Abstract
Keywords
Introduction
The rising atmospheric concentration of carbon dioxide (CO2) is one of the primary drivers of global climate change. According to the Intergovernmental Panel on Climate Change (IPCC), anthropogenic CO2 emissions account for more than 75% of total greenhouse gas emissions, most of which originate from the combustion of fossil fuels (IPCC, 2022). To mitigate global warming, the development and implementation of effective carbon capture and storage strategies are essential. Among these, post-combustion CO2 capture has been extensively investigated because it can be directly applied to flue gases from power plants and industrial facilities (Rubin et al., 2012). Conventional aqueous amine scrubbing remains the most mature technology; however, it suffers from several drawbacks, including high energy consumption during regeneration, solvent degradation, and equipment corrosion (Rochelle, 2009). These limitations have motivated intensive research into solid sorbents as more energy-efficient and environmentally benign alternatives (Wang et al., 2014).
Porous solid adsorbents such as zeolites, mesoporous silica, metal–organic frameworks (MOFs), and activated carbons (ACs) have shown considerable promise for CO2 capture (Choi et al., 2009; Li et al., 2009; Sevilla and Mokaya, 2014). Although MOFs and zeolites can exhibit very high adsorption capacities and highly tunable pore architectures, their large-scale deployment is often hindered by high synthesis costs, moisture sensitivity, and limited long-term stability (Li, 2016; Sabouni et al., 2014). In contrast, AC has emerged as one of the most attractive candidates due to its low cost, the wide availability of precursors (including agricultural residues, forestry and food wastes, polymers, and industrial by-products), high thermal and chemical stability, resistance to water vapor, and facile regeneration. Beyond CO2 capture, ACs are widely employed in wastewater treatment and the removal of pharmaceuticals and other pollutants, highlighting their versatility as low-cost sorbents (Hosseinian Naeini and Hosseini Moradi, 2023; Rashidi and Yusup, 2016; Serafin et al., 2017). Furthermore, their CO2 uptake and selectivity can be markedly improved through physical or chemical activation, surface functionalization, and heteroatom doping (e.g., N, S, O) (Wickramaratne and Jaroniec, 2013).
In recent years (2022–2025), significant efforts have been devoted to developing advanced ACs for CO2 capture. Biomass-derived carbons prepared from sawdust, tea residues, fruit peels, nut shells, and palm residues have been converted into highly microporous adsorbents with specific surface areas above 1800 m2 g−1 and CO2 uptakes exceeding 6–9 mmol g−1 under near-ambient conditions (Aimikhe et al., 2024; Gorbounova et al., 2023; Lim et al., 2022; Lotfinezhad et al., 2024; Mochizuki et al., 2022; Zhang et al., 2024). Simultaneously, waste-derived precursors such as surgical masks (Ruhaimi and Ab Aziz, 2024), post-consumer plastics (Li et al., 2024), and tire pyrolysis char (Foorginezhad et al., 2024) have been transformed into low-cost sorbents that simultaneously address waste management and CO2 mitigation challenges. Strategies including nitrogen plasma treatment (Serafin et al., 2023b), ammonia doping (Serafin et al., 2023a), amino acid functionalization (Tahmasebpoor et al., 2023), and the deposition of metal oxides or MOFs onto AC surfaces (Khoshraftar and Ghaemi, 2022; Patel et al., 2023) have been employed to enhance CO2 affinity and CO2/N2 selectivity, reaching values up to ∼160 in certain systems. These modifications exploit the synergistic effects of ultramicropores (<0.7 nm) for molecular sieving and basic surface sites for strengthened interactions with CO2.
Thermodynamic investigations from numerous studies demonstrate that CO2 adsorption on ACs is predominantly governed by physisorption, with isosteric heats of adsorption (Qst) typically ranging from 15 to 40 kJ mol−1, thereby facilitating relatively easy regeneration (Tahsin et al., 2025). Moreover, many advanced ACs exhibit excellent cyclic stability, with capacity retention of more than 90–99% after 10–50 adsorption–desorption cycles, which underscores their potential for practical deployment (Gorbounova et al., 2023; Ruhaimi and Ab Aziz, 2024; Serafin et al., 2023b). Several of these sorbents perform comparably to, or better than, conventional ACs and certain MOFs under humid or mixed-gas conditions, further supporting their applicability in real flue gas environments.
Despite these advances, several challenges remain: (i) achieving an optimal balance between high surface area and sufficient surface functionality without excessive pore blockage; (ii) ensuring long-term stability under realistic flue gas conditions, including high humidity and the presence of contaminants such as SO2 and O2; and (iii) developing scalable synthesis routes that are both environmentally friendly and economically viable (Tahsin et al., 2025). Addressing these issues requires systematic studies that compare different precursors, activation protocols, doping strategies, and operating conditions.
The present review focuses on recent developments (2022–2025) in AC and its derivatives for CO2 sequestration. It critically examines 30 representative studies based on diverse biomass- and waste-derived precursors, incorporating various surface modification and composite formation strategies, to provide a comprehensive analysis of structure–property–performance relationships in AC-based sorbents. The discussion highlights key advances, existing limitations, and future research directions aimed at the rational design of sustainable and efficient carbon-based adsorbents for practical CO2 capture applications.
Fundamentals of AC for CO2 capture
AC is a highly porous carbonaceous material whose extensive surface area, tunable pore structure, and versatile surface chemistry make it particularly effective for gas adsorption. The mechanism of CO2 capture on AC is governed by its textural properties, surface functional groups, and the predominant physisorption interactions between CO2 molecules and pore walls.
Textural properties
The efficiency of CO2 uptake in AC is strongly influenced by its pore structure, especially the presence of micropores (<2 nm) and, more critically, ultramicropores (<0.7 nm). These narrow pores generate enhanced van der Waals interactions due to their confined geometry, enabling stronger adsorption potentials (Aimikhe et al., 2024; Foorginezhad et al., 2024; Serafin and Cruz, 2022). Numerous studies have consistently demonstrated that ultramicropores play a more decisive role in CO2 adsorption than mesopores or macropores, particularly under near-ambient pressures (Li et al., 2009; Wickramaratne and Jaroniec, 2013). For example, an oak-leaf-derived AC with a specific surface area of 1842 m2 g−1 and a micropore volume of 0.64 cm3 g−1 exhibited CO2 uptake exceeding 6 mmol g−1, primarily attributed to its ultramicropores centered around ∼0.6 nm (Serafin and Cruz, 2022). Similarly, a semi-coke-derived AC showed a high CO2/N2 selectivity of 34 despite its moderate brunauer-emmett-teller (BET) surface area (590 m2 g−1), owing to its abundant narrow pores (∼0.55 nm) that preferentially accommodate CO2 molecules (Jing et al., 2022). These findings clearly indicate that tailoring the pore size distribution—rather than simply maximizing BET surface area—is essential for optimizing CO2 capture performance (Sevilla and Mokaya, 2014).
As illustrated in Figure 1, AC typically features a hierarchical pore structure consisting of micropores (<2 nm), mesopores (2–50 nm), and macropores (>50 nm). Macropores facilitate the initial diffusion of CO2 into the particle, mesopores promote molecular transport within the structure, and micropores—especially ultramicropores—serve as the primary adsorption sites. This hierarchical porosity enhances diffusion, mass transfer, and pore filling, all of which collectively contribute to the overall CO2 adsorption efficiency.

Schematic illustration of the hierarchical pore structure of activated carbon, showing the roles of macropores, mesopores, and micropores in facilitating CO2 diffusion, transport, and adsorption.
Surface chemistry
In addition to textural control, surface functional groups play a crucial role in tuning the CO2 affinity of ACs. Oxygen-containing groups (–OH, –COOH, –C = O) can enhance physisorption by strengthening dipole–quadrupole interactions between CO2 and the carbon surface. Heteroatom doping with elements such as N, S, and O introduces basic sites that further reinforce acid–base interactions with CO2 molecules (Bai et al., 2023; Hosseini Moradi et al., 2023; Li et al., 2024; Lim et al., 2022; Lotfinezhad et al., 2024; Mochizuki et al., 2022; Ruhaimi and Ab Aziz, 2024). Nitrogen functionalities are particularly effective: pyridinic and pyrrolic nitrogen provide lone-pair electrons that interact favorably with the quadrupole moment of CO2, whereas graphitic nitrogen usually contributes less to adsorption enhancement (Li et al., 2024; Lim et al., 2022; Lotfinezhad et al., 2024). For instance, plasma-treated AC enriched in pyridinic/pyrrolic nitrogen exhibited a ∼32% increase in CO2 uptake compared with the pristine material (Lim et al., 2022). Sulfur-doped carbons derived from polyphenylene sulfide (PPS) have shown Qst values of up to ∼41 kJ mol−1, indicating the presence of relatively strong binding sites while still maintaining reversible adsorption behavior (Bai et al., 2023).
Adsorption mechanisms
CO2 uptake on ACs proceeds via two primary pathways: (i) physisorption, mainly governed by confinement and dispersion forces in ultramicropores, and (ii) chemisorption, occurring at specifically engineered basic sites or in composite phases. The relative contribution of each pathway is dictated by pore structure, surface heteroatom content, and operating conditions (temperature, pressure, and gas composition) (Hosseinian Naeini and Hosseini Moradi, 2023; Li et al., 2009; Rashidi and Yusup, 2016; Serafin et al., 2017; Wickramaratne and Jaroniec, 2013).
Physisorption predominates under near-ambient temperature and pressure. It is driven by van der Waals interactions and pore filling within ultramicropores (<0.7 nm), where the overlap between the CO2 quadrupole and the pore walls maximizes the adsorption potential. Consequently, ultramicropore engineering correlates more closely with CO2 capacity than total BET surface area, as demonstrated in several recent systems (e.g., oak-leaf- and semi-coke-derived ACs), where narrow pores enhanced both uptake and/or CO2/N2 selectivity (Jing et al., 2022; Serafin and Cruz, 2022; Wickramaratne and Jaroniec, 2013). Typical isosteric heats of adsorption (Qst) for ACs fall in the range of 20–35 kJ mol−1, which is characteristic of physisorption with fast kinetics and relatively easy regeneration (Lim et al., 2023; Tahsin et al., 2025; Weldekidan et al., 2023; Xiao et al., 2022).
Chemisorption contributions become significant when basic surface sites or reactive phases are introduced. Oxygenated groups (–OH, –COOH, –C = O) can enhance dipole–quadrupole interactions, while pyridinic and pyrrolic nitrogen species provide localized basicity that increases CO2 affinity and selectivity. This has been demonstrated in nitrogen-plasma-functionalized and ammonia-treated carbons, where uptake was enhanced without substantial loss of porosity (Lim et al., 2022; Mochizuki et al., 2022). Urea-assisted N-doping similarly increases the fraction of pyrrolic nitrogen and improves CO2 capture performance (Li et al., 2024). Beyond nitrogen, oxidized sulfur species in S-doped carbons (e.g., derived from PPS resin) have been reported to raise Qst values to ∼38 kJ mol−1 while preserving reversibility (Bai et al., 2023). In certain bio-derived carbons rich in heteroatoms (e.g., crustacean-shell-based ACs), Qst values can reach approximately 41–49 kJ mol−1, approaching a partial chemisorption regime that enhances selectivity at the expense of higher regeneration energy requirements (Shao, 2024).
Composite strategies introduce additional synergistic mechanisms. MOF–AC hybrids (e.g., Mg-MOF-74/AC) combine the intrinsic microporosity of AC with open metal sites that bind CO2 more strongly, thereby improving performance under mixed-gas conditions (Zhang et al., 2024). Likewise, alkaline metal-oxide-loaded carbons (e.g., NiO/MgO–AC) provide Lewis basic sites that promote stronger CO2 interactions at elevated pressures; in humid environments, these sites can form bicarbonate-like species, thereby increasing high-pressure capacities while keeping the enthalpy of adsorption within a regenerable range (Ghaemi et al., 2022). Thermodynamic analyses across various systems consistently indicate exothermic and spontaneous adsorption (ΔH < 0, ΔG < 0), with magnitudes reflecting the balance between textural confinement and binding-site strength (Khoshraftar and Ghaemi, 2022; Vijayaraj et al., 2024).
In summary, CO2 capture on ACs follows a cooperative dual-mode mechanism: ultramicropores supply the backbone of physisorption capacity, while specific heteroatom functionalities and composite phases introduce tunable chemisorption that enhances selectivity. The design of high-performance ACs therefore requires simultaneous optimization of pore size distribution and surface chemistry to remain within an effective Qst window (typically 20–35 kJ mol−1), avoiding excessively strong binding that would hinder energy-efficient regeneration (Bai et al., 2023; Ghaemi et al., 2022; Li et al., 2024; Lim et al., 2022; Mochizuki et al., 2022; Shao, 2024).
Isotherm and kinetic models
Understanding how structural features influence CO2 adsorption performance requires appropriate modeling of adsorption equilibria and kinetics. AC-based sorbents typically follow the Langmuir or Toth isotherm models, reflecting monolayer adsorption on energetically heterogeneous surfaces (Gorbounova et al., 2023; Patel et al., 2023). For systems exhibiting wider pressure ranges or heterogeneous site distributions, the Freundlich and Sips isotherms are frequently employed to provide more accurate fitting (Khoshraftar and Ghaemi, 2022; Ruhaimi and Ab Aziz, 2024).
Kinetic studies generally indicate that CO2 adsorption on ACs follows pseudo-second-order or linear driving force models, suggesting that both pore diffusion and surface interaction processes contribute to the overall adsorption rate (Serafin et al., 2023a; Xiao et al., 2022). For example, wild-sugarcane-derived AC exhibited pseudo-second-order behavior with a high correlation coefficient (
Recent advances in ACs
Between 2022 and 2025, research on ACs for CO2 capture has expanded rapidly, with significant progress in precursor selection, activation strategies, and surface functionalization. Recent studies can be broadly grouped into four thematic categories: biomass-derived, waste-derived, heteroatom-doped, and composite/functionalized carbons. In this section, we summarize key advances within these categories, emphasizing structure–performance relationships (e.g., surface area, ultramicroporosity, heteroatom speciation) and practical performance metrics such as adsorption capacity, CO2/N2 selectivity, and cyclic stability/regenerability.
Biomass-derived ACs
A wide range of agricultural and forestry residues has been converted into highly microporous ACs that perform efficiently under near-ambient conditions. Mango and almond shells (Aimikhe et al., 2024), as well as bottom-ash-derived carbons (Gorbounova et al., 2023), have demonstrated the feasibility of using low-cost biomass feedstocks with potential for scale-up. Sawdust-based AC prepared via CO2 activation achieved a CO2 uptake of 9.2 mmol g−1 at 25 °C and 1 bar, with a CO2/N2 selectivity of ∼40, highlighting the critical role of ultramicropores (<0.7 nm) and a well-balanced micro/mesoporous network for effective mass transfer (Foorginezhad et al., 2024).
Olive-stone-derived carbons obtained through “bio-organic” activation exhibited CO2/N2 selectivity values up to ∼161 and capacities of ∼6 mmol g−1. The exceptionally high CO2/N2 selectivity (up to 161) reported for olive-stone-derived ACs prepared via
Collectively, these studies support the general conclusion that combining diverse biomass precursors with carefully controlled pore engineering typically yields CO2 capacities in the range of ∼4–7 mmol g−1 at low pressures and near-ambient temperatures, while maintaining favorable selectivity and potential for sustainable, low-cost production.
Waste-derived ACs
Transforming hazardous or problematic wastes into CO2 sorbents represents an important step toward circular and sustainable carbon management. Post-consumer plastics treated with KOH yielded CO2 uptakes of ∼1.4 mmol g−1 at 15 °C, with performance strongly influenced by the generation of new micropores and the incorporation of oxygen-containing surface groups (Ligero et al., 2023). AC prepared from discarded surgical masks exhibited a CO2 uptake of 3.9 mmol g−1 at 0 °C and showed excellent cyclic stability over 20 adsorption–desorption cycles (Serafin et al., 2022).
Tire-derived char supports functionalized with polyethyleneimine (PEI) favored amine-mediated CO2 capture at elevated temperatures, achieving capacities up to ∼54 mg g−1 at 75 °C, thereby underscoring the importance of matching surface chemistry with operating temperature (Sirinwaranon et al., 2023). Steam-activated semi-coke-based AC with a characteristic pore width of ∼0.55 nm delivered a CO2/N2 selectivity of ≈34 and robust cyclic stability, outperforming a commercial benchmark despite its lower S_BET, due to its higher fraction of ultramicropores (Jing et al., 2022). Incorporation of SiO2 nanoparticles into waste-tea-derived AC improved flow properties and maintained ∼94–95% of the initial capacity over 25 cycles, a critical feature for fluidized-bed applications in industrial processes (Tahmasebpoor et al., 2023).
Collectively, these studies demonstrate that diverse waste streams can be valorized into tailored porous carbons with appropriate textural and surface chemistries suitable for both low-temperature physisorption and higher-temperature amine-assisted CO2 capture, thereby coupling waste management with greenhouse gas mitigation.
Heteroatom-doped ACs
Heteroatom doping—particularly with nitrogen—remains a powerful strategy for enhancing the CO2 affinity of ACs. Plasma-treated AC has been shown to increase both CO2 capacity and ideal adsorbed solution theory (IAST) selectivity by enriching pyridinic and pyrrolic nitrogen functionalities without significantly compromising porosity (Lim et al., 2022). In sawdust-derived AC subjected to ammonia treatment, an optimal treatment temperature of ∼400 °C was identified, at which the material exhibited a CO2 uptake of 665 mg g−1 at 20 °C while preserving its microporous structure. At higher treatment temperatures, although the overall nitrogen content increased, pore collapse led to reduced adsorption capacity, illustrating the intrinsic trade-off between surface chemistry and textural integrity (Mochizuki et al., 2022).
Urea-assisted nitrogen doping of carbons derived from date/jujube seeds (Lotfinezhad et al., 2024) and bio-oil residues (Li et al., 2024) consistently enhanced CO2 uptake and CO2/N2 selectivity (up to ∼14). In these systems, pyrrolic nitrogen was frequently identified as the dominant contributor, with Qst values remaining within the physisorption regime. Beyond nitrogen, sulfur-doped carbons synthesized from PPS retained 3–6 wt% sulfur and achieved CO2 capacities of 3.6–5.1 mmol g−1 (0–25 °C), with IAST selectivities of ∼19, indicating that oxidized sulfur species can strengthen CO2 binding while preserving regenerability (Bai et al., 2023). Under breakthrough conditions, amino-acid functionalization (e.g., egg-white-protein-derived amide groups) increased the CO2 capacity by ∼76% relative to the parent AC, due to the introduction of additional basic sites; however, excessive loading led to pore blockage and performance deterioration (MohamedHatta et al., 2023).
Overall, these findings highlight that pyridinic and pyrrolic nitrogen, as well as oxidized sulfur species, are particularly effective in boosting CO2 adsorption and selectivity, provided that ultramicroporosity is maintained. This underscores the need to concurrently optimize heteroatom speciation and pore architecture in the design of high-performance AC-based sorbents.
Composite and functionalized carbons
Composite and functionalized ACs exploit synergistic effects between hierarchical porosity and specialized binding sites. Analogous hybridization concepts are widely employed in other fields such as energy storage, where the combination of carbon frameworks with conductive nanostructures (e.g., laser-induced graphene decorated with silver nanowires) has been shown to markedly improve conductivity and cycling stability (Hosseini Moradi et al., 2022).
In the context of CO2 capture, AC/MOF composites (e.g., Mg-MOF-74/AC) have demonstrated enhanced stability and CO2/N2 selectivity (∼32) through the coexistence of physisorption in the carbon micropores and chemisorption at open metal sites, while maintaining accessible micro–mesoporous networks (Zhang et al., 2024). Similar design principles are observed in photocatalytic systems, where constructing p–n heterojunctions (e.g., ZnO/NiCo2O4) improves charge separation and overall performance (Hosseini Moradi, 2024); by analogy, combining AC with functional inorganic phases can optimize transport and binding in CO2 sorbents.
Metal-oxide impregnation (e.g., NiO, MgO) introduces Lewis basic sites that strengthen interactions with CO2, particularly at elevated pressures, leading to uptake capacities up to ∼5.9 mmol g−1 at 10 bar while keeping the enthalpy of adsorption within a regenerable range (Ghaemi et al., 2022). In pistachio-shell-derived carbons, Hill/Freundlich isotherm modeling combined with response surface methodology/artificial neural networks has been used to predict and optimize adsorption behavior, providing quantitative design windows for pressure-driven capture processes (Khoshraftar and Ghaemi, 2022). Physicochemical activation routes (KOH ± CO2) applied to pine sawdust have clarified the relative influence of micropore fraction versus total S_BET, yielding capacities of 6.35 mmol g−1 at 0 °C and IAST selectivities of 10–19, thereby reinforcing the dominant role of ultramicropores in determining performance (Patel et al., 2023).
Bio-derived carbons from crab and shrimp shells exhibited high specific surface areas (∼1700m2 g−1) and substantial pyrrolic-N content, resulting in CO2 uptakes of ∼4.3–5.1 mmol g−1 at 298–273 K and IAST selectivities of ∼32, as confirmed by dynamic breakthrough separations (Shao, 2024). Process-oriented innovations such as SiO2-promoted fluidizable ACs (Tahmasebpoor et al., 2023) and flow-/temperature-matched amine or oxide functionalities (Ghaemi et al., 2022; Sirinwaranon et al., 2023) further demonstrate the translation of material-level advances into forms compatible with industrial reactor configurations (e.g., fluidized beds and fixed-bed columns).
Taken together, three recurring design themes emerge from these advances:
Ultramicropore engineering (<0.7 nm) generally exerts a stronger influence than total S_BET on CO2 capture under ambient-pressure conditions (Foorginezhad et al., 2024; Jing et al., 2022; Serafin and Cruz, 2022; Serafin et al., 2023a). Targeted heteroatom speciation—particularly pyridinic/pyrrolic nitrogen and oxidized sulfur species—enhances CO2 affinity and selectivity, provided that ultramicroporosity is preserved and excessive pore blockage is avoided (Bai et al., 2023; Li et al., 2024; Lim et al., 2022; Lotfinezhad et al., 2024; Mochizuki et al., 2022; Ruhaimi and Ab Aziz, 2024). Composite architectures incorporating MOFs, metal oxides, amines, or inorganic nanoparticles enable tuning of the capacity–selectivity–regenerability balance to match specific operating windows, from low-temperature physisorption to higher-temperature chemisorption-dominated regimes (Ghaemi et al., 2022; Sirinwaranon et al., 2023; Tahmasebpoor et al., 2023; Zhang et al., 2024).
Table 1 summarizes the precursors used for AC synthesis in recent studies, the activation routes employed, and the subsequent modification or composite strategies. It highlights the diversity of feedstocks—from agricultural residues to industrial and post-consumer wastes—as well as post-synthesis treatments such as heteroatom doping, amine impregnation, and MOF/metal-oxide incorporation that collectively define the structure–property–performance landscape of AC-based CO2 sorbents.
Precursors, activation methods, and modification strategies employed for the synthesis of activated carbons (2022–2025).
Mechanisms and structure–performance relationships
The efficacy of ACs for CO2 capture is governed by a complex interplay among pore structure, surface chemistry, adsorption energetics, and cyclic stability. Recent studies published between 2022 and 2025 (Aimikhe et al., 2024; Bai et al., 2023; Foorginezhad et al., 2024; Ghaemi et al., 2022; Gorbounova et al., 2023; Hosseini Moradi, 2024; Hosseini Moradi et al., 2022; Hosseini Moradi et al., 2023; Ismail et al., 2022; Jing et al., 2022; Khoshraftar and Ghaemi, 2022; Li et al., 2024; Ligero et al., 2023; Lim et al., 2022; Lim et al., 2023; Lotfinezhad et al., 2024; Mochizuki et al., 2022; MohamedHatta et al., 2023; Patel et al., 2023; Ruhaimi and Ab Aziz, 2024; Serafin et al., 2022; Serafin and Cruz, 2022; Serafin et al., 2023a, 2023b; Shao, 2024; Sirinwaranon et al., 2023; Swapna et al., 2024; Tahmasebpoor et al., 2023; Tahsin et al., 2025; Vijayaraj et al., 2024; Weldekidan et al., 2023; Xiao et al., 2022; Zhang et al., 2024) provide sufficiently detailed data sets to elucidate these interdependencies and identify the key structure–property relationships that control CO2 adsorption capacity and selectivity.
Importance of pore size distribution
Although a large specific surface area is often regarded as beneficial for gas adsorption, numerous studies have demonstrated that, under near-ambient conditions, ultramicropores (<0.7 nm) play a more critical role than the total BET surface area in determining CO2 uptake. As illustrated in Figure 2, semi-coke-derived AC with a moderate BET surface area of 590 m2 g−1 achieved a CO2 uptake of 1.80 mmol g−1 at 40 °C due to its high proportion of narrow micropores (∼0.55 nm) (Jing et al., 2022). Likewise, oak-leaf-derived carbons (S_BET = 1842 m2 g−1, V_micro = 0.64 cm3 g−1) exhibited CO2 capacities exceeding 6 mmol g−1 under near-ambient conditions (Serafin and Cruz, 2022).

Correlation between micropore volume and CO2 adsorption capacity of activated carbons, based on 24 recent studies (2022–2025). All values are reported at 25 °C and 1 bar.
In contrast, certain composite materials possessing relatively high surface areas but lower ultramicropore volumes displayed inferior adsorption performance (Ligero et al., 2023). These observations collectively emphasize that the distribution of pore volume—particularly the abundance of ultramicropores—is more strongly correlated with CO2 uptake than the absolute value of BET surface area alone.
There is a clear positive correlation between micropore volume (Vₘ□crₒ) and CO2 uptake; however, the substantial scatter across data sets highlights the importance of pore-size distribution and surface chemistry. For example, Foorginezhad et al. (Foorginezhad et al., 2024) reported a very high CO2 uptake of 9.2 mmol g−1 at a moderate Vₘ□crₒ of 0.69 cm3 g−1, suggesting an optimized ultramicropore distribution combined with favorable surface functionalities. In contrast, Sirinwaranon et al. (2023) observed only 0.95 mmol g−1 at a comparable micropore volume (0.43 cm3 g−1), likely due to pore blockage, suboptimal pore connectivity, or less favorable surface chemistry. These comparisons demonstrate that CO2 adsorption is governed not only by total micropore volume but also by the interplay between pore-size distribution, accessibility, and chemical characteristics of the carbon surface.
As shown in Figure 3, BET surface area exhibits only a modest overall trend: CO2 uptake generally increases when S_BET exceeds ∼1700m2 g−1, yet substantial variability persists within the intermediate range (600–1400 m2 g−1). For instance, some carbons with S_BET above 1300 m2 g−1 exhibited capacities as low as 1.45 mmol g−1, whereas others with similar surface areas reached capacities up to ∼4.7 mmol g−1. These discrepancies confirm that BET surface area alone is not a reliable predictor of CO2 adsorption performance. Instead, ultramicropore distribution, pore accessibility, and surface functional groups exert far more decisive influences on adsorption behavior.

Correlation between BET surface area and CO2 adsorption capacity of activated carbons reported in recent studies (2022–2025), all measured at 25 °C and 1 bar.
Table 2 provides a comparative summary of the textural properties—including BET surface area and micropore volume—and the CO2 uptake capacities of ACs reported between 2022 and 2025 under standardized ambient conditions (25 °C, 1 bar). The data reveal broad variations in BET surface area (248–2433 m2 g−1) and micropore volume (0.08–0.71 cm3 g−1), accompanied by CO2 adsorption capacities ranging from 0.57 to 9.2 mmol g−1. Overall, ACs containing a higher proportion of ultramicropores (≤0.7 nm), combined with well-optimized surface chemistry, consistently exhibit superior adsorption performance. These results reinforce the conclusion that pore-size distribution and surface functionalization are more influential determinants of CO2 uptake than total BET area alone. The data set serves as a useful benchmark for establishing structure–performance correlations across both biomass-derived and waste-derived ACs.
Textural properties and CO2 adsorption capacities of activated carbons reported in recent studies (2022–2025) under ambient conditions (25 °C, 1 bar).
All data are obtained from representative studies. All CO2 uptake values are standardized to approximately 25 °C and 1 bar.
Effect of surface chemistry
Textural optimization alone cannot fully account for the variations observed in CO2 adsorption performance; surface functional groups exert a significant additional influence on adsorption affinity. Oxygen-containing groups such as –OH, –COOH, and –C = O enhance CO2 binding by strengthening dipole–quadrupole interactions. Heteroatom doping—particularly with nitrogen and sulfur—further increases adsorption strength by introducing localized basic sites that interact favorably with the quadrupolar CO2 molecule.
Plasma-treated ACs enriched in pyridinic and pyrrolic nitrogen functionalities have demonstrated more than a 30% increase in CO2 uptake relative to untreated materials (Lim et al., 2022). Ammonia-treated carbons exhibit their highest adsorption capacities when pyridinic-N is maximized without inducing pore collapse, highlighting the delicate balance between chemical modification and textural preservation (Mochizuki et al., 2022). Urea-assisted nitrogen doping of bio-oil–derived carbons yielded high pyrrolic-N contents and CO2 uptakes of up to 6.2 mmol g−1 at 0 °C (Li et al., 2024). Similarly, sulfur-doped carbons synthesized from PPS retained oxidized sulfur species, resulting in Qst values ranging from 22 to 41 kJ mol−1—indicative of strengthened yet reversible adsorption interactions (Bai et al., 2023). Collectively, these findings demonstrate that pyridinic and pyrrolic nitrogen, together with oxidized sulfur functionalities, represent the most effective chemisorption sites, provided that sufficient and accessible microporosity is maintained to support these interactions.
Recent advances have emphasized the critical role of surface wettability (hydrophilicity vs hydrophobicity) and associated confined-water phenomena in determining CO2 adsorption behavior in ACs. A landmark study revealed that instead of rendering carbon nanopores strictly hydrophobic, the deliberate engineering of polar surface sites enabled the formation of local surface-bound water nano-films, which in turn acted as additional CO2 trapping sites under humid conditions (3000 ppm CO2, 75% RH) in a polar carbon architecture (Zheng et al., 2024). The hydrophilic carbon showed anomalous enhancement of CO2 capture (compared to dry conditions), overturning the conventional avoidance of water in physisorption systems. This finding indicates that for ACs—and particularly biomaterial-derived carbons exposed to flue gas moisture—controlled hydrophilicity combined with tailored polar functionalities can be a strategic route to both enhancing uptake and maintaining stability under humid conditions. Incorporating this paradigm shifts the focus from purely hydrophobicity to a more nuanced design space of
Thermodynamics of CO2 adsorption
Thermodynamic analysis, as listed in Table 3, provides essential insight into the strength and mechanism of CO2–adsorbent interactions. Among the 30 representative studies reviewed, only eleven explicitly report isosteric heats of adsorption (Qst), yet these data sets collectively reveal a clear and coherent picture of how pore structure and surface chemistry govern CO2 binding in ACs.
Representative isosteric heats of adsorption (Qst) for AC-based CO2 sorbents reported between 2022 and 2025.
Across a wide range of biomass- and waste-derived precursors, most AC-based sorbents exhibit Qst values within the 20–35 kJ mol−1 regime—widely recognized as the optimal thermodynamic “sweet spot” for physisorption. Materials in this window bind CO2 strongly enough to ensure high uptake at near-ambient pressures while preserving fast adsorption kinetics and low regeneration energies. Representative systems include oak-leaf ACs (23–32 kJ mol−1) (Serafin and Cruz, 2022), fern-leaf ACs (27–32 kJ mol−1) (Serafin et al., 2023a), pine-sawdust carbons (23–33 kJ mol−1) (Patel et al., 2023), and nitrogen-doped porous carbons prepared via solvent-free melt polycondensation (25–30 kJ mol−1) (Xiao et al., 2022). These sorbents—despite their distinct precursor chemistries—display convergent thermodynamic behavior shaped by ultramicropore (<0.7 nm) enrichment and moderate basic functionalities.
Other nitrogen-containing carbons demonstrate slightly weaker interactions. For instance, urea-modified bio-oil carbons (15–22 kJ mol−1) (Li et al., 2024) fall on the lower edge of the physisorption window, consistent with a higher fraction of less-basic nitrogen species. By contrast, sorbents incorporating highly reactive heteroatoms exhibit significantly stronger binding energies. Sulfur-doped carbons from PPS (22–41 kJ mol−1) (Bai et al., 2023) show elevated Qst values arising from oxidized sulfur species that enhance dipole–quadrupole interactions with CO2. Even more pronounced interactions were reported for crustacean-shell–derived hierarchical carbons (41–49 kJ mol−1) (Shao, 2024), where pyrrolic-N, Ca-based functionalities, and ultramicroporosity act synergistically to strengthen CO2 binding—approaching the boundary between strong physisorption and partial chemisorption.
A similar dual-regime behavior appears in pine-needle biochar–derived carbons (18–42 kJ mol−1) (Lim et al., 2023), where low-temperature activation retains Ca(OH)2 and nitrogen functionalities that elevate Qst to >40 kJ mol−1, while higher-temperature activation produces micropore-dominated structures with Qst values in the 30–36 kJ mol−1 range. Mild heteroatom enrichment also influences Qst in lemon-peel–derived carbons, in which KOH + alum activation yields 23 kJ mol−1 whereas pure KOH activation increases Qst to 35 kJ mol−1 (Weldekidan et al., 2023).
Collectively, these results define a robust thermodynamic framework for AC-based CO2 capture:
Qst < 20 kJ mol−1 → weak physisorption, low affinity. Qst = 20–35 kJ mol−1 → Qst > 40 kJ mol−1 → enhanced selectivity but increased regeneration energy; often linked to heteroatom-rich or mineral-assisted sites (as in Bai et al., 2023; Lim et al., 2023; Shao, 2024).
These thermodynamic insights highlight the need for simultaneous optimization of ultramicropore volume, surface basicity, and heteroatom speciation to maintain strong yet reversible CO2 adsorption. Sorbents engineered to remain within the 20–35 kJ mol−1 Qst —particularly those dominated by ultramicropores and controlled N- or O-functionalities—show the greatest promise for delivering energy-efficient, cyclable, and industrially scalable CO2 capture performance
Selectivity and competitive adsorption
CO2/N2 selectivity is a critical performance indicator for post-combustion CO2 capture, as flue gas streams typically contain a high proportion of N2. The compiled data (Figure 4) show substantial variability in selectivity values reported for AC-based sorbents, which can be primarily attributed to differences in precursor type, pore-size distribution, and surface chemistry. Figure 4 compares CO2/N2 selectivity values for representative ACs reported between 2020 and 2025 under near-ambient conditions, revealing clear structure–performance trends.

Reported CO2/N2 selectivity values of activated carbons from recent studies (2020–2025) under near-ambient conditions.
Materials engineered with high fractions of ultramicropores (<0.7 nm), in combination with targeted surface functionalities, consistently exhibit enhanced selectivity. Olive-stone-derived ACs (Serafin et al., 2023b) demonstrate an exceptional selectivity of ∼161, significantly outperforming most biomass- and waste-derived carbons, which generally lie within the range of 20–80. In contrast, carbons derived from waste surgical masks (Serafin et al., 2022) and MOF/AC composites (Li et al., 2024) show more moderate selectivity values, emphasizing the strong influence of precursor identity and post-synthetic modification techniques. These observations reinforce the conclusion that achieving superior CO2/N2 separation performance requires a synergistic balance of optimized ultramicroporosity and purposeful surface functionalization—particularly heteroatom doping and bio-organic activation routes that introduce basic or polar sites capable of selectively interacting with CO2.
Overall, the reviewed studies demonstrate that high CO2/N2 selectivity arises from the synergistic interplay between ultramicroporosity and appropriately engineered basic surface functionalities. In contrast, materials that depend primarily on high BET surface area—without deliberate control over pore-size distribution or surface chemistry—tend to exhibit only moderate separation factors. These findings underscore the importance of rational pore design and targeted heteroatom doping in tailoring ACs for effective CO2/N2 separation under realistic flue-gas conditions.
Stability and regeneration
The cyclic stability of ACs is a critical parameter for their practical deployment in CO2 capture systems. Across the studies reviewed, most AC-based sorbents retain approximately 90–99% of their initial CO2 uptake after repeated adsorption–desorption cycles, reflecting the predominance of physisorption-driven interactions, which enable facile and energy-efficient regeneration.
For example, mask-derived AC reported by Serafin et al. (2022) maintained nearly its full uptake capacity after 20 cycles, while oak-leaf-derived carbons (Serafin and Cruz, 2022) preserved ∼99% of their original capacity after 30 cycles. Similarly, waste-tea-derived AC enhanced with SiO2 nanoparticles (Tahmasebpoor et al., 2023) retained 94.5% of its capacity after 25 cycles and exhibited improved fluidization behavior—an advantageous property for large-scale reactor applications. Nitrogen-doped ACs produced via ammonia treatment or plasma activation also demonstrated strong cyclic stability, maintaining >95% of their CO2 uptake after 5–10 cycles (Lim et al., 2022), indicating that N-containing functionalities remain stable when the microporous network is preserved. In contrast, sorbents functionalized with amines—such as PEI-modified tire-char carbons—experienced gradual performance deterioration due to pore blockage, amine volatilization, and oxidative degradation. This highlights the inherent trade-off between achieving high initial uptake through chemisorptive interactions and maintaining long-term structural and chemical stability. Carbons exhibiting very high isosteric heats of adsorption, such as crustacean-shell-derived materials with Qst values of 41–49 kJ mol−1 (Shao, 2024), are thermally and chemically robust but require higher regeneration energy. S-doped porous carbons derived from PPS resin exhibited minimal capacity loss after five cycles, demonstrating short-term durability under moderate physisorptive conditions (Bai et al., 2023).
Overall, the evidence indicates that ACs combining abundant ultramicropores with stable heteroatom functionalities—operating primarily through physisorption—offer the most favorable balance of high capacity, low regeneration energy, and long-term cyclic stability. These characteristics underscore their strong potential for industrial post-combustion CO2 capture, where repeated adsorption–desorption cycling is essential. It should also be stressed that the vast majority of cyclic stability and regeneration tests reported for AC-based sorbents have been performed under simplified gas compositions, often using dry CO2 or binary CO2/N2 mixtures over a relatively small number of cycles. Long-term dynamic operation in the presence of realistic concentrations of SO2, NOₓ, and water vapor is rarely examined in a systematic manner. Consequently, the true working capacity, deactivation rate, and regeneration penalty of ACs in industrial post-combustion capture units are still poorly quantified. Addressing this knowledge gap will require extended breakthrough and cycling campaigns (up to hundreds of cycles) under fully representative CO2/N2/H2O/SO2/NOₓ feeds, so that material-level properties can be rigorously linked to process-level performance and lifetime in real flue-gas environments.
Integrated structure–performance map
The performance of ACs in CO2 capture cannot be attributed to a single parameter; rather, it emerges from the coupled effects of pore structure, surface chemistry, adsorption energetics, and operational stability. The analyses presented in Sections 4.1–4.5 enable the construction of a structure–performance framework that can guide the rational design of advanced sorbents.
First, pore architecture plays a dominant role. Ultramicropores (<0.7 nm) are consistently associated with the highest CO2 uptakes under near-ambient conditions, whereas total BET surface area alone is an unreliable predictor of performance. This underscores the importance of deliberately engineering the micropore size distribution instead of merely maximizing overall surface area.
Second, surface chemistry provides complementary benefits. Pyridinic and pyrrolic nitrogen functionalities, oxidized sulfur species, and oxygen-containing groups generate favorable acid–base and dipole–quadrupole interactions that significantly enhance CO2 affinity and CO2/N2 selectivity. However, excessive heteroatom doping or heavy amine impregnation can lead to pore blockage and reduced accessibility, highlighting the need to balance chemical modification with the preservation of open porosity.
Third, thermodynamic parameters govern the trade-off between binding strength and regenerability. Most ACs exhibit optimal performance when the isosteric heat of adsorption (Qst) lies in the range of 20–35 kJ mol−1, which affords sufficiently strong CO2 binding while still enabling energy-efficient desorption. Materials with higher Qst values (>40 kJ mol−1) may offer improved selectivity but typically require greater regeneration energy, potentially compromising process-level energy efficiency.
Finally, cyclic stability integrates these factors under realistic operating conditions. ACs featuring tailored ultramicroporosity and stable heteroatom functionalities, with adsorption dominated by physisorption, routinely exhibit ≥95% capacity retention over multiple cycles. In contrast, heavily functionalized sorbents with very high Qst or high amine loadings can suffer gradual performance degradation due to pore blockage, oxidative side reactions, or active-site loss.
Taken together, these observations define a practical design map for advanced AC-based sorbents:
generate a high fraction of ultramicropores to maximize capacity; introduce targeted heteroatom functionalities to enhance selectivity; maintain adsorption energies within the 20–35 kJ mol−1 window to ensure regenerability; and verify multi-cycle stability under relevant operating conditions.
This unified perspective indicates that the most promising ACs are those that achieve a balanced optimization across all four dimensions—structure, chemistry, energetics, and stability—thereby paving the way for scalable and environmentally sustainable CO2 capture technologies.
Integrated quantitative comparison of precursor types, activation methods, and performance metrics
To provide a unified evaluation framework and enable horizontal comparison across the 30 representative studies reviewed, the key performance metrics were quantitatively consolidated and examined collectively. Three principal variables—precursor category, activation route, and resulting textural/surface attributes—were compared against common adsorption indicators (CO2 uptake at 25 °C and 1 bar, CO2/N2 selectivity, ultramicropore fraction, and stability).
Biomass-derived precursors activated by KOH yield the highest overall performance, with averaged BET surface areas of 1100–1700 m2 g−1, micropore volumes in the range of 0.45–0.70 cm3 g−1, and CO2 uptakes of 5.0–7.5 mmol g−1. Waste-derived feedstocks activated by KOH show slightly lower textural metrics (BET typically 800–1400 m2 g−1), but comparable uptakes (3.5–6.0 mmol g−1) owing to their high ultramicropore fraction. In contrast, CO2/steam physical activation provides superior sustainability but produces narrower microporosity (0.20–0.45 cm3 g−1) and reduced uptakes of 2.5–4.5 mmol g−1.
A comparison across activation methods shows that KOH activation consistently provides the greatest ultramicropore development and selectivity (up to ∼160), while H3PO4 activation yields broader micro–mesopore distributions that favor moderate capacities but improved cyclic stability. Composite formation (AC/MOF or AC/oxide hybrids) enhances selectivity and high-pressure adsorption but does not surpass KOH-ACs under ambient-pressure conditions.
A cross-study analysis also indicates that CO2 uptake correlates more strongly with ultramicropore volume (R ≈ 0.82) than with BET surface area (R ≈ 0.41), confirming ultramicroporosity as the dominant controlling parameter. Moreover, nitrogen- or sulfur-doping increases selectivity by 20–70% when introduced without significant pore blockage.
This consolidated evaluation framework provides a unified basis for comparing diverse CO2 sorbents and highlights the precursor–activation combinations that most efficiently produce ultramicroporous structures suited for near-ambient CO2 capture. It also reveals the trade-offs among activation intensity, surface functionality, and sustainability, thereby offering clearer design guidance than isolated data sets.
Challenges and future perspectives
Despite the significant progress made in developing ACs for CO2 capture, several challenges remain before these materials can be deployed at industrial scale. These challenges relate to material design, real-world performance, process integration, and scalability.
Cost-Effectiveness and scalability
Although biomass and waste-derived precursors offer inherent environmental benefits, the life-cycle cost and environmental footprint of their conversion into AC remain strongly dependent on the activation route. KOH activation, for example, typically requires 650–850 °C and reagent-to-precursor ratios of 3–5 kg KOH per kg of carbonized biomass, corresponding to an energy demand of approximately 3.2–5.5 MJ kg−1 and generating significant alkaline wastewater streams during post-washing. Only a few pilot-scale studies report partial chemical recovery (40–60% KOH recycling), and fully closed-loop reagent management is rarely demonstrated. These factors indicate that the overall environmental advantage of biomass-derived ACs is highly sensitive to process configuration, reagent recovery efficiency, and the extent of low-temperature or green activation steps used.
Performance under realistic flue gas conditions
Most laboratory studies evaluate CO2 adsorption using pure gas streams under idealized conditions. However, real flue gas contains multiple impurities—such as H2O vapor, SO2, NOₓ, and O2—that can significantly influence adsorption behavior. Despite the clear practical importance of such multicomponent effects, the quantitative database available for ACs remains surprisingly sparse. Among the 30 representative studies surveyed in this review, only a few report CO2 adsorption or breakthrough behavior in the presence of defined amounts of SO2 and NOₓ, and these experiments are typically conducted at one or two fixed impurity concentrations and temperatures. As a result, the existing literature allows only qualitative or semi-quantitative conclusions to be drawn regarding impurity effects: acidic gases are known to strongly interact with basic surface sites, to accelerate the deactivation of N-rich or amine-functionalized carbons, and to lower the effective CO2 working capacity, whereas more hydrophobic or only mildly basic ACs tend to exhibit better tolerance. However, there are currently insufficient systematic data to derive robust correlations between impurity concentration, temperature, and dynamic CO2 uptake or selectivity without over-interpreting isolated results. In the present review, we therefore deliberately refrain from proposing empirical fits or design equations and instead emphasize this lack of comprehensive parametric studies as a critical gap that must be addressed before reliable process-level models for industrial flue-gas capture can be established. ACs generally exhibit superior moisture tolerance compared with zeolites or many MOFs, yet their selectivity and long-term stability under multi-component flue gas conditions remain insufficiently characterized. Robust assessment of industrial feasibility therefore requires extended testing under humid, impurity-rich environments to evaluate competitive adsorption effects, pore blocking, oxidative degradation, and cyclic stability under operationally relevant conditions.
Balancing textural and chemical optimization
A recurring challenge in recent research is achieving an optimal balance between textural engineering and chemical functionalization. Excessive heteroatom doping or heavy amine loading can enhance CO2 affinity but may simultaneously obstruct ultramicropores, reducing accessible adsorption sites and impairing diffusion. Future efforts should adopt integrated design strategies that simultaneously optimize ultramicropore volume while incorporating heteroatom functionalities in a controlled manner. Advanced computational tools—including molecular simulations, density functional theory, and machine-learning-assisted optimization—can accelerate the rational tuning of pore structures and surface chemistries, enabling targeted design of high-performance sorbents without compromising pore accessibility.
Energy-efficient regeneration
Although most ACs operate within a favorable Qst window (20–35 kJ mol−1), sorbents with higher adsorption enthalpies (>40 kJ mol−1) require more energy for regeneration, which can diminish overall process efficiency. The development of “smart” sorbents with tunable binding strengths—either through tailored surface functionalities or controlled pore environments—represents a promising strategy to mitigate regeneration costs. In parallel, the integration of advanced swing adsorption processes (e.g., temperature swing adsorption, vacuum swing adsorption, or pressure swing adsorption) can further reduce energy penalties by aligning regeneration conditions with the thermodynamic characteristics of the sorbent.
Integration with emerging CO2 capture technologies
Emerging CO2 capture technologies such as direct air capture (DAC) and modular, small-scale capture units demand sorbents that combine high selectivity with low regeneration energy. ACs—particularly those derived from abundant biomass and waste feedstocks—are strong candidates for these applications, provided that ultramicroporosity and stable heteroatom functionalities can be reliably engineered. Future research should explore hybrid systems, such as AC/MOF and AC/polymer composites, to exploit synergistic effects in adsorptive capacity, selectivity, and processability, thereby broadening the application space from post-combustion capture to DAC and decentralized capture platforms.
Environmental and sustainability considerations
Although the conversion of agricultural residues, plastics, and medical wastes into ACs aligns with circular-economy principles, the environmental footprint of activation agents (e.g., KOH, ZnCl2, and H3PO4) and post-processing steps (particularly washing and neutralization) must be carefully evaluated. Transitioning toward greener activation methods—such as physical activation, bio-derived activating agents, or low-impact chemical routes—and ensuring safe treatment, recycling, or recovery of process by-products will be essential for the long-term sustainability and regulatory acceptance of AC-based CO2 sorbents.
The future of AC-based CO2 sorbents will depend on holistic optimization, in which textural properties, surface chemistry, thermodynamic efficiency, and operational stability are improved in a coordinated manner. Realizing this vision will require: (i) valorization of green and waste-derived precursors; (ii) data-driven and simulation-assisted materials design; and (iii) rigorous validation under industrially relevant conditions and process configurations. By integrating these elements, laboratory-scale advances in ACs can be translated into practical, scalable, and environmentally sustainable solutions for CO2 capture across power, industrial, and emerging DAC applications.
It is also important to acknowledge that comprehensive life-cycle assessments (LCA) and life-cycle cost analyses (LCC) for AC synthesis remain scarce. Most published reports provide either qualitative claims of sustainability or partial data (e.g., activation temperature, reagent consumption, washing steps) that cannot be directly integrated into a unified environmental model. Furthermore, the stability and scalability of precursor supply—such as seasonal agricultural residues or geographically dispersed waste streams—introduce logistical and transportation-related impacts that are seldom quantified. As a result, the long-term environmental advantage of biomass-derived ACs can only be fully validated through systematic cradle-to-gate LCA/LCC studies, which represent a critical research gap for guiding industrial deployment and technical transformation.
Breakthrough performance and practical applicability
Beyond equilibrium isotherms, which are typically measured under idealized conditions, fixed-bed breakthrough experiments provide the most realistic measure of how ACs perform in continuous CO2 capture processes. Breakthrough curves directly probe mass-transfer resistance, bed utilization, column hydrodynamics, and the influence of gas-phase composition, all of which determine the usable capacity of a sorbent in a real unit rather than its theoretical maximum uptake. In practice, dynamic capacities obtained from breakthrough tests are often substantially lower than equilibrium values, and the shape of the breakthrough front (sharp versus tailing) reveals whether pore diffusion, surface reaction, or external film resistance is rate-limiting.
Recent studies on heteroatom-doped carbons nicely illustrate these points. For example, N,S-codoped coconut-shell ACs showed high equilibrium uptakes (∼4.4 mmol g−1 at 25 °C and 1 bar), but breakthrough tests in a packed bed (10 vol% CO2 in N2, 25 °C, 1 bar, 10 mL min−1) yielded a dynamic capacity of only ∼0.97 mmol g−1, i.e., roughly one quarter of the static capacity (Shao et al., 2025). The corresponding breakthrough curve was very steep, with minimal tailing, indicating fast mass transfer and efficient bed utilization, and the sorbent retained >99% of its capacity over at least five cycles, confirming the robustness of physisorption-dominated uptake. A similar behavior was reported for B-doped porous carbons (WSCPM-900-2), where an equilibrium uptake of ∼3.15 mmol g−1 at 25 °C translated into a dynamic breakthrough capacity of ∼0.85 mmol g−1 under 10 vol% CO2/N2 at 1 bar (Wang et al., 2025). Again, a sharp breakthrough front and excellent multi-cycle stability demonstrated favorable mass-transfer characteristics and structural durability, while simultaneously highlighting the systematic gap between equilibrium and in-process capacities.
These examples emphasize that, for biomass- and waste-derived ACs, breakthrough testing is indispensable for assessing practical usability. Materials that appear promising based on equilibrium isotherms alone may deliver much lower working capacities once flow, contact time, and multicomponent competitive adsorption are accounted for. Systematic breakthrough measurements under realistic post-combustion conditions (e.g., 10–15% CO2 in N2 with water vapor and trace SO2/NOₓ), combined with multi-cycle testing, should therefore become a standard part of sorbent evaluation protocols. Incorporating such dynamic metrics will be crucial for bridging the current gap between laboratory-scale adsorption data and the design of industrially relevant CO2 capture processes based on ACs. In addition, almost all breakthrough studies considered to date have been carried out in the absence of SO2 and NOₓ, which further limits the direct transferability of the reported dynamic capacities to industrial flue-gas conditions and reinforces the need for impurity-resolved breakthrough testing.
Conclusion
Over the past three years (2022–2025), research on ACs for CO2 capture has expanded rapidly, driven by the use of diverse biomass and waste precursors, innovative activation strategies, and targeted surface functionalization. This review has synthesized findings from 30 representative studies, elucidating clear structure–performance relationships and outlining design principles that can guide the development of next-generation AC-based sorbents.
The analysis leads to three central conclusions:
Ultramicropores (<0.7 nm) constitute the most critical structural feature, as they consistently enable high CO2 uptake under near-ambient pressures. In contrast, total BET surface area alone is an unreliable predictor of performance. Surface chemistry, particularly the presence of pyridinic and pyrrolic nitrogen as well as oxidized sulfur groups, substantially enhances CO2 affinity and CO2/N2 selectivity when these functionalities are introduced without compromising accessible microporosity. Thermodynamic efficiency, characterized by isosteric heats of adsorption (Qst) in the range of 20–35 kJ mol−1, provides an optimal compromise between strong binding and facile regeneration, which underpins the excellent multi-cycle stability (>90–99% capacity retention) observed for many AC sorbents.
Despite these advances, several challenges must be addressed before large-scale implementation is realized. Key issues include the scalability and cost-effectiveness of synthesis routes, performance under realistic flue gas conditions, and further reduction of regeneration energy demands. Addressing these challenges will require integrated strategies that combine sustainable precursor utilization, controlled pore engineering, optimized heteroatom functionalization, and systematic long-term testing under industrially relevant conditions.
ACs—especially those derived from renewable and waste resources—are uniquely positioned to contribute to carbon mitigation efforts. By coupling materials innovation with process-level optimization and integration, AC-based sorbents can transition from promising laboratory prototypes to scalable, sustainable, and economically viable solutions for CO2 separation in both point-source capture and direct air capture applications.
Footnotes
Funding
The authors received no financial support for the research, authorship, and/or publication of this article.
Declaration of conflicting interests
The authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.
