methanol solution with porous nickel metal foam breakup gas bubbles mechanically initiating hydrodynamic mass transfer area for CO₂ uptake (Alguacil, 2023). Hollow fibre membrane containing semi permeable barrier is used for separation on CO₂ from natural gas. They are made up of a supporting porous layer, a bounded selective membrane, and circular cross-section channels. The two possible pathways in this configuration are absorption and desorption in the membrane bundle known as the module, in both cases, the gas flow is either parallel or cross-path giving it advantages over other membranes for absorption and separation of CO₂ (Jaiswar et al., 2023) graphene oxide, the functionalised group of graphene, are used for CO₂ separation. With their microstructural properties controlled it can act as a molecular sieve to separate CO₂ from flue gas and also the introduction of amine and oxygen group into the graphene layer enhances the process (Ali et al., 2019). Fullerene with 60 carbon atoms which are arranged in a structure similar to a soccer ball, due to the unique electronic, photonic and magnetic properties, along with its derivatives helps sequester and separate CO₂ (Ahmed et al., 2025). Fluorene-based derivatives with fluorenyl having more active sites for cross linking reaction with carbon attracting carboxyl group makes these structural features for development of functional polymer including electron-withdrawing groups to improve CO₂ absorption and separation (Hou S. et al., 2025). CNTs are another highly used nanofillers in membranes to enhance gas separation properties due to their unique tubular build and thermos-mechanical durability. The gas separation properties of CNTs are enhanced due to high specific area, rapid slip rates, smooth surface and large Van der Waals space (Li et al., 2025). However, incorporating CNTs into polymeric membrane often have compatibility issues which often require modification to formulate stable and robust membranes (Wang et al., 2023). CNT-ZIF-L nanofillers on Pebax MMM have shown high gas diffusivity owing to the disruption in the Pebax polymer chain. The permeability of CO₂ (161.3 Barrer) and CO₂/N₂ selectivity (51.4) was much higher than unmodified Pebax membrane (Cheng et al., 2023). CNTs diffused in zeolitic imidazolate continuous MMM had CO₂/N₂ selectivity of 31.2, which was more than 2019 Robeson upper limit (Li et al., 2025). Wet phase inversion method synthesis of MMM using cellulose acetate butyrate infused with multi walled CNTs also showed efficient CO₂ separation performance along with being cost effective. CO₂ permeance of 377.62 GPU and CO₂/N₂ selectivity of 13.17 was displayed by this MMM (Jawad et al., 2025).

6.3 Carbon based membranes

Porous carbon-based membranes are an alternative to conventional membranes and are environment friendly with higher recyclability and low cost (Wen et al., 2024). The porous carbon materials have high adsorption ability and superior surface kinetics that makes them a suitable option for large scale industrial processes (Sharma and Dhir, 2021). Incorporation of heteroatoms into carbon matrix significantly improves active sites and surface polarity for acid-base interactions that aid in CO₂ adsorption (Fang et al., 2023). Owing to its easy green synthesis and high CO₂ adsorption capabilities, incorporation of porous carbon into various membrane matrix is now emerging as a new avenue for CC from industries.

6.3.1 Porous carbon membranes

Porous carbon (PC) has been gaining popularity in adsorption domain due to their excellent surface morphology and porosity. Nitrogen doping of PC is a recent development in enhancing the adsorption active sites. In a study by Wang et al. (2022) nitrogen doped PC was formulated and modified with KOH and further mixed with Pebax for MMM production. The modified PC showed a high BET surface area of 1229.36 m²/g. The CO₂ permeability of the MMM was found to be 533 Barrer which was higher than Pebax membrane and the CO₂/N₂ membrane selectivity was 56.4. These properties rendered the membrane CO₂ separation efficiency nearing the Robson upper limit. The thermal conversion of ionic liquids-polymer membranes to PC membranes with nitrogen doping from the nitril present in the ionic liquid is another recent development. The MMM thus fabricated had good selectivity and high permeation, reaching the Robeson trade off upper boundary (Zhao et al., 2018).

6.3.2 Activated carbon-based membranes

The physical and chemical alteration of biochar with high temperature treatment using oxidizing gases or chemical impregnating followed by exposing it to high temperature leads to formation of activated carbon (AC) with enhanced functional properties to capture CO₂ (Lewis et al., 2021). CO₂ being an acidic gas, has high affinity towards base, therefore adding metal oxides like CaO, MgO, CuO, NiO, to AC helps in the selective adsorption of acidic CO₂. It enhances surface characteristics and promotes the interaction of AC with CO₂ (Wang et al., 2021). Studies have been conducted in formulating of AC from biowaste and incorporating them into MMMs for CO₂ separation. Wastes such as rice and wheat husks, tea and soft drink refuse, municipal wastes (Jomekian et al., 2023a; Jomekian et al., 2023b) have been utilised to fabricate AC fillers for MMMs.

Biomass waste treated with KOH and ZnCl₂ leads to AC powders formation, which when introduced into the PVA and PES matrix forms excellent MMM for CO₂ separation. This MMM showed a high CO₂ permeance as well as CO₂/CH₄ selectivity (Jomekian et al., 2023a). In another study by Jomekian et al (2023c), AC prepared from tea and carbonated drink waste was mixed with PVA to make MMM for CO₂ separation with high cost-effectiveness.

6.3.3 Biochar-based membranes

Biochar prepared from bio waste is an excellent adsorbent which is ecofriendly and has low cost of production (Barman et al., 2021). These porous materials have defined porosity with excellent surface adsorption property. Moreover, biochar facilitates various modification and engineering of its surface to enhance adsorption efficiency which can be utilised in CC technology (Li et al., 2026). Biochar production from waste also addresses waste management issues and adheres to the circular economy framework. Biochar is generally produced through the thermochemical conversion of organic biomass in an oxygen-limited environment (Mohanty et al., 2025). Biomass with high lignocellulosic content is usually agro-food in origin (Afshar and Mofatteh, 2024). During carbonisation certain volatile component of biomass gets decomposed while the rest gets preserved and the carbon content of the biochar depends on the choice of biomass as per required in the final product (Weber and Quicker, 2018). The important factor for the selection of good biomass is its ease of availably and economic feasible. Other precursor properties that are accessed before production of biochar include moisture content and organic compounds present in the biomass (Nath et al., 2022). Biomass with high lignocellulosic properties is usually selected for its carbon content and high porosity to capture CO₂ from atmosphere. Feed stocks such as rice husk and coconut husk, sugarcane bagasse are selected for producing high yield bio graphite membrane (Fathy et al., 2024). With sugarcane bagasse directly immersed in iron nitrate solution, dried and carbonised in vacuum muffle furnace for higher temperature of 1000° later acid washing and ionised water washing performed (Gai et al., 2021).

Biochar can be formulated via various methods that include Hydrothermal Carbonization (HTC), Pyrolysis, catalytic impregnation and most commonly combustion in a limited O₂ atmosphere in a muffle furnace (Demirbas and Arin, 2002). Hydrothermal carbonization is a thermochemical conversion process for biomass to yield a solid coal-like product (Funke and Ziegler, 2010). Also known as wet pyrolysis, this process treats biomass in a high-pressure, water-based environment. Biomass is submerged in water and heated to 180 °C–250 °C under high pressure. It produces hydrochar that does not require the biomass to be dried beforehand (Khan et al., 2024). In pyrolysis the produced biochar has a high energy content that is sometimes comparable to the coal utilized as fuel feedstocks in industries. Because of its high carbon content and microporous structure, biochar can be used in a variety of industrial settings (Yoganivashini et al., 2025). The rate at which soil sequesters carbon is also accelerated when biochar is added (Tripathi et al., 2016). Catalytic graphitization of bio-materials is an effective method to reduce the temperature and production time, maintaining high graphite quality (Shi et al., 2025). The presence of a catalyst provides an exciting route for adjusting graphene’s atomic and molecular characteristics at temperatures below 1000 °C, iron-catalyzed graphitization of biomass yields highly graphitic biochar (Ghogia et al., 2023). The most common procedure of producing biochar is dried biomass are packed into a sealed ceramic crucible with fitting lid to create a reductive atmosphere and carbonized at higher temperature of 450–850 °C are preferred which maximise fixed carbon in the biochar (Iloabachie et al., 2018; Barman et al., 2021). Various studies have shown that acid or alkali treated biochar shows higher adsorption capacities (Barman et al., 2021; Amer et al., 2024).

Various studies have indicated that biochar is a cost-effective adsorbent with immense potential for CC. Some of the recent studies which focus on biochar formulation from waste biomass and subsequent modification for CO₂ separation is shown in Table 3.

Incorporation of biochar into membranes for CO₂ separation is rather a new area of research. Mixed matrix membrane with a biochar component is being investigated for their potential as excellent CO₂ sequester. Biochar has abundant surface functional groups such as amino and carboxyl groups that adsorbed CO₂ via Lewis acid-base bonding that can improve gas separation capacity of membranes (Shao et al., 2025).

Treated biochar is incorporated into polymer membrane, namely, Pebax to form the MMM. The first study that used biochar in a membrane was by He et al. (2022). The biochar was prepared by catalytic hydrogenolysis of peanuts with a zeolite (ZSM-5) acting as a catalyst. This biochar residue after removal of bio-oil and other products were cast into membranes using ethyl cellulose. The MMM fabricated was showed best permeability of CO₂ at 300 °C when the permeability test was run for 3 h which was 79.53 Barrer. This was likely caused by lignin depolymerization at higher temperature and longer duration opening up gas channels. However, it was observed that the selectivity reduced as compared to pure ethyl cellulose membrane due to agglomeration of particles and pore clogging. Compared to non-hybrid membranes, the gas separation factor of the MMM for CO₂/CH₄ and CO₂/N₂ were 9.97 and 20.01 respectively were higher, but the permeability performance did not reach the Robeson upper limit. The mechanism of gas transport in this biochar-based MMM was through solution-diffusion transfer. It was finally concluded that though the gas separation performance of the biochar based MMM was not the best compared to other literature, this attempt was done to open up a new path of waste valorisation. The next attempt at making biochar infused MMM was done by Jha et al. (2024) where pine needle biochar was prepared by pyrolysis and functionalized by salt treatment. The membrane was cast using Pebax 1657 which is one of the most promising polymer matrixes in CO₂ separation process. The adsorption ability of the MMM was obviously higher than that of pure Pebax 1657 with the best CO₂ permeability of 114 Barrer achieved with MMM containing 20 wt% biochar. This was nearly 79% increase from pure Pebax 1657 membrane. The selectivity of the MMM was seen to increase with temperature and highest values of 32 and 94 were achieved for CO₂/CH₄ and CO₂/N₂ respectively. It was also observed that the permeability increased with increasing amount of biochar in the membrane.

Based on this Shao et al. (2025) also utilised Pebax-1657 for fabrication of biochar based MMM, however the biochar preparation was done using ball mill process with H₂O₂ modifications. The raw biomass used was wheat straw which was carbonized at 600 °C prior to modification. The ball milling and H₂O₂ modification was found to increase hydrophilicity of the biochar that facilitated compatibility with the polymer and also added carboxylic functional group to adsorption surface. The gas separation mechanism was solution-diffusion transport as reported in earlier studies. Best results of membrane permeability of 97.75 Barrer and CO₂/N₂ selectivity of 62.3 was seen in MMM with 3 wt% biochar at 25 °C under 0.2 MPa.

The membrane also showed a positive co-relation of gas separation with temperature owing to the polymer properties. It a molecular simulation study using biochar, it has been found that biochar has higher affinity for CO₂ as compared to N₂ or CH₄; also, the density of biochar impacts the adsorption of CO₂ (Barzegar and Feyzi, 2025). A comparative analysis of the various biochar-based membranes from the literature is shown in Table 4.

With the promising results displayed by the biochar-based membranes, this area requires more research as a greener alternative to commercial membranes with focus on waste valorisation.

6.3.4 Biomass induced graphene membrane

Biomass with high lignocellulosic properties is usually selected for its carbon content and high porosity that facilitate efficient capture CO₂ from atmosphere. Both rice and coconut husk have been used for producing high yield bio graphite membrane (Fathy et al., 2024). Slow pyrolysis at temperature between 400 and 900 forms a carbon residue called biochar (Cai et al., 2017). However, at much higher temperature ability to capture and adsorption the CO₂ is much more efficient. Biochar to graphitization requires a metal catalyst such as NiCl₃ or iron that help the carbon atom in biochar to realign itself contributing to more efficient way to form bio graphite (Kumila et al., 2023). The formed bio graphite undergoes acid wash for purification and dissolving the remaining metal (Cao et al., 2023). The bio graphite flake thus produced are combined with chitosan or other cellulose nanofibrils that acts as binder to hold the structure and form a bio graphite membrane (Tayeb et al., 2018). Other method also includes hummers method to form bio derived graphene oxide that can further form membranes for CO₂ capture (Dong et al., 2016). Optimized biomass-derived graphene can achieve CO₂ permeance exceeding traditional polymer limits (Koçak et al., 2026; Fan et al., 2024).

6.3.5 Carbon molecular sieve

Carbon molecular sieve is a highly specialised nanoporous activated carbon adsorbent which separates gas molecule according to their properties along with vapour and aqueous separation (Tu et al., 2021). Carbon molecular sieves are mostly formulated from polymeric membranes through their carbonization (Chuah et al., 2021). Selectivity and adsorption capacity of the constituent material determines the carbon molecular sieve efficiency. The capacity of the membrane to adsorb a particular gas from a gas mixture is determined by its pore size distribution, which indicates membrane selectivity and this property depend largely on the pore distribution of the carbon in the carbon molecular sieve. This pore distribution is enhanced during production and thus effecting the adsorption capability of the sieve (Mohamed et al., 2010).

Carbon molecular sieves can cross the Robeson Upper limit without compromising the structural integrity of the membrane, which is often seen in polymeric membranes that swell when subjected to high CO₂ concentration (Rahimalimamaghani et al., 2023b). Modification of these sieves have been done in recent times to enhance CO₂ capturing abilities.

Fluorine modified porous carbon molecular sieve have shown high permeability and selectivity for CO₂ separation. The addition of aliphatic/aromatic trifluoromethyl groups substituents increase the porosity of the carbon molecular sieve structure by promoting pore formation through the release of fluorine-containing gases during carbonization. The incorporation of non-linear terphenyl monomer disrupt the chain packing within the polymer backbone thus influencing the overall microstructure (Xu et al., 2025). Hybrid carbon molecular sieve membranes using ZIF-8 (Zeolitic Imidazolate Framework-8) crystals as fillers are also used for CO₂ separation. ZIF-8-derived hybrid carbon molecular sieve membranes (ZHCMSMs) shows increased permeability of CO₂. ZHCMSMs membrane carbonized at 600 °C showed good separating efficiency for CO₂/CH₄ and optimal ratio of CO₂ permeability to CO₂/CH₄ selectivity (Yin et al., 2026). SAPO-34 zeolites fillers with Carbon molecular sieves MMM have also been found to be efficient CO₂ separator with increase in both selectivity and permeability (Chuah et al., 2021). A comparative analysis of the CO₂ separation ability of different membranes is shown in Table 5.

7 Techno-economic analysis

The comparative analysis of the cost of membrane preparation, membrane efficiency and CO₂ capture cost is crucial for any membrane study. Membrane based CO₂ capture offers one of the most competitive capture costs among the available technologies, with an estimated cost of US$ 42–50 per ton of CO₂. This cost is lower than that of absorption (US$ 44–$71 per ton) and biological capture (US$ 88–$116 per ton), while being comparable to adsorption (US$ 37–$57 per ton). Although cryogenic separation has the lowest reported minimum cost (US$ 12 per ton), its overall cost range is very wide (US$ 12–$150 per ton) because of its high-energy demand and dependence on process scale and operating conditions. The relatively low and stable cost of membrane technology is mainly due to its simple model, easy design and the absence of chemical solvent regeneration (Park et al., 2025).

In this context material used for membrane preparation is an important consideration. Advanced materials such as nanotubes, graphene and mixed matrix membranes (MMM) can enhance the overall CO₂ permeability and efficiency and reduce the overall cost (Micari et al., 2026; Budhathoki et al., 2019; Raganati and Ammendola, 2024). Watson et al. (2024) studied the techno-economics of a range of membranes based on their performance index. Their study revealed that membranes with selectivity >30 do not have much variations in the economic aspect. However, they found that membranes with permeance >1000GPU and selectivity ranging from 20 to 30 was ideal for achieving low capture cost of $20-$55 per ton. These membranes also exhibited higher energy efficiencies of 150-500 kWh per ton. Another factor influencing process economics is the scalability of the membranes formulated. Cost per unit manufacturing of membranes can be significantly reduced from scaling up membrane production, making this a more acceptable industrial process (Raganati and Ammendola, 2024).

The cost of carbon capture, energy penalties and sustainability of CO₂ separation membranes mainly depend on the type of membrane material used, operating conditions such as pressure across the membrane, temperature and rate of flow, mechanism of separation and the life span (Song et al., 2017). Through techno-economic assessment Micari et al. (2026) calculate the capture costs of a pyridinic-graphene membranes hosting pyridinic nitrogen. Results show that capture cost can reach up to US$ 50–100perton of CO₂ for natural gas power plants and US$ 25–$50perton of CO₂ for coal and cement plants. Adhikari et al. (2023) developed a polymeric membrane based on poly [bis((2-methoxyethoxy)ethoxy)phosphazene] (MEEP) which showed a capture cost of US$ 50.1/metric ton for 99.8% purity of CO₂ from a 1% CO₂ feed source in nitrogen (N₂). They also concluded that capture cost using the Pebax-based membrane was found to be 464% higher, cryogenic capture was 60%–140% higher, pressure swing adsorption was 55%–165% higher and chemical absorption was 10%–110% higher than MEEP-based membrane capture, respectively. Han and Ho (2019) developed an amine-containing facilitated transport membrane which showed a capture cost of US$ 41.75/tonne. In another study, Asadi and Kazempoor (2021) conducted a comprehensive techno-economic assessment of various membrane-based CO₂ separation processes, which indicated that the configuration incorporating feed compression and a counter-current membrane module with sweep gas is the most cost-effective alternative, achieving a CO₂ capture cost of US$ 22.76 t^-1 CO₂.

The energy penalty of membrane-based CO₂ capture process is found to be 10%–30% of a power plant’s gross electrical output, based on process configuration, membrane performance, and flue gas composition. In contrast to conventional solvent-based capture technology, the energy cost associated with membrane-based CO₂ separation is normally lower because these processes depend mainly on electric energy. Industrial energy goals targets to drive down the energy penalty associated with membrane processes to <15% compared to 10%–30% energy penalty associated with first generation post-combustion capture (Belaissaoui et al., 2013; Naims, 2016). Recent studies have shown that a hybrid process that incorporates membranes with other CO₂ capture methods such as adsorption, can enhance the overall performance of the system, making it more cost effective (Zhang et al., 2020).

Life cycle assessment (LCA) of membranes is crucial in accessing economic and environmental sustainability of the process. It gives insight into the long-term benefits of the selected membrane material and process design that can surpass the cost of membrane preparation. LCA can address the bottlenecking of capital cost and capture cost which limits most membrane processes in industrial backdrop (Raganati and Ammendola, 2024). Lastly, the most important consideration to be taken into account is the sustainability of the material being used to formulate the membrane. LCA assessment of polymeric membrane shows excessive energy consumption and greater environmental impact, though somewhat addressing the issue of global warming by CO₂ capture. However future membrane development should focus on greener materials and low energy system design to lower operational costs of CC (Fu et al., 2024). Recent research is focused on preparing environmentally benign and cost-effective alternative materials which has high efficiency. Various carbon-based biodegradable materials such as biochar, activated carbons and bio-polymers are being utilized for CO₂ separation (Jha et al., 2024; Amin, 2023; Cigala et al., 2024). These membranes address the economic issue along with being eco-friendly making them an attractive alternative.

8 Conclusion

The review provides an extensive assessment of the principle, classification and applications of various membrane-based technologies for the separation and capture of CO₂. Recent developments of carbon capture technologies such as Polymeric membrane, Inorganic membrane, mixed matrix membranes (MMM), metal organic frameworks (MOFs) based membrane, carbon-based membranes are discussed with their advantage and limitations in terms of selectivity, stability and scalability. Polymeric membranes remain the most used commercially viable options for CO₂ capture because of their operational simplicity, low cost and scalability but the performance is limited by the permeability–selectivity trade-off and susceptibility towards plasticization. Inorganic membranes show efficient carbon capture and storage properties, although some challenges related to high cost, brittle structure, fabrication and compatibility between filter and polymer matrix hinder large-scale use. Carbon molecular sieve membranes also show promising results for CO₂ separation but needs improved reproducibility and scalability. MMMs are among the most efficient membranes developed, because they combine porous filters such as MOFs, zeolites, graphene derivatives with polymer matrices improving both permeability and selectivity. Based on recent research in this field, it is clear that there has been a shift from designing membranes with high separation efficiency to designing membranes with an optimum balance between permeability, selectivity, durability, ease of processing, and sustainability. Biomass-based carbon membranes have gained a lot of popularity because of their minimum impact on the environment; sustainable nature and their contribution towards circular economy. Hybrid membranes with multiple CC mechanism are being preferred for their higher efficiency and ability to cross the Robeson’s upper limit. Among all the organic carbon-based membranes, biochar membrane shows highly encouraging results for effective CO₂ capture and green synthesis. Biochar membranes derived from thermochemical conversion of waste biomass contains rich porous structure with changeable surface chemistry, numerous surface functional groups and outstanding stability. A range of waste materials can be used for easily formulation of biochar, promoting circular economy. Regardless of the exceptionally favourable characteristics, the scientific research related to CO₂ separation using biochar-based membranes are scarce. Most of the available studies deals with the adsorption properties of biochar rather than using it as a membrane material to separate pollutants creating a distinct knowledge gap regarding biochar membrane technology. Overall, the research and developments in membrane materials have created various new opportunities for energy-efficient and green CO₂ separation processes. Although, no existing membranes are able to justify all criteria needed for large-scale industrial development due to various limitations, biochar-based membranes have emerged as an ecofriendly alternative. Future research should therefore aim in developing stable, scalable, cost effective and environmentally viable membrane materials for carbon capture and separation. This review highlights the recent advancement, mechanisms, advantages, limitations and future prospects of various membrane materials for carbon capture with special emphasis on biochar-based membrane by providing a roadmap for the development of next-generation membrane materials that are environmentally benign and cost effective.

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