Scalable, Durable, and Malleable PVMDMS@PVP Aerogel Catalyst for CO2 Capture and Successive Gas-Phase Cycloaddition Reaction

Scalable, Durable, and Malleable PVMDMS@PVP Aerogel Catalyst for CO2 Capture and Successive Gas-Phase Cycloaddition Reaction | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Scalable, Durable, and Malleable PVMDMS@PVP Aerogel Catalyst for CO 2 Capture and Successive Gas-Phase Cycloaddition Reaction Kyung Hoon Min, Byeongseok Kim, Kyoung Tae Park, Kyeongseok Min, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6847440/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Oct, 2025 Read the published version in Advanced Composites and Hybrid Materials → Version 1 posted 9 You are reading this latest preprint version Abstract A structurally robust PVMDMS@PVP aerogel catalyst was developed by incorporating polyethyleneimine (PEI) and an ionic liquid, followed by Zn 2+ impregnation, for integrated carbon dioxide (CO 2 ) capture and catalytic conversion. The solvent-resistant framework maintains high CO 2 adsorption capacity and structural integrity across 50 thermal cycles over a broad temperature range (0–130°C). Breakthrough experiments confirm excellent CO 2 /N 2 selectivity (5078) under mixed-gas flow at 100°C. Zn 2+ -functionalized aerogels enable gas-phase cycloaddition of CO 2 with epoxides, achieving >99% selectivity for propylene carbonate over 1978 hours of continuous operation. Notably, the carbonate product was directly applied as an electrolyte in lithium-ion batteries, validating its electrochemical utility. The aerogel preserved its pore structure, catalytic activity, and monolithic form even after scale-up, demonstrating superior mechanical and chemical durability. This work presents a scalable, multifunctional aerogel catalyst platform that combines long-term stability, high CO 2 adsorption efficiency, and battery-relevant carbonate production for advanced CO 2 capture and utilization technologies. Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction The combustion of fossil fuels is a major source of carbon dioxide (CO 2 ) emissions, which in turn trigger global climate change and exacerbate environmental and energy issues 1,2,3,4 . While carbon capture and storage (CCS) technologies are essential for achieving the targets set by the Paris Agreement 5,6,7 , existing systems face operational challenges, particularly in natural gas combined cycle (NGCC) power plants where CO 2 concentrations are only about 4% 8,9,10 . In addition, the flue gases from these plants contain high levels of oxygen (~12.4%) and moisture (~8.4%), causing, for example, aqueous amine solutions to degrade leading to reduced efficiency and increased maintenance costs 11 . Recently, porous solid materials such as zeolites, metal organic frameworks (MOFs), and silica-based aerogels have garnered considerable attention as candidates for CO 2 capture and utilization due to their high surface areas, tunable chemical functionalities, and relatively low regeneration energy requirements 12,13,14,15 . However, MOFs suffer from thermal and chemical instability, and zeolites and conventional silica aerogels are often limited by mechanical fragility, shrinkage and cracking during drying, and severe structural degradation upon exposure to solvents 16,17 . These limitations significantly hinder their practical application in CO 2 capture and conversion systems that require repeated functionalization, solvent processing, or scale-up. In particular, conventional silica-based aerogels frequently experience irreversible collapse of their porous networks during solvent impregnation and ambient pressure drying due to capillary stress and weak gel skeletons, resulting in diminished surface area, reduced accessibility of active sites, and compromised catalytic performance 18,19 . Therefore, there is a growing need for next-generation hybrid materials that not only exhibit excellent structural and chemical stability but also integrate CO 2 capture and catalytic conversion capabilities within a single platform. Meanwhile, there is growing interest in integrated approaches that not only capture CO 2 but also convert it into high-value chemicals. Such approaches can enhance overall process efficiency and significantly reduce emissions, thereby advancing a circular carbon economy. Among these, cycloaddition reactions have garnered considerable attention due to their relatively low energy demands and their ability to produce cyclic carbonates high-value chemicals that serve as essential precursors for pharmaceuticals, polymers, and other advanced materials 20 . Consequently, the development of new adsorbents with robust thermal and chemical stability, high structural integrity, and excellent scalability is critical for the advancement of CCS and CO 2 utilization technologies. In this study, we address these challenges by incorporating the functional polymer polyvinylpyrrolidone (PVP) into the sol–gel synthesis process of polyvinylmethyldimethoxysilane (PVMDMS)-based aerogels. Through tautomerization, PVP forms strong covalent bonds with PVMDMS precursors 21 , thereby mitigating shrinkage and cracking while significantly enhancing resistance to both polar and non-polar solvents. Additionally, the impregnation of polyethyleneimine (PEI) and [EMIm]Br, coupled with the introduction of Zn 2+ , enhanced the catalytic activity and selectivity of the aerogel for the cycloaddition reaction of CO 2 and epoxides. Experimental results demonstrate that this aerogel operates stably over a wide temperature range of 50–130°C and exhibits excellent cyclic performance during CO 2 desorption processes. These findings highlight the potential of this innovative aerogel as a high-performance sorbent and catalyst support for CO 2 capture and conversion in environmental and energy applications. Furthermore, the scalability and robustness of this material underscore its potential for integration into large-scale industrial processes, offering a sustainable pathway for carbon management technologies. Methods Synthesis of PVMDMS@PVP aerogels The synthesis of the PVMDMS precursor began by placing 12.12 g of VMDMS and 0.705 g of di-tert-butyl peroxide (DTBP) into a 50 mL liner. The mixture was purged with argon for 10 minutes to remove oxygen, followed by stirring at 400 rpm for 5 minutes. The prepared liner containing the mixture was placed into an autoclave and subjected to radical polymerization at 120°C for 48 hours. After the reaction, the autoclave was cooled to room temperature, and the resulting precursor was collected for further processing. For the sol-gel process, 3 g of the recovered precursor was dispersed in 11.04 g of benzyl alcohol (BnOH). Subsequently, 0.6 g of polyvinylpyrrolidone (PVP, Mw: 40,000 g/mol) was added to the solution and stirred until fully dissolved. To initiate the sol-gel reaction, 0.197 g of distilled water and 0.6205 g of tetramethylammonium hydroxide (TMAOH, 10 wt% in H 2 O) were added to the mixture, which was stirred for 5 minutes. The resulting sol was then transferred into 20 mL vials and subjected to aging in an oven at 100°C for 5 days. Following the aging process, the solid gels were washed three times with isopropyl alcohol (IPA), each washing lasting 8 hours, to remove residual solvents and impurities. Finally, the aerogels were dried at room temperature for 2 days, yielding the final PVMDMS@PVP aerogel. Synthesis of PVMDMS@PVP Aerogel Film To fabricate the PVMDMS@PVP aerogel film, a precursor sol was prepared following the composition described in Section 2.2.1 and stirred at 400 rpm for 10 minutes at room temperature to ensure homogeneity. The sol was then cast into a polypropylene (PP) mold (Ø 80 mm) to a height of less than 5 mm, facilitating the formation of a thin film. Gelation was confirmed by the transition from a fluid sol to a non-flowing gel. The resulting wet gel was aged in benzyl alcohol at 100 °C for 5 days in a convection oven to promote crosslinking and reinforce the silica framework. After aging, the gel was washed with isopropyl alcohol every 12 hours for 3 days to remove unreacted species and residual solvent. Finally, the film was dried under ambient temperature and pressure to obtain the PVMDMS@PVP aerogel. Synthesis of PVMDMS@PVP Aerogel Fiber To synthesize the PVMDMS@PVP aerogel fiber, the precursor sol was prepared according to the composition described in Section 2.2.1 and stirred at 400 rpm for 10 minutes at room temperature to ensure uniform mixing. The sol was then loaded into a syringe fitted with a 29-gauge needle (inner diameter ~0.18 mm) and continuously injected at a flow rate of 1 mL·min⁻¹ into an aqueous tetramethylammonium hydroxide (TMAOH) solution (pH 12), where immediate gelation occurred upon contact. The resulting gel fibers were gently collected and transferred into benzyl alcohol for aging at 100 °C for 5 days in a convection oven to reinforce the silica network. After aging, the fibers were washed with isopropyl alcohol every 12 hours for 3 days to remove unreacted species and residual by-products. The final aerogel fibers were obtained by drying under ambient temperature and pressure. Synthesis of [EMIm]Br 1-Methylimidazole was measured into a 2 or 3-neck flask, to which a magnetic stir bar is added. A condenser was attached to one neck, and the other neck was sealed with a rubber septum. Bromoethane was then added dropwise. The molar ratio was set to 1:1.2 for this experiment. The mixture was vigorously stirred at room temperature while adding bromoethane dropwise. After the addition was completed, the stirring was continued overnight. Physical impregnation with PEI, [EMIm]Br, and Zn 2+ Solution A was prepared by dissolving polyethyleneimine (PEI) and zinc acetate in 20 mL of methanol at 40°C with stirring at 450 rpm for 30 min, while Solution B was obtained by dissolving the ionic liquid (IL) in another 20 mL of methanol at 40°C, 450 rpm for 10 min. After mixing Solutions A and B at 40°C for a designated time, the as-synthesized aerogels (1 g) were immersed in the combined solution and stirred (200 rpm) at 40°C for 4 h, followed by a 12 h modification step at the same temperature. For impregnation with PEI, a total of 2 g of PEI (per 1 g of aerogel) was introduced, where 2 g was taken as 100%. From the total 2 g of PEI, x% consisted of PEI with a molecular weight of 25,000 g/mol (PEI25k), while the remaining (100−x)% was PEI with a molecular weight of 2,000 g/mol (PEI2000). Additionally, the ionic liquid (IL) was added at y% relative to this total PEI (2 g), forming a mixture denoted as “25k x% – IL y%.” After the modification process, the samples were dried at 80°C under an argon (or nitrogen) flow until the aerogel color changed from yellow to white, indicating successful impregnation and solvent removal. Characterization The morphology of the aerogel and impregnated aerogel was examined using field emission scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy (SEM-EDS; S-4300SE, Hitachi, Japan) at the Core Facility Center for Sustainable Energy Materials of the Korea Basic Science Institute (KBSI). To prevent charging effects, the samples were sputter-coated with a thin layer of platinum (4 nm) using a sputter coater (Quorum Technologies Ltd, Q150T-S, UK) prior to analysis. The SEM was operated at an accelerating voltage of 15 kV, providing a resolution of 1.5 nm. Additionally, TEM images were obtained using a Philips CM200 transmission electron microscope (Philips Electronics, Netherlands) operated at an acceleration voltage of 200 kV. Aerogel samples were dispersed in ethanol via ultrasonication, drop-cast onto a copper TEM grid, and dried at room temperature prior to analysis. Thermal properties were measured using a TGA 4000 thermogravimetric analyzer (PerkinElmer, USA). TG curves were obtained by increasing the temperature at a rate of 10°C/min from 30 to 800°C under a flow of pure N 2 gas at 20 ml/min. Nitrogen adsorption-desorption isotherms were obtained using a BELSORP-max (MicrotracBEL Corp., Japan) instrument at −196°C. The samples were pretreated at 120°C under vacuum for 12 hours prior to measurement. The specific surface area (SSA) was calculated from the adsorption branch using the standard Brunauer-Emmett-Teller (BET) theory, while the pore size distribution and total pore volume were determined using the Barrett-Joyner-Halenda (BJH) method based on the adsorption isotherm. ¹H and ¹³C NMR spectra were recorded on a Bruker Avance III 400 MHz spectrometer (Bruker Corporation, Germany) using CDCl₃ as the solvent. The amount of Zn²⁺ leached from the impregnated aerogel was measured using inductively coupled plasma-optical emission spectrometry (ICP-OES; OPTIMA 7300 DV, PerkinElmer, USA). Similarly, the amount of Br – leached from the impregnated aerogel was measured using ion chromatography (IC; ICS-3000, Dionex Korea, South Korea). Synthesis and versatile moldability of PVMDMS@PVP aerogels The PVMDMS@PVP aerogel was synthesized via a sol–gel reaction in which polyvinylpyrrolidone (PVP) undergoes tautomerization under basic conditions and forms covalent bonds with the PVMDMS precursor, resulting in a chemically crosslinked hybrid network (Fig. 1a). This structural configuration enhanced both the formability and the stability of the aerogel. The PVMDMS@PVP aerogel could be readily molded into various macroscopic shapes, including monoliths, films, and continuous fibers, while maintaining uniform internal pore structures in all forms, as confirmed by SEM analysis (Fig. 1b–d). The covalently bonded hybrid framework also contributed to improved thermal and structural stability. Thermogravimetric analysis (Fig. S1) showed that the introduction of PVP led to a higher decomposition onset temperature and greater residual weight at 700 ºC compared to pristine PVMDMS. Drying behavior was evaluated under ambient and supercritical CO 2 conditions. As shown in Fig. S2, the pristine PVMDMS aerogel underwent substantial shrinkage and collapse during ambient drying, whereas PVMDMS@PVP aerogels retained their original shape with minimal deformation. Quantitative shrinkage analysis (Fig. S3) revealed that PVMDMS-AD samples exhibited a shrinkage ratio of approximately 50%, while PVMDMS@PVP-AD samples showed less than 5%. These results suggest that the hybrid network formed via tautomerization improves not only processability but also thermal and structural stability by mitigating capillary stress during drying. Shape retention of PVMDMS@PVP aerogels under solvent exposure To evaluate the structural durability of the aerogels under solvent exposure, PVMDMS and PVMDMS@PVP aerogels were first immersed in methanol and dried under ambient conditions. As shown in Fig. 2a, the pristine PVMDMS aerogel exhibited significant shrinkage and pore collapse following solvent treatment, indicating poor resistance to capillary stress. In contrast, the PVMDMS@PVP aerogel retained its porous structure with minimal deformation, suggesting improved solvent tolerance due to the covalently crosslinked hybrid framework. To further examine the effect of PVP concentration on structural preservation, aerogels containing 0 to 20 wt% PVP were subjected to the same methanol soaking and drying procedure. As shown in Fig. 2b–f, samples with ≤10 wt% PVP displayed visible cracking, deformation, or fragmentation after drying, whereas those with 15–20 wt% maintained their original monolithic form. These results indicate that a minimum threshold of PVP is required to prevent structural failure during solvent induced stress. The solvent compatibility of the PVMDMS@PVP aerogel was subsequently evaluated using a series of polar (acetone, methanol, DMSO, DMF) and non-polar (THF, cyclohexane) solvents. In Fig. 2g–l, each panel presents three images: the top shows the aerogel prior to solvent exposure, the middle shows the sample after soaking and ambient drying, and the bottom provides SEM images of the internal pore network. In all solvent systems tested, the aerogels retained their macroscopic shape without noticeable shrinkage or surface cracking. SEM analysis further confirmed that the internal porous structures remained intact under all solvent conditions, regardless of polarity. Carbon Dioxide Adsorption and Recyclability Building on the excellent solvent compatibility of the PVMDMS@PVP aerogel, its CO 2 adsorption performance was evaluated after impregnation with polyethyleneimine (PEI) and [EMIm]Br over a temperature range of 50–130°C. At 50°C, the aerogel containing low-viscosity PEI exhibited the highest CO2 uptake of 6.42 mmol/g (Fig. 3a), attributed to the greater availability of amine groups and enhanced interaction with CO 2 . Despite limited diffusion at low temperatures, PEI 2000 enabled effective amine activation. As the temperature increased, the composition combining 25k PEI (30%), 2000 PEI (70%), and [EMIm]Br showed superior performance (Fig. 3b–d), reaching 3.64 mmol/g at 130°C. This improvement is associated with the thermal stability of 25k PEI and the ionic-dipole interactions provided by [EMIm]Br, which help maintain CO 2 –amine binding and suppress desorption at elevated temperatures. CO 2 adsorption was further examined under 421 ppm and 4% CO 2 using logarithmic-scale plots (Fig. 3e–h). At low concentrations and high temperatures, adsorption capacity decreased significantly due to the exothermic nature of chemisorption and limited CO 2 availability. At high concentrations, the number of accessible amine sites became the dominant factor affecting capacity. The reusability of the aerogel was assessed over 50 adsorption–desorption cycles (Fig. 3i). The 25k 30%-IL12.5% composition maintained 82.92% of its initial capacity, while PEI 2000 and 25k 30% without IL showed reduced retention (41.89% and 61.67%, respectively), indicating that [EMIm]Br plays a key role in stabilizing the structure and active sites. Fig. 3j presents a comparative summary of CO 2 adsorption capacities across all tested temperatures. Notably, the 25k–IL composition, in conjunction with the structurally robust PVMDMS@PVP aerogel support, exhibited consistently high performance within the elevated temperature range of 70–130°C. Gas-Phase Cycloaddition Reaction of Epoxide and Carbon Dioxide Zn 2+ -impregnated 25k 30%-IL12.5%-based PVMDMS@PVP aerogel catalyst was employed to evaluate the catalytic performance and stability in the cycloaddition reaction of CO 2 and propylene oxide (PO). The catalytic mechanism involves a synergistic interaction between the porous structure of aerogel, Zn 2+ , PEI, and [EMIm]Br, which enables efficient coupling of CO 2 and PO at the active interface to yield propylene carbonate (PC) (Fig. 4a). The gas-phase reaction benefits not only from the high surface area and open pore network provided by the aerogel but also from the strong interactions among the active components. This synergistic effect serves as a key factor in achieving high catalytic performance. In batch reactor experiments, the aerogel catalyst showed a remarkable durability up to 100 cycles (395.3 hours) without deterioration of the catalyst performance. Even the reaction kinetics demonstrated a slight improvement, with the complete consumption time of the reactants decreasing from 242 minutes to 236 minutes per a single reaction cycle (Fig. 4b). This modest reduction in reaction time indicates that the optimal catalytic environment integrating Zn 2+ , PEI, and [EMIm]Br effectively promotes contact between CO 2 and PO. Such improvements in reactant diffusion and active site stabilization appear to have a meaningful impact on the overall reaction rate, particularly in systems where mass transfer is critical. A more detailed analysis of the reaction activity revealed that the Zn 2+ loading is a critical parameter for optimizing both catalytic performance and selectivity. The absence of any one component among PEI, [EMIm]Br, and Zn 2+ resulted in negligible reaction progress, emphasizing that each plays an indispensable role. In this system, PEI and [EMIm]Br not only enhance CO 2 adsorption but also facilitate the rapid delivery of CO 2 to the active Zn 2+ sites, which in turn anchor the PO molecules. This functional combination ensures that both the adsorption and activation of CO 2 occur simultaneously, thereby maximizing the reaction efficiency and enabling the production of high-purity PC (Fig. 4c). In continuous flow experiments, the CO 2 consumption rate increased with temperature from 10.2 ml/min at 50°C to 13 ml/min at 100°C (Fig. 4d). However, the highest CO 2 consumption and cumulative PC production were observed at 50°C. At this temperature, 42.5 kg of PC was produced using 3 g of the catalyst, compared to 36.5 kg and 26.5 kg at 70°C and 100°C, respectively. Moreover, NMR analysis of PC produced at 70°C confirmed that the PC possessed a purity exceeding 99% (Fig. 3e and Fig. 3f), and the transparent nature of the product further indicates excellent consistency and quality in the continuous flow system (Fig. 4g). Furthermore, the turnover number (TON) of the aerogel catalyst is exceptionally higher at 50°C compared to conventional catalysts such as MOFs (Fig. 4h) for a prolonged time. This overwhelming performance is attributed to the unique structural characteristics of the PVMDMS@PVP aerogel catalyst. The aerogel not only provides a highly porous scaffold that facilitates CO 2 diffusion but also ensures the long-term stability of the active sites, thereby extending the lifetime of catalyst. Breakthrough Measurement and Selectivity The 25k 30%-IL12.5%-based PVMDMS@PVP aerogel exhibits excellent CO 2 selectivity and adsorption performance under various gas compositions and temperature conditions. At 50°C, breakthrough experiments revealed that CO 2 breakthrough times were 77.5 min/g for CO 2 /N 2 (4/96), 45.0 min/g for CO 2 /N 2 (15/85), and 70 min/g for CO 2 /N 2 /O 2 (6/78/16) (Fig. 5a–Fig. 5d). Correspondingly, the maximum adsorption capacities reached 5.30 mmol/g for CO 2 /N 2 (15/85) and 3.41 mmol/g for CO 2 /N 2 /O 2 (6/78/16). As the temperature increased to 70°C and further to 100°C, both the breakthrough times and maximum adsorption capacities increased significantly, indicating a strong temperature dependence (Fig. 5e–Fig. 5l). At 70°C, breakthrough times extended to 300 min/g for CO 2 /N 2 (4/96), 113 min/g for CO 2 /N 2 (15/85), and 225 min/g for CO 2 /N 2 /O 2 (6/78/16), with maximum adsorption capacities of 12.93 mmol/g for CO 2 /N 2 (15/85) and 9.81 mmol/g for CO 2 /N 2 /O 2 (6/78/16). At 100°C, breakthrough times were recorded as 300 min/g for CO 2 /N 2 (4/96), 100 min/g for CO 2 /N 2 (15/85), and 210 min/g for CO 2 /N 2 /O 2 (6/78/16), with corresponding maximum adsorption capacities of 10.85 mmol/g and 8.97 mmol/g, respectively. From the molecular simulation for calculating the interaction between the competing gases, CO 2 interacts significantly more strongly with the aerogel than N 2 in presence of PEI (Fig. S40). The interaction energies for CO 2 are substantially lower than those for N 2 , confirming a thermodynamic preference for CO 2 adsorption. The presence of [EMIm]Br intensifies these interactions by modifying the local energy landscape at the active sites, further stabilizing CO 2 binding. The inherent beneficial properties of the aerogel, such as its high surface area and well-defined pore structure, play a critical role in achieving selective CO 2 adsorption. In addition, benchmarking against various sorbents at 100°C revealed that the aerogel achieved selectivity values of 5516 for CO 2 /N 2 (4/96) and 5078 for CO 2 /N 2 /O 2 (6/78/16) (Fig. 5m). This performance significantly surpasses conventional sorbents such as polymers, ZIF-8, and ionic liquids. The synergistic combination of the silica-based aerogel, strong acid–base interactions of PEI, and dipole effects of [EMIm]Br further enhances its selective adsorption capabilities. The high porosity of the aerogel facilitates rapid CO 2 diffusion into the internal structure, while the strong interactions between amine-functionalized PEI and CO 2 ensure efficient adsorption and retention. Scale-Up and Adsorption Applications Under Ambient Conditions The scalability study of the PVMDMS@PVP aerogel, which was manufactured approximately 10-fold in size, demonstrates that the unique chemical and structural modifications introduced during the sol–gel process involving the tautomerization of PVP, serving as a skeleton of the aerogel, are valid even at a larger scale (Fig. 6a, top). This successful scale-up maintaining uniform morphology and structural integrity is often a major challenge in translating laboratory-scale materials to industrial applications. The visual evidence provided by the comparative images confirms that the integration of PVP not only promotes a homogeneous structure at the microscale but also effectively translates these benefits to a macroscopic level. The stability observed after the impregnation process (Fig. 6a, bottom) further underlines the robustness of the aerogel, suggesting that its intrinsic properties are not compromised by scale-up. In continuous reaction experiments conducted at 70°C, the scaled-up aerogel exhibited remarkable stability over extended operation periods. The production of 18.42 kg of PC for 180 hours, while maintaining a reaction selectivity exceeding 99% (Fig. 6b), highlights the promising potential of the aerogel catalyst for long-term industrial applications. Furthermore, the purity of the produced PC, validated through both 1H-NMR and 13C-NMR analyses (Fig. 6c and Fig. 6d), confirms that the catalyst can consistently deliver high-quality end products. We assembled the NCM523//graphite lithium-ion batteries (LIB) using commercial and synthesized PC electrolyte (1 M LiPF6). As shown in the Fig. S44, after the 100-cycle operation, the reversible specific capacity of LIB assembled with commercial PC was found to be 99.6 mAh/g, offering a high coulombic efficiency near 100%. Notably, the synthesized PC-based LIB also exhibited the comparable cell performance, exhibiting high specific capacity of 98.7 mAh/g. The cycling performance of both cells show similar degradation tendency and lithium storage performance. Beyond its performance in continuous reactions, the scalability of the PVMDMS@PVP aerogel extends to its potential applications in low CO 2 concentration capture and direct air capture (DAC) systems. In a controlled glovebox environment, the aerogel was evaluated under static conditions i.e., in the absence of convective flow CO 2 concentrations were monitored in real time as the temperature varied (Fig. 6e). The results indicate that the porous structure, along with its surface-active sites, effectively adsorbs CO 2 even without the aid of convective mixing, as schematically represented in Fig. 6f. This is particularly significant for DAC applications where the system may operate in enclosed chambers with minimal air flow. Experimentally, the aerogel reduced the CO 2 concentration from an initial 1000 ppm to 395 ppm within 83 hours (Fig. 6g), demonstrating its excellent CO 2 absorption under low conditions. Discussion This study demonstrates the development of a structurally reinforced and functionally integrated PVMDMS@PVP aerogel system capable of both CO 2 capture and catalytic conversion. The use of PVP during the sol–gel synthesis enabled covalent crosslinking within the PVMDMS network via tautomerization, significantly enhancing the resistance of the aerogel to capillary stress, solvent-induced collapse, and thermal deformation. The resulting hybrid framework exhibited excellent shape retention under both ambient drying and diverse solvent exposures, addressing a critical limitation of conventional silica-based aerogels. Moreover, the aerogel maintained uniform pore structures and macroscopic integrity after scale-up, confirming the structural scalability of the aerogel. Upon functionalization with polyethyleneimine (PEI) and [EMIm]Br, the aerogel exhibited high CO 2 uptake across a wide temperature range, with the 25k–IL composition delivering stable adsorption performance and selectivity between 70–130°C. The preserved pore accessibility and chemical stability under thermal stress contributed to this performance, while reusability over 50 cycles demonstrated long-term operational reliability. The high compatibility of this system with mixed-gas conditions and its exceptional selectivity further highlight the effectiveness of the aerogel support in enabling gas-specific adsorption through synergistic acid–base and dipole interactions. Beyond adsorption, the same PVMDMS@PVP aerogel enabled the gas-phase cycloaddition of CO 2 with epoxides by incorporating Zn²⁺ into the active matrix. The integrated presence of PEI, [EMIm]Br, and Zn 2+ promoted effective activation and conversion of CO 2 at mild conditions, achieving over 99% selectivity for propylene carbonate even under continuous flow operation. Notably, the catalyst-maintained stability over 100 cycles and achieved high TON values at 50°C under continuous operation, surpassing benchmark previously reported systems. This bifunctional reactivity adsorption and chemical transformation within a single, structurally resilient framework represents a significant advancement for CO 2 utilization technologies. This work establishes an integrated aerogel platform that uniquely combines mechanical robustness, scalable architecture, and dual functionality. By unifying CO 2 capture and catalytic conversion into a single material, the PVMDMS@PVP system provides a practical, high-performance approach for industrial carbon management applications. Declarations Author contributions: Conceptualization: Kyung Hoon Min, Sang Eun Shim, Yingjie Qian Methodology: Kyung Hoon Min, Byeongseok Kim Investigation: Kyung Hoon Min, Byeongseok Kim, Kyoung Tae Park, Sung-Hyeon Baeck Computational analysis: Yongjin Lee Visualization: Kyung Hoon Min, Haryeong Choi, Kyeongseok Min Project administration: Hyung-Ho Park Funding procurement: Sang Eun Shim Supervision: Sang Eun Shim, Yingjie Qian Writing – original draft: Kyung Hoon Min Writing – review & editing: Kyung Hoon Min, Sang Eun Shim, Yingjie Qian Funding This work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government (MSIT) (RS-2020-NR049541) and the National Research Foundation of Korea(NRF) grant funded by the Korea government (MEST) (No. RS-2024-00431381). Data availability Data supporting this study are provided as Source data or included in Supplementary Information. 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Supplementary Files Supportinginformation.pdf Cite Share Download PDF Status: Published Journal Publication published 01 Oct, 2025 Read the published version in Advanced Composites and Hybrid Materials → Version 1 posted Editorial decision: Revision requested 29 Jul, 2025 Reviews received at journal 08 Jul, 2025 Reviews received at journal 24 Jun, 2025 Reviewers agreed at journal 24 Jun, 2025 Reviewers agreed at journal 24 Jun, 2025 Reviewers invited by journal 23 Jun, 2025 Editor assigned by journal 19 Jun, 2025 Submission checks completed at journal 11 Jun, 2025 First submitted to journal 08 Jun, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6847440","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":475587495,"identity":"5bc1d3b2-cd82-4575-9fb5-e1e0c1e170f2","order_by":0,"name":"Kyung Hoon Min","email":"","orcid":"","institution":"Inha University","correspondingAuthor":false,"prefix":"","firstName":"Kyung","middleName":"Hoon","lastName":"Min","suffix":""},{"id":475587496,"identity":"85b35c98-8fd6-4d1c-96c5-a786c3946146","order_by":1,"name":"Byeongseok Kim","email":"","orcid":"","institution":"Inha University","correspondingAuthor":false,"prefix":"","firstName":"Byeongseok","middleName":"","lastName":"Kim","suffix":""},{"id":475587497,"identity":"c1105750-257b-42b1-90bf-de13028839ed","order_by":2,"name":"Kyoung Tae Park","email":"","orcid":"","institution":"Inha University","correspondingAuthor":false,"prefix":"","firstName":"Kyoung","middleName":"Tae","lastName":"Park","suffix":""},{"id":475587499,"identity":"8d1a79fb-26cb-43c3-9550-d23cd6bd3bc6","order_by":3,"name":"Kyeongseok Min","email":"","orcid":"","institution":"Inha University","correspondingAuthor":false,"prefix":"","firstName":"Kyeongseok","middleName":"","lastName":"Min","suffix":""},{"id":475587500,"identity":"3ac9cc23-66bf-4641-a116-dbaf5dd3ef74","order_by":4,"name":"Haryeong Choi","email":"","orcid":"","institution":"Yonsei University","correspondingAuthor":false,"prefix":"","firstName":"Haryeong","middleName":"","lastName":"Choi","suffix":""},{"id":475587501,"identity":"a6416b99-d5df-4071-8687-bb98002e8bef","order_by":5,"name":"Hyung-Ho Park","email":"","orcid":"","institution":"Yonsei University","correspondingAuthor":false,"prefix":"","firstName":"Hyung-Ho","middleName":"","lastName":"Park","suffix":""},{"id":475587502,"identity":"dc73cdb2-dffd-47f1-a5a2-f89883b3acc8","order_by":6,"name":"Yongjin Lee","email":"","orcid":"","institution":"Inha University","correspondingAuthor":false,"prefix":"","firstName":"Yongjin","middleName":"","lastName":"Lee","suffix":""},{"id":475587503,"identity":"bad88ba1-2643-465f-a822-04e59e89ff25","order_by":7,"name":"Sung-Hyeon Baeck","email":"","orcid":"","institution":"Inha University","correspondingAuthor":false,"prefix":"","firstName":"Sung-Hyeon","middleName":"","lastName":"Baeck","suffix":""},{"id":475587504,"identity":"69f53718-0b66-430c-9c69-4b53087e8c54","order_by":8,"name":"Sang Eun Shim","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAvUlEQVRIiWNgGAWjYHACNoYEBhseBgkIz4BYLWmkamFgOMxAvBb59vZnDx7mnJcxl25+wPCjhsHYvIGAFoMzZ8wNErfd5rGcc8yAsecYg5nMAUJaJHLYJEBaDG4kGDDwNjDYSBB02Pznz4BazgG1pH9g/EuMFoYbDGZALQeAWnIMmIG2mBHUYnAmB6QlGaSl4LDMMQljwg5rP/5M8uc2O3ugwzY+fFNjYziDoMOQwQF47IyCUTAKRsEooAwAAKcaOmLcmwI5AAAAAElFTkSuQmCC","orcid":"","institution":"Inha University","correspondingAuthor":true,"prefix":"","firstName":"Sang","middleName":"Eun","lastName":"Shim","suffix":""},{"id":475587505,"identity":"2a883e9c-8e6e-4a36-b20c-54f973477a4b","order_by":9,"name":"Yingjie Qian","email":"","orcid":"","institution":"Inha University","correspondingAuthor":false,"prefix":"","firstName":"Yingjie","middleName":"","lastName":"Qian","suffix":""}],"badges":[],"createdAt":"2025-06-08 12:38:15","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6847440/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6847440/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s42114-025-01443-6","type":"published","date":"2025-10-01T15:58:11+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":85472214,"identity":"1de259ef-e285-4f0f-a3e7-10bf61f06745","added_by":"auto","created_at":"2025-06-26 09:24:20","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":156481,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSynthesis of PVMDMS@PVP aerogel, moldability, and solvent stability of aerogel.\u003c/strong\u003e (\u003cstrong\u003ea\u003c/strong\u003e) Procedure for the synthesis of PVMDMS@PVP aerogel. (\u003cstrong\u003eb\u003c/strong\u003e, \u003cstrong\u003ec\u003c/strong\u003e and \u003cstrong\u003ed\u003c/strong\u003e) Photographs of aerogels and SEM images of internal pore structure of various shapes.\u003c/p\u003e","description":"","filename":"image1.tiff.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6847440/v1/1957a863787ab1d62b23cb1e.jpg"},{"id":85472216,"identity":"6bc96ea5-a8f6-42ce-bf81-405070d805d2","added_by":"auto","created_at":"2025-06-26 09:24:20","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":723830,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eStructural reinforcement of PVMDMS aerogels through PVP incorporation and solvent resistance evaluation. \u003c/strong\u003e(\u003cstrong\u003ea\u003c/strong\u003e) Schematic illustration and corresponding SEM images comparing the structural evolution of PVMDMS and PVMDMS@PVP aerogels before and after methanol impregnation followed by ambient drying. (\u003cstrong\u003eb\u003c/strong\u003e–\u003cstrong\u003ef\u003c/strong\u003e) Photographs showing the physical integrity of aerogels with varying PVP contents after methanol impregnation and drying: (\u003cstrong\u003eb\u003c/strong\u003e) 0 wt%, (\u003cstrong\u003ec\u003c/strong\u003e) 5 wt%, (\u003cstrong\u003ed\u003c/strong\u003e) 10 wt%, (\u003cstrong\u003ee\u003c/strong\u003e) 15 wt%, and (\u003cstrong\u003ef\u003c/strong\u003e) 20 wt%. (\u003cstrong\u003eg\u003c/strong\u003e–\u003cstrong\u003el\u003c/strong\u003e) Solvent resistance evaluation of PVMDMS@PVP aerogels. Top row: aerogels prior to solvent impregnation in various solvents. Middle row: photographs of aerogels after solvent impregnation and ambient drying. Bottom row: SEM images of the dried aerogels.\u003c/p\u003e","description":"","filename":"image2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6847440/v1/f5211d53043e35824f072a28.jpeg"},{"id":85472883,"identity":"a0cda9e4-a98d-4503-bc2b-421768b1b727","added_by":"auto","created_at":"2025-06-26 09:32:20","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":386972,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e adsorption isotherms in various temperatures and recycling performances of aerogel. \u003c/strong\u003e(\u003cstrong\u003ea\u003c/strong\u003e to \u003cstrong\u003ed\u003c/strong\u003e) CO\u003csub\u003e2\u003c/sub\u003e adsorption isotherms at 50, 70, 100, and 130℃. (\u003cstrong\u003ee\u003c/strong\u003e to \u003cstrong\u003eh\u003c/strong\u003e) CO\u003csub\u003e2\u003c/sub\u003e adsorption isotherms at 50, 70, 100, and 130℃ in log scale. (\u003cstrong\u003ei\u003c/strong\u003e) Cyclic test of CO\u003csub\u003e2\u003c/sub\u003e adsorption at 100℃. (\u003cstrong\u003ej\u003c/strong\u003e) Comparison of CO\u003csub\u003e2\u003c/sub\u003e adsorption capacities on the PVMDMS@PVP aerogel and other sorbents at various temperatures.\u003c/p\u003e","description":"","filename":"image3.tiff.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6847440/v1/7572ca41ba0913549306c40a.jpg"},{"id":85472217,"identity":"9df23299-77bd-4e4b-898f-dca35520cd45","added_by":"auto","created_at":"2025-06-26 09:24:20","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":366041,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eKinetic data and catalytic ability on CO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e cycloaddition with PEI-IL-Zn/aerogel catalysts. (a) \u003c/strong\u003eIllustration of the catalytic reaction process between the aerogel catalyst and CO\u003csub\u003e2\u003c/sub\u003e.\u003cstrong\u003e (b) \u003c/strong\u003eKinetic data in the catalytic reaction in a batch reactor.\u003cstrong\u003e (c) \u003c/strong\u003eSelectivity and conversion for the catalytic reaction based on each impregnating material.\u003cstrong\u003e (d) \u003c/strong\u003eKinetic and output data in catalytic reaction in a continuous reactor.\u003cstrong\u003e (e \u003c/strong\u003eand\u003cstrong\u003e f) \u003c/strong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR and \u003csup\u003e13\u003c/sup\u003eC-NMR data for the continuous reactor at 70℃.\u003cstrong\u003e (g) \u003c/strong\u003ePhotograph of the 100℃ products.\u003cstrong\u003e (h) \u003c/strong\u003eComparison of CO\u003csub\u003e2\u003c/sub\u003e cycloaddition on the PVMDMS@PVP aerogel support and other sorbents at various temperatures.\u003c/p\u003e","description":"","filename":"image4.tiff.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6847440/v1/3bf0b733a2aaa57774a4d335.jpg"},{"id":85472219,"identity":"eb9215db-afb3-4197-b0f3-9bf59c52942c","added_by":"auto","created_at":"2025-06-26 09:24:20","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":470657,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAdsorption breakthrough analysis in various conditions.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e to \u003cstrong\u003ed,\u003c/strong\u003e Dynamic CO\u003csub\u003e2\u003c/sub\u003e breakthrough profiles at different compositions at 50℃ with a flow rate of 20 ml/min. \u003cstrong\u003ee\u003c/strong\u003e to \u003cstrong\u003eh,\u003c/strong\u003e Dynamic CO\u003csub\u003e2\u003c/sub\u003e breakthrough profiles at different compositions at 70℃ with a flow rate of 20 ml/min. \u003cstrong\u003ei\u003c/strong\u003e to \u003cstrong\u003el,\u003c/strong\u003e Dynamic CO\u003csub\u003e2\u003c/sub\u003e breakthrough profiles at different compositions at 100℃ with a flow rate of 20 ml/min. \u003cstrong\u003em\u003c/strong\u003e, Comparison of CO\u003csub\u003e2\u003c/sub\u003e selectivity on the PVMDMS@PVP aerogel and other absorbents at various gas compositions.\u003c/p\u003e","description":"","filename":"image5.tiff.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6847440/v1/fbe66f123fd95336f7346948.jpg"},{"id":85472884,"identity":"31545bf0-9108-411b-bab7-1bcb26b647e7","added_by":"auto","created_at":"2025-06-26 09:32:20","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":253097,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScale-up of PVMDMS@PVP aerogel catalyst and DAC ability. a, \u003c/strong\u003eThe photographs of the PVMDMS@PVP aerogel catalyst, the scaled-up PVMDMS@PVP aerogel, and the impregnated scaled-up PVMDMS@PVP aerogel\u003cstrong\u003e. b, \u003c/strong\u003eVariations in selectivity and PC generation in a continuous reactor operating at 70ºC with scaled-up aerogel catalyst.\u003cstrong\u003e c \u003c/strong\u003eand\u003cstrong\u003e d, \u003c/strong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR and \u003csup\u003e13\u003c/sup\u003eC-NMR data of PC generated from the continuous reactor at 70℃ with scaled-up aerogel catalyst.\u003cstrong\u003e e \u003c/strong\u003eand\u003cstrong\u003e f, \u003c/strong\u003eSchematic diagram of a glovebox for direct air capture and the gradient of CO\u003csub\u003e2\u003c/sub\u003e concentration around the aerogel catalyst.\u003cstrong\u003e g, \u003c/strong\u003eProfile of the change in CO\u003csub\u003e2\u003c/sub\u003e concentration in glove box.\u003c/p\u003e","description":"","filename":"image6.tiff.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6847440/v1/c9fc737ee54d06c93fc00450.jpg"},{"id":92883904,"identity":"2876def3-f016-45c5-a957-d996b03b94cc","added_by":"auto","created_at":"2025-10-06 16:10:44","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3440464,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6847440/v1/8d566599-703e-44d9-b64e-9529818dd885.pdf"},{"id":85472238,"identity":"f8856cd7-0a07-4b75-ac85-d3b126b57b00","added_by":"auto","created_at":"2025-06-26 09:24:21","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":27348413,"visible":true,"origin":"","legend":"","description":"","filename":"Supportinginformation.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6847440/v1/01853536fa1451dcc3036185.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eScalable, Durable, and Malleable PVMDMS@PVP Aerogel Catalyst for CO\u003csub\u003e2\u003c/sub\u003e Capture and Successive Gas-Phase Cycloaddition Reaction\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe combustion of fossil fuels is a major source of carbon dioxide (CO\u003csub\u003e2\u003c/sub\u003e) emissions, which in turn trigger global climate change and exacerbate environmental and energy issues\u003csup\u003e1,2,3,4\u003c/sup\u003e. While carbon capture and storage (CCS) technologies are essential for achieving the targets set by the Paris Agreement\u003csup\u003e5,6,7\u003c/sup\u003e, existing systems face operational challenges, particularly in natural gas combined cycle (NGCC) power plants where CO\u003csub\u003e2\u003c/sub\u003e concentrations are only about 4%\u003csup\u003e8,9,10\u003c/sup\u003e. In addition, the flue gases from these plants contain high levels of oxygen (~12.4%) and moisture (~8.4%), causing, for example, aqueous amine solutions to degrade leading to reduced efficiency and increased maintenance costs\u003csup\u003e11\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eRecently, porous solid materials such as zeolites, metal organic frameworks (MOFs), and silica-based aerogels have garnered considerable attention as candidates for CO\u003csub\u003e2\u003c/sub\u003e capture and utilization due to their high surface areas, tunable chemical functionalities, and relatively low regeneration energy requirements\u003csup\u003e12,13,14,15\u003c/sup\u003e. However, MOFs suffer from thermal and chemical instability, and zeolites and conventional silica aerogels are often limited by mechanical fragility, shrinkage and cracking during drying, and severe structural degradation upon exposure to solvents\u003csup\u003e16,17\u003c/sup\u003e.\u0026nbsp;These limitations significantly hinder their practical application in CO\u003csub\u003e2\u003c/sub\u003e capture and conversion systems that require repeated functionalization, solvent processing, or scale-up. In particular, conventional silica-based aerogels frequently experience irreversible collapse of their porous networks during solvent impregnation and ambient pressure drying due to capillary stress and weak gel skeletons, resulting in diminished surface area, reduced accessibility of active sites, and compromised catalytic performance\u003csup\u003e18,19\u003c/sup\u003e. Therefore, there is a growing need for next-generation hybrid materials that not only exhibit excellent structural and chemical stability but also integrate CO\u003csub\u003e2\u003c/sub\u003e capture and catalytic conversion capabilities within a single platform.\u003c/p\u003e\n\u003cp\u003eMeanwhile, there is growing interest in integrated approaches that not only capture CO\u003csub\u003e2\u003c/sub\u003e but also convert it into high-value chemicals. Such approaches can enhance overall process efficiency and significantly reduce emissions, thereby advancing a circular carbon economy. Among these, cycloaddition reactions have garnered considerable attention due to their relatively low energy demands and their ability to produce cyclic carbonates high-value chemicals that serve as essential precursors for pharmaceuticals, polymers, and other advanced materials\u003csup\u003e20\u003c/sup\u003e. Consequently, the development of new adsorbents with robust thermal and chemical stability, high structural integrity, and excellent scalability is critical for the advancement of CCS and CO\u003csub\u003e2\u003c/sub\u003e utilization technologies.\u003c/p\u003e\n\u003cp\u003eIn this study, we address these challenges by incorporating the functional polymer polyvinylpyrrolidone (PVP) into the sol\u0026ndash;gel synthesis process of polyvinylmethyldimethoxysilane (PVMDMS)-based aerogels. Through tautomerization, PVP forms strong covalent bonds with PVMDMS precursors\u003csup\u003e21\u003c/sup\u003e, thereby mitigating shrinkage and cracking while significantly enhancing resistance to both polar and non-polar solvents. Additionally, the impregnation of polyethyleneimine (PEI) and [EMIm]Br, coupled with the introduction of Zn\u003csup\u003e2+\u003c/sup\u003e, enhanced the catalytic activity and selectivity of the aerogel for the cycloaddition reaction of CO\u003csub\u003e2\u003c/sub\u003e and epoxides. Experimental results demonstrate that this aerogel operates stably over a wide temperature range of 50\u0026ndash;130\u0026deg;C and exhibits excellent cyclic performance during CO\u003csub\u003e2\u003c/sub\u003e desorption processes. These findings highlight the potential of this innovative aerogel as a high-performance sorbent and catalyst support for CO\u003csub\u003e2\u003c/sub\u003e capture and conversion in environmental and energy applications. Furthermore, the scalability and robustness of this material underscore its potential for integration into large-scale industrial processes, offering a sustainable pathway for carbon management technologies.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cstrong\u003eSynthesis of PVMDMS@PVP aerogels\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe synthesis of the PVMDMS precursor began by placing 12.12 g of VMDMS and 0.705 g of di-tert-butyl peroxide (DTBP) into a 50 mL liner. The mixture was purged with argon for 10 minutes to remove oxygen, followed by stirring at 400 rpm for 5 minutes. The prepared liner containing the mixture was placed into an autoclave and subjected to radical polymerization at 120\u0026deg;C for 48 hours. After the reaction, the autoclave was cooled to room temperature, and the resulting precursor was collected for further processing.\u003c/p\u003e\n\u003cp\u003eFor the sol-gel process, 3 g of the recovered precursor was dispersed in 11.04 g of benzyl alcohol (BnOH). Subsequently, 0.6 g of polyvinylpyrrolidone (PVP, Mw: 40,000 g/mol) was added to the solution and stirred until fully dissolved. To initiate the sol-gel reaction, 0.197 g of distilled water and 0.6205 g of tetramethylammonium hydroxide (TMAOH, 10 wt% in H\u003csub\u003e2\u003c/sub\u003eO) were added to the mixture, which was stirred for 5 minutes. The resulting sol was then transferred into 20 mL vials and subjected to aging in an oven at 100\u0026deg;C for 5 days.\u003c/p\u003e\n\u003cp\u003eFollowing the aging process, the solid gels were washed three times with isopropyl alcohol (IPA), each washing lasting 8 hours, to remove residual solvents and impurities. Finally, the aerogels were dried at room temperature for 2 days, yielding the final PVMDMS@PVP aerogel.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of PVMDMS@PVP Aerogel Film\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo fabricate the PVMDMS@PVP aerogel film, a precursor sol was prepared following the composition described in Section 2.2.1 and stirred at 400 rpm for 10 minutes at room temperature to ensure homogeneity. The sol was then cast into a polypropylene (PP) mold (\u0026Oslash; 80 mm) to a height of less than 5 mm, facilitating the formation of a thin film. Gelation was confirmed by the transition from a fluid sol to a non-flowing gel. The resulting wet gel was aged in benzyl alcohol at 100 \u0026deg;C for 5 days in a convection oven to promote crosslinking and reinforce the silica framework. After aging, the gel was washed with isopropyl alcohol every 12 hours for 3 days to remove unreacted species and residual solvent. Finally, the film was dried under ambient temperature and pressure to obtain the PVMDMS@PVP aerogel. \u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of PVMDMS@PVP Aerogel Fiber\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo synthesize the PVMDMS@PVP aerogel fiber, the precursor sol was prepared according to the composition described in Section 2.2.1 and stirred at 400 rpm for 10 minutes at room temperature to ensure uniform mixing. The sol was then loaded into a syringe fitted with a 29-gauge needle (inner diameter ~0.18 mm) and continuously injected at a flow rate of 1 mL\u0026middot;min⁻\u0026sup1; into an aqueous tetramethylammonium hydroxide (TMAOH) solution (pH 12), where immediate gelation occurred upon contact. The resulting gel fibers were gently collected and transferred into benzyl alcohol for aging at 100 \u0026deg;C for 5 days in a convection oven to reinforce the silica network. After aging, the fibers were washed with isopropyl alcohol every 12 hours for 3 days to remove unreacted species and residual by-products. The final aerogel fibers were obtained by drying under ambient temperature and pressure.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of [EMIm]Br\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e1-Methylimidazole was measured into a 2 or 3-neck flask, to which a magnetic stir bar is added. A condenser was attached to one neck, and the other neck was sealed with a rubber septum. Bromoethane was then added dropwise. The molar ratio was set to 1:1.2 for this experiment. The mixture was vigorously stirred at room temperature while adding bromoethane dropwise. After the addition was completed, the stirring was continued overnight.\u003cbr\u003e \u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePhysical impregnation with PEI, [EMIm]Br, and Zn\u003csup\u003e2+\u003c/sup\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSolution A was prepared by dissolving polyethyleneimine (PEI) and zinc acetate in 20 mL of methanol at 40\u0026deg;C with stirring at 450 rpm for 30 min, while Solution B was obtained by dissolving the ionic liquid (IL) in another 20 mL of methanol at 40\u0026deg;C, 450 rpm for 10 min. After mixing Solutions A and B at 40\u0026deg;C for a designated time, the as-synthesized aerogels (1 g) were immersed in the combined solution and stirred (200 rpm) at 40\u0026deg;C for 4 h, followed by a 12 h modification step at the same temperature. For impregnation with PEI, a total of 2 g of PEI (per 1 g of aerogel) was introduced, where 2 g was taken as 100%. From the total 2 g of PEI, x% consisted of PEI with a molecular weight of 25,000 g/mol (PEI25k), while the remaining (100\u0026minus;x)% was PEI with a molecular weight of 2,000 g/mol (PEI2000). Additionally, the ionic liquid (IL) was added at y% relative to this total PEI (2 g), forming a mixture denoted as \u0026ldquo;25k x% \u0026ndash; IL y%.\u0026rdquo; After the modification process, the samples were dried at 80\u0026deg;C under an argon (or nitrogen) flow until the aerogel color changed from yellow to white, indicating successful impregnation and solvent removal.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCharacterization\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe morphology of the aerogel and impregnated aerogel was examined using field emission scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy (SEM-EDS; S-4300SE, Hitachi, Japan) at the Core Facility Center for Sustainable Energy Materials of the Korea Basic Science Institute (KBSI). To prevent charging effects, the samples were sputter-coated with a thin layer of platinum (4 nm) using a sputter coater (Quorum Technologies Ltd, Q150T-S, UK) prior to analysis. The SEM was operated at an accelerating voltage of 15 kV, providing a resolution of 1.5 nm. Additionally, TEM images were obtained using a Philips CM200 transmission electron microscope (Philips Electronics, Netherlands) operated at an acceleration voltage of 200 kV. Aerogel samples were dispersed in ethanol via ultrasonication, drop-cast onto a copper TEM grid, and dried at room temperature prior to analysis. Thermal properties were measured using a TGA 4000 thermogravimetric analyzer (PerkinElmer, USA). TG curves were obtained by increasing the temperature at a rate of 10\u0026deg;C/min from 30 to 800\u0026deg;C under a flow of pure N\u003csub\u003e2\u003c/sub\u003e gas at 20 ml/min. Nitrogen adsorption-desorption isotherms were obtained using a BELSORP-max (MicrotracBEL Corp., Japan) instrument at \u0026minus;196\u0026deg;C. The samples were pretreated at 120\u0026deg;C under vacuum for 12 hours prior to measurement. The specific surface area (SSA) was calculated from the adsorption branch using the standard Brunauer-Emmett-Teller (BET) theory, while the pore size distribution and total pore volume were determined using the Barrett-Joyner-Halenda (BJH) method based on the adsorption isotherm. \u0026sup1;H and \u0026sup1;\u0026sup3;C NMR spectra were recorded on a Bruker Avance III 400 MHz spectrometer (Bruker Corporation, Germany) using CDCl₃ as the solvent. The amount of Zn\u0026sup2;⁺ leached from the impregnated aerogel was measured using inductively coupled plasma-optical emission spectrometry (ICP-OES; OPTIMA 7300 DV, PerkinElmer, USA). Similarly, the amount of Br\u003csup\u003e\u0026ndash;\u003c/sup\u003e leached from the impregnated aerogel was measured using ion chromatography (IC; ICS-3000, Dionex Korea, South Korea).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis and versatile moldability of PVMDMS@PVP aerogels\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe PVMDMS@PVP aerogel was synthesized via a sol\u0026ndash;gel reaction in which polyvinylpyrrolidone (PVP) undergoes tautomerization under basic conditions and forms covalent bonds with the PVMDMS precursor, resulting in a chemically crosslinked hybrid network (Fig. 1a). This structural configuration enhanced both the formability and the stability of the aerogel. The PVMDMS@PVP aerogel could be readily molded into various macroscopic shapes, including monoliths, films, and continuous fibers, while maintaining uniform internal pore structures in all forms, as confirmed by SEM analysis (Fig. 1b\u0026ndash;d). The covalently bonded hybrid framework also contributed to improved thermal and structural stability. Thermogravimetric analysis (Fig. S1) showed that the introduction of PVP led to a higher decomposition onset temperature and greater residual weight at 700 \u0026ordm;C compared to pristine PVMDMS. Drying behavior was evaluated under ambient and supercritical CO\u003csub\u003e2\u003c/sub\u003e conditions. As shown in Fig. S2, the pristine PVMDMS aerogel underwent substantial shrinkage and collapse during ambient drying, whereas PVMDMS@PVP aerogels retained their original shape with minimal deformation. Quantitative shrinkage analysis (Fig. S3) revealed that PVMDMS-AD samples exhibited a shrinkage ratio of approximately 50%, while PVMDMS@PVP-AD samples showed less than 5%. These results suggest that the hybrid network formed via tautomerization improves not only processability but also thermal and structural stability by mitigating capillary stress during drying.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eShape retention of PVMDMS@PVP aerogels under solvent exposure\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo evaluate the structural durability of the aerogels under solvent exposure, PVMDMS and PVMDMS@PVP aerogels were first immersed in methanol and dried under ambient conditions. As shown in Fig. 2a, the pristine PVMDMS aerogel exhibited significant shrinkage and pore collapse following solvent treatment, indicating poor resistance to capillary stress. In contrast, the PVMDMS@PVP aerogel retained its porous structure with minimal deformation, suggesting improved solvent tolerance due to the covalently crosslinked hybrid framework.\u003c/p\u003e\n\u003cp\u003eTo further examine the effect of PVP concentration on structural preservation, aerogels containing 0 to 20 wt% PVP were subjected to the same methanol soaking and drying procedure. As shown in Fig. 2b\u0026ndash;f, samples with \u0026le;10 wt% PVP displayed visible cracking, deformation, or fragmentation after drying, whereas those with 15\u0026ndash;20 wt% maintained their original monolithic form. These results indicate that a minimum threshold of PVP is required to prevent structural failure during solvent induced stress.\u003c/p\u003e\n\u003cp\u003eThe solvent compatibility of the PVMDMS@PVP aerogel was subsequently evaluated using a series of polar (acetone, methanol, DMSO, DMF) and non-polar (THF, cyclohexane) solvents. In Fig. 2g\u0026ndash;l, each panel presents three images: the top shows the aerogel prior to solvent exposure, the middle shows the sample after soaking and ambient drying, and the bottom provides SEM images of the internal pore network. In all solvent systems tested, the aerogels retained their macroscopic shape without noticeable shrinkage or surface cracking. SEM analysis further confirmed that the internal porous structures remained intact under all solvent conditions, regardless of polarity.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCarbon Dioxide Adsorption and Recyclability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eBuilding on the excellent solvent compatibility of the PVMDMS@PVP aerogel, its CO\u003csub\u003e2\u003c/sub\u003e adsorption performance was evaluated after impregnation with polyethyleneimine (PEI) and [EMIm]Br over a temperature range of 50\u0026ndash;130\u0026deg;C. At 50\u0026deg;C, the aerogel containing low-viscosity PEI exhibited the highest CO2 uptake of 6.42 mmol/g (Fig. 3a), attributed to the greater availability of amine groups and enhanced interaction with CO\u003csub\u003e2\u003c/sub\u003e. Despite limited diffusion at low temperatures, PEI 2000 enabled effective amine activation. As the temperature increased, the composition combining 25k PEI (30%), 2000 PEI (70%), and [EMIm]Br showed superior performance (Fig. 3b\u0026ndash;d), reaching 3.64 mmol/g at 130\u0026deg;C. This improvement is associated with the thermal stability of 25k PEI and the ionic-dipole interactions provided by [EMIm]Br, which help maintain CO\u003csub\u003e2\u003c/sub\u003e\u0026ndash;amine binding and suppress desorption at elevated temperatures.\u003c/p\u003e\n\u003cp\u003eCO\u003csub\u003e2\u003c/sub\u003e adsorption was further examined under 421 ppm and 4% CO\u003csub\u003e2\u003c/sub\u003e using logarithmic-scale plots (Fig. 3e\u0026ndash;h). At low concentrations and high temperatures, adsorption capacity decreased significantly due to the exothermic nature of chemisorption and limited CO\u003csub\u003e2\u003c/sub\u003e availability. At high concentrations, the number of accessible amine sites became the dominant factor affecting capacity.\u003c/p\u003e\n\u003cp\u003eThe reusability of the aerogel was assessed over 50 adsorption\u0026ndash;desorption cycles (Fig. 3i). The 25k 30%-IL12.5% composition maintained 82.92% of its initial capacity, while PEI 2000 and 25k 30% without IL showed reduced retention (41.89% and 61.67%, respectively), indicating that [EMIm]Br plays a key role in stabilizing the structure and active sites. Fig. 3j presents a comparative summary of CO\u003csub\u003e2\u003c/sub\u003e adsorption capacities across all tested temperatures. Notably, the 25k\u0026ndash;IL composition, in conjunction with the structurally robust PVMDMS@PVP aerogel support, exhibited consistently high performance within the elevated temperature range of 70\u0026ndash;130\u0026deg;C.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eGas-Phase Cycloaddition Reaction of Epoxide and Carbon Dioxide\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eZn\u003csup\u003e2+\u003c/sup\u003e-impregnated 25k 30%-IL12.5%-based PVMDMS@PVP aerogel catalyst was employed to evaluate the catalytic performance and stability in the cycloaddition reaction of CO\u003csub\u003e2\u003c/sub\u003e and propylene oxide (PO). The catalytic mechanism involves a synergistic interaction between the porous structure of aerogel, Zn\u003csup\u003e2+\u003c/sup\u003e, PEI, and [EMIm]Br, which enables efficient coupling of CO\u003csub\u003e2\u003c/sub\u003e and PO at the active interface to yield propylene carbonate (PC) (Fig. 4a). The gas-phase reaction benefits not only from the high surface area and open pore network provided by the aerogel but also from the strong interactions among the active components. This synergistic effect serves as a key factor in achieving high catalytic performance.\u003c/p\u003e\n\u003cp\u003eIn batch reactor experiments, the aerogel catalyst showed a remarkable durability up to 100 cycles (395.3 hours) without deterioration of the catalyst performance. Even the reaction kinetics demonstrated a slight improvement, with the complete consumption time of the reactants decreasing from 242 minutes to 236 minutes per a single reaction cycle (Fig. 4b). This modest reduction in reaction time indicates that the optimal catalytic environment integrating Zn\u003csup\u003e2+\u003c/sup\u003e, PEI, and [EMIm]Br effectively promotes contact between CO\u003csub\u003e2\u003c/sub\u003e and PO. Such improvements in reactant diffusion and active site stabilization appear to have a meaningful impact on the overall reaction rate, particularly in systems where mass transfer is critical.\u003c/p\u003e\n\u003cp\u003eA more detailed analysis of the reaction activity revealed that the Zn\u003csup\u003e2+\u003c/sup\u003e loading is a critical parameter for optimizing both catalytic performance and selectivity. The absence of any one component among PEI, [EMIm]Br, and Zn\u003csup\u003e2+\u003c/sup\u003e resulted in negligible reaction progress, emphasizing that each plays an indispensable role. In this system, PEI and [EMIm]Br not only enhance CO\u003csub\u003e2\u003c/sub\u003e adsorption but also facilitate the rapid delivery of CO\u003csub\u003e2\u003c/sub\u003e to the active Zn\u003csup\u003e2+\u003c/sup\u003e sites, which in turn anchor the PO molecules. This functional combination ensures that both the adsorption and activation of CO\u003csub\u003e2\u003c/sub\u003e occur simultaneously, thereby maximizing the reaction efficiency and enabling the production of high-purity PC (Fig. 4c).\u003c/p\u003e\n\u003cp\u003eIn continuous flow experiments, the CO\u003csub\u003e2\u003c/sub\u003e consumption rate increased with temperature from 10.2 ml/min at 50\u0026deg;C to 13 ml/min at 100\u0026deg;C (Fig. 4d). However, the highest CO\u003csub\u003e2\u003c/sub\u003e consumption and cumulative PC production were observed at 50\u0026deg;C. At this temperature, 42.5 kg of PC was produced using 3 g of the catalyst, compared to 36.5 kg and 26.5 kg at 70\u0026deg;C and 100\u0026deg;C, respectively. Moreover, NMR analysis of PC produced at 70\u0026deg;C confirmed that the PC possessed a purity exceeding 99% (Fig. 3e and Fig. 3f), and the transparent nature of the product further indicates excellent consistency and quality in the continuous flow system (Fig. 4g). Furthermore, the turnover number (TON) of the aerogel catalyst is exceptionally higher at 50\u0026deg;C compared to conventional catalysts such as MOFs (Fig. 4h) for a prolonged time. This overwhelming performance is attributed to the unique structural characteristics of the PVMDMS@PVP aerogel catalyst. The aerogel not only provides a highly porous scaffold that facilitates CO\u003csub\u003e2\u003c/sub\u003e diffusion but also ensures the long-term stability of the active sites, thereby extending the lifetime of catalyst.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eBreakthrough Measurement and Selectivity\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe 25k 30%-IL12.5%-based PVMDMS@PVP aerogel exhibits excellent CO\u003csub\u003e2\u003c/sub\u003e selectivity and adsorption performance under various gas compositions and temperature conditions. At 50\u0026deg;C, breakthrough experiments revealed that CO\u003csub\u003e2\u003c/sub\u003e breakthrough times were 77.5 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (4/96), 45.0 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (15/85), and 70 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e/O\u003csub\u003e2\u003c/sub\u003e (6/78/16) (Fig. 5a\u0026ndash;Fig. 5d). Correspondingly, the maximum adsorption capacities reached 5.30 mmol/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (15/85) and 3.41 mmol/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e/O\u003csub\u003e2\u003c/sub\u003e (6/78/16).\u003c/p\u003e\n\u003cp\u003eAs the temperature increased to 70\u0026deg;C and further to 100\u0026deg;C, both the breakthrough times and maximum adsorption capacities increased significantly, indicating a strong temperature dependence (Fig. 5e\u0026ndash;Fig. 5l). At 70\u0026deg;C, breakthrough times extended to 300 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (4/96), 113 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (15/85), and 225 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e/O\u003csub\u003e2\u003c/sub\u003e (6/78/16), with maximum adsorption capacities of 12.93 mmol/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (15/85) and 9.81 mmol/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e/O\u003csub\u003e2\u003c/sub\u003e (6/78/16). At 100\u0026deg;C, breakthrough times were recorded as 300 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (4/96), 100 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (15/85), and 210 min/g for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e/O\u003csub\u003e2\u003c/sub\u003e (6/78/16), with corresponding maximum adsorption capacities of 10.85 mmol/g and 8.97 mmol/g, respectively.\u003c/p\u003e\n\u003cp\u003eFrom the molecular simulation for calculating the interaction between the competing gases, CO\u003csub\u003e2\u003c/sub\u003e interacts significantly more strongly with the aerogel than N\u003csub\u003e2\u003c/sub\u003e in presence of PEI (Fig. S40). The interaction energies for CO\u003csub\u003e2\u003c/sub\u003e are substantially lower than those for N\u003csub\u003e2\u003c/sub\u003e, confirming a thermodynamic preference for CO\u003csub\u003e2\u003c/sub\u003e adsorption. The presence of [EMIm]Br intensifies these interactions by modifying the local energy landscape at the active sites, further stabilizing CO\u003csub\u003e2\u003c/sub\u003e binding. The inherent beneficial properties of the aerogel, such as its high surface area and well-defined pore structure, play a critical role in achieving selective CO\u003csub\u003e2\u003c/sub\u003e adsorption.\u003c/p\u003e\n\u003cp\u003eIn addition, benchmarking against various sorbents at 100\u0026deg;C revealed that the aerogel achieved selectivity values of 5516 for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e (4/96) and 5078 for CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e/O\u003csub\u003e2\u003c/sub\u003e (6/78/16) (Fig. 5m). This performance significantly surpasses conventional sorbents such as polymers, ZIF-8, and ionic liquids. The synergistic combination of the silica-based aerogel, strong acid\u0026ndash;base interactions of PEI, and dipole effects of [EMIm]Br further enhances its selective adsorption capabilities. The high porosity of the aerogel facilitates rapid CO\u003csub\u003e2\u003c/sub\u003e diffusion into the internal structure, while the strong interactions between amine-functionalized PEI and CO\u003csub\u003e2\u003c/sub\u003e ensure efficient adsorption and retention.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eScale-Up and Adsorption Applications Under Ambient Conditions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe scalability study of the PVMDMS@PVP aerogel, which was manufactured approximately 10-fold in size, demonstrates that the unique chemical and structural modifications introduced during the sol\u0026ndash;gel process involving the tautomerization of PVP, serving as a skeleton of the aerogel, are valid even at a larger scale (Fig. 6a, top). This successful scale-up maintaining uniform morphology and structural integrity is often a major challenge in translating laboratory-scale materials to industrial applications. The visual evidence provided by the comparative images confirms that the integration of PVP not only promotes a homogeneous structure at the microscale but also effectively translates these benefits to a macroscopic level. The stability observed after the impregnation process (Fig. 6a, bottom) further underlines the robustness of the aerogel, suggesting that its intrinsic properties are not compromised by scale-up.\u003c/p\u003e\n\u003cp\u003eIn continuous reaction experiments conducted at 70\u0026deg;C, the scaled-up aerogel exhibited remarkable stability over extended operation periods. The production of 18.42 kg of PC for 180 hours, while maintaining a reaction selectivity exceeding 99% (Fig. 6b), highlights the promising potential of the aerogel catalyst for long-term industrial applications. Furthermore, the purity of the produced PC, validated through both 1H-NMR and 13C-NMR analyses (Fig. 6c and Fig. 6d), confirms that the catalyst can consistently deliver high-quality end products. We assembled the NCM523//graphite lithium-ion batteries (LIB) using commercial and synthesized PC electrolyte (1 M LiPF6). As shown in the Fig. S44, after the 100-cycle operation, the reversible specific capacity of LIB assembled with commercial PC was found to be 99.6 mAh/g, offering a high coulombic efficiency near 100%. Notably, the synthesized PC-based LIB also exhibited the comparable cell performance, exhibiting high specific capacity of 98.7 mAh/g. The cycling performance of both cells show similar degradation tendency and lithium storage performance. \u003c/p\u003e\n\u003cp\u003eBeyond its performance in continuous reactions, the scalability of the PVMDMS@PVP aerogel extends to its potential applications in low CO\u003csub\u003e2\u003c/sub\u003e concentration capture and direct air capture (DAC) systems. In a controlled glovebox environment, the aerogel was evaluated under static conditions i.e., in the absence of convective flow CO\u003csub\u003e2\u003c/sub\u003e concentrations were monitored in real time as the temperature varied (Fig. 6e). The results indicate that the porous structure, along with its surface-active sites, effectively adsorbs CO\u003csub\u003e2\u003c/sub\u003e even without the aid of convective mixing, as schematically represented in Fig. 6f. This is particularly significant for DAC applications where the system may operate in enclosed chambers with minimal air flow. Experimentally, the aerogel reduced the CO\u003csub\u003e2\u003c/sub\u003e concentration from an initial 1000 ppm to 395 ppm within 83 hours (Fig. 6g), demonstrating its excellent CO\u003csub\u003e2\u003c/sub\u003e absorption under low conditions.\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eThis study demonstrates the development of a structurally reinforced and functionally integrated PVMDMS@PVP aerogel system capable of both CO\u003csub\u003e2\u003c/sub\u003e capture and catalytic conversion. The use of PVP during the sol\u0026ndash;gel synthesis enabled covalent crosslinking within the PVMDMS network via tautomerization, significantly enhancing the resistance of the aerogel to capillary stress, solvent-induced collapse, and thermal deformation. The resulting hybrid framework exhibited excellent shape retention under both ambient drying and diverse solvent exposures, addressing a critical limitation of conventional silica-based aerogels. Moreover, the aerogel maintained uniform pore structures and macroscopic integrity after scale-up, confirming the structural scalability of the aerogel.\u003c/p\u003e\n\u003cp\u003eUpon functionalization with polyethyleneimine (PEI) and [EMIm]Br, the aerogel exhibited high CO\u003csub\u003e2\u003c/sub\u003e uptake across a wide temperature range, with the 25k\u0026ndash;IL composition delivering stable adsorption performance and selectivity between 70\u0026ndash;130\u0026deg;C. The preserved pore accessibility and chemical stability under thermal stress contributed to this performance, while reusability over 50 cycles demonstrated long-term operational reliability. The high compatibility of this system with mixed-gas conditions and its exceptional selectivity further highlight the effectiveness of the aerogel support in enabling gas-specific adsorption through synergistic acid\u0026ndash;base and dipole interactions.\u003c/p\u003e\n\u003cp\u003eBeyond adsorption, the same PVMDMS@PVP aerogel enabled the gas-phase cycloaddition of CO\u003csub\u003e2\u003c/sub\u003e with epoxides by incorporating Zn\u0026sup2;⁺ into the active matrix. The integrated presence of PEI, [EMIm]Br, and Zn\u003csup\u003e2+\u003c/sup\u003e promoted effective activation and conversion of CO\u003csub\u003e2\u003c/sub\u003e at mild conditions, achieving over 99% selectivity for propylene carbonate even under continuous flow operation. Notably, the catalyst-maintained stability over 100 cycles and achieved high TON values at 50\u0026deg;C under continuous operation, surpassing benchmark previously reported systems. This bifunctional reactivity adsorption and chemical transformation within a single, structurally resilient framework represents a significant advancement for CO\u003csub\u003e2\u003c/sub\u003e utilization technologies.\u003c/p\u003e\n\u003cp\u003eThis work establishes an integrated aerogel platform that uniquely combines mechanical robustness, scalable architecture, and dual functionality. By unifying CO\u003csub\u003e2\u003c/sub\u003e capture and catalytic conversion into a single material, the PVMDMS@PVP system provides a practical, high-performance approach for industrial carbon management applications.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor contributions:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eConceptualization: Kyung Hoon Min, Sang Eun Shim, Yingjie Qian\u003c/p\u003e\n\u003cp\u003eMethodology: Kyung Hoon Min, Byeongseok Kim\u003c/p\u003e\n\u003cp\u003eInvestigation: Kyung Hoon Min, Byeongseok Kim, Kyoung Tae Park, Sung-Hyeon Baeck\u003c/p\u003e\n\u003cp\u003eComputational analysis: Yongjin Lee\u003c/p\u003e\n\u003cp\u003eVisualization: Kyung Hoon Min, Haryeong Choi, Kyeongseok Min\u003c/p\u003e\n\u003cp\u003eProject administration: Hyung-Ho Park\u003c/p\u003e\n\u003cp\u003eFunding procurement: Sang Eun Shim\u003c/p\u003e\n\u003cp\u003eSupervision: Sang Eun Shim, Yingjie Qian\u003c/p\u003e\n\u003cp\u003eWriting – original draft: Kyung Hoon Min\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eWriting – review \u0026amp; editing: Kyung Hoon Min, Sang Eun Shim, Yingjie Qian\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government (MSIT) (RS-2020-NR049541) and the National Research Foundation of Korea(NRF) grant funded by the Korea government (MEST) (No. RS-2024-00431381).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eData supporting this study are provided as Source data or included in Supplementary Information. 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A plant leaf-mimetic membrane with controllable gas permeation for efficient preservation of perishable products. \u003cem\u003eACS Nano\u003c/em\u003e \u003cstrong\u003e15\u003c/strong\u003e, 8742\u0026ndash;8752 (2021).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-6847440/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6847440/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA structurally robust PVMDMS@PVP aerogel catalyst was developed by incorporating polyethyleneimine (PEI) and an ionic liquid, followed by Zn\u003csup\u003e2+\u003c/sup\u003e impregnation, for integrated carbon dioxide (CO\u003csub\u003e2\u003c/sub\u003e) capture and catalytic conversion. The solvent-resistant framework maintains high CO\u003csub\u003e2\u003c/sub\u003e adsorption capacity and structural integrity across 50 thermal cycles over a broad temperature range (0–130°C). Breakthrough experiments confirm excellent CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e selectivity (5078) under mixed-gas flow at 100°C. Zn\u003csup\u003e2+\u003c/sup\u003e-functionalized aerogels enable gas-phase cycloaddition of CO\u003csub\u003e2\u003c/sub\u003e with epoxides, achieving \u0026gt;99% selectivity for propylene carbonate over 1978 hours of continuous operation. Notably, the carbonate product was directly applied as an electrolyte in lithium-ion batteries, validating its electrochemical utility. The aerogel preserved its pore structure, catalytic activity, and monolithic form even after scale-up, demonstrating superior mechanical and chemical durability. This work presents a scalable, multifunctional aerogel catalyst platform that combines long-term stability, high CO\u003csub\u003e2\u003c/sub\u003e adsorption efficiency, and battery-relevant carbonate production for advanced CO\u003csub\u003e2\u003c/sub\u003e capture and utilization technologies.\u003c/p\u003e","manuscriptTitle":"Scalable, Durable, and Malleable PVMDMS@PVP Aerogel Catalyst for CO2 Capture and Successive Gas-Phase Cycloaddition Reaction","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-26 09:24:15","doi":"10.21203/rs.3.rs-6847440/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-07-30T02:51:35+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-07-08T10:48:41+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-06-24T07:25:59+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"65147903323263668124150307797184699527","date":"2025-06-24T05:24:52+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"202965469105126481916865189541047756631","date":"2025-06-24T04:43:49+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-06-24T02:23:42+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-06-19T11:00:01+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-06-12T03:36:30+00:00","index":"","fulltext":""},{"type":"submitted","content":"Advanced Composites and Hybrid Materials","date":"2025-06-08T12:29:39+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"3ff1f28d-c7ff-4196-b554-bf23abb1c4ff","owner":[],"postedDate":"June 26th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-10-06T16:04:54+00:00","versionOfRecord":{"articleIdentity":"rs-6847440","link":"https://doi.org/10.1007/s42114-025-01443-6","journal":{"identity":"advanced-composites-and-hybrid-materials","isVorOnly":false,"title":"Advanced Composites and Hybrid Materials"},"publishedOn":"2025-10-01 15:58:11","publishedOnDateReadable":"October 1st, 2025"},"versionCreatedAt":"2025-06-26 09:24:15","video":"","vorDoi":"10.1007/s42114-025-01443-6","vorDoiUrl":"https://doi.org/10.1007/s42114-025-01443-6","workflowStages":[]},"version":"v1","identity":"rs-6847440","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6847440","identity":"rs-6847440","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}