CO2 capture with post-modified consumer acrylonitrile plastics

CO2 capture with post-modified consumer acrylonitrile plastics | 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 Physical Sciences - Article CO 2 capture with post-modified consumer acrylonitrile plastics Troels Skrydstrup, Simon Pedersen, Clemens Kaussler, Ruth Ebenbauer, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5626417/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Carbon capture and storage (CCS) is considered an indispensable tool for abating climate change caused by human activity. With annual CO2-emissions exceeding 37 gigatons, there is an urgent need for accessing sorbents on a million-ton production scale. Solid amine-based CO2-adsorbents are advantageous compared to conventional aqueous absorbents due to an energetically more facile regeneration and greater stability. However, synthesis of solid adsorbents is still comparatively costly and of lower production capacity. Here we report the transition metal catalysed hydrogenation or combined hydrocyanation/hydrogenation of abundant but difficult-to-recycle consumer nitrile plastics, rubbers, and textiles, to generate solid amine adsorbents that capture and release CO2 by thermal swing adsorption. The protocol is showcased with nitrile gloves, LEGO® bricks, kitchenware plastic, and acrylic textiles, taking advantage of the nitrogen already present in these polymers. These amine materials display CO2-capacities up to an average of 2.98 mmol/g, while some can match or even surpass the working capacity of a commercial benchmark adsorbent, Lewatit VP OC 1065, when subjected to simulated flue gas at 90 °C. Furthermore, excellent adsorbent stabilities towards harmful NO2 and SO2 flue gas components are observed. We anticipate our work will provide a potential pathway forward to rapidly accessing new solid adsorbents from consumer plastics for managing CO2-emissions. Physical sciences/Chemistry/Catalysis/Homogeneous catalysis Physical sciences/Chemistry/Polymer chemistry Physical sciences/Chemistry/Environmental chemistry/Pollution remediation Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology Physical sciences/Chemistry/Green chemistry/Sustainability Figures Figure 1 Figure 2 Figure 3 Figure 4 Full Text For mitigating global warming to the 1.5−2.0 °C target of the Paris Agreement, the Intergovernmental Panel on Climate Change (IPCC) estimates a yearly requirement of 5−16 Gt carbon dioxide removal (CDR) by 2050. CCS-technologies such as bioenergy carbon capture and storage (BECCS) and direct air capture (DAC) are key for achieving this goal 1,9 . These gigaton-scale targets are far from the current yearly capture capacities of CCS, BECCS, and DAC, consisting of 50 M, 2 Mt, and 0.047 Mt, respectively 10−13 . Today, point source carbon capture technologies operating at industrial capacity rely on aqueous solutions of small-molecule amines, e.g. monoethanolamine (MEA), but suffer from sorbent leaching, corrosion, decomposition, and a high energy penalty for sorbent regeneration 3 . Next-generation solid adsorbents including amine-grafted or -impregnated supported materials, metal-organic frameworks (MOFs), or self-supported poly(amines), abate the problems of conventional carbon capture 3 . However, today only the liquid absorbents, such as MEA, have reached a commercial scale technology readiness level (TRL) of 9 14 . One unifying trait for most liquid- and solid amine sorbents, is their synthetic dependency on fossil-based resources for production. Attaining the multi-gigaton per-year CCS- and CDR-targets will require significant scaling of adsorbent production to the million-ton level, leading to further environmental challenges unless a switch to sustainable resources is made. Concurrent with global warming, there are growing concerns about the adverse impact of accumulating plastic waste on the environment and human health 15 . In 2022, the total combined production capacity of plastics reached a staggering 400 million tons, of which only 9% corresponded to recycled polymeric materials 16 . Landfilling and incineration remain the most common means of disposal of end-of-life consumer plastic-, rubber-, and textile products. Polymers comprised of nitrogen-containing functionalities could ideally be converted through catalytic processes into solid amine adsorbents for use in CCS, thus in effect solving one problem with the other 17 . Undeniably, this is challenging due to multiple factors as these materials were originally not designed for carbon capture purposes. While different consumer plastics may be composed of the same monomers, other factors such as thermosetting, co-monomers, and additives complicate their use as one uniform feedstock, in strong contrast to fossil fuel derived base chemicals. Despite these challenges, consumer products made from acrylonitrile monomers were identified as promising raw materials for accessing polymers structurally similar to the CO 2 -adsorbing poly(allylamine) (PAA) (Fig. 1a) 18 . These acrylonitrile-based materials, which had a combined yearly output of 14.2 million tons in 2022 19−21 , could be upcycled to the corresponding poly(amine) CO 2 -adsorbent through a single catalytic hydrogenation step. Catalytic nitrile hydrogenation has to date been confined to small molecule substrates besides one recent example for non-vulcanised and soluble nitrile butadiene rubber (NBR) 22−24 . Through a screening, we found that the hydrogenation conditions developed by Beller et al. using catalytic RuMACHO ® ( RuC1 ) were effective for the conversion of an NBR sample ( NBR1 , Fig. 1b) 25 . The desired poly(amine) structure ( H-NBR1 ) was confirmed by infrared- (IR) and 13 C cross polarisation magic angle spinning nuclear magnetic resonance ( 13 C CP/MAS NMR) spectroscopic analysis (Fig. 1c and 1d, see full characterisation of H-NBR1 , pp. S88−97 of the SI), while formation of the 13 C-labelled carbamate was determined by the appearance of a chemical shift at 165 ppm from exposing cryogenically milled H-NBR1 to 13 CO 2 . Although not visible by IR- or 13 C CP/MAS NMR analysis for H-NBR1 , the formation of secondary and/or tertiary amines, leading to a thermoset material occurs to a minor degree through a previously reported amine-imine crosslinking side-reaction 25 . The production of a basic gas phase was observed after the reaction, indicating ammonia evolution (see the SI, Fig. S7). The affinity of H-NBR1 towards CO 2 was confirmed by thermogravimetric analysis (TGA) using a flow of CO 2 at temperatures of 25 °C, 50 °C, and 90 °C, showing up to an average 2.98 mmol/g CO 2 -capacity (Fig. 1e). To further complement this nitrile hydrogenation strategy towards poly(amines), a nickel-catalysed hydrocyanation protocol 26−28 was adapted to introduce nitriles to styrene-butadiene rubber (SBR) using ex situ-generated HCN gas within a two-chamber reactor system 29 . This protocol displayed an average conversion of 44% of butadiene to alkyl nitriles for an SBR-sample ( SBR1 , see the SI, pp. S81−S83 and Fig. 1f). The hydrocyanated polymer could then be hydrogenated to the corresponding poly(amine) applying similar conditions to the NBR-reduction. In one example, SBR1 was reacted with a mixture of H 13 CN/H 12 CN in a 1:4 ratio, thus generating a partially labelled H 12/13 CN-SBR1 product which allowed tracking of the 13 C-enriched chemical shift by 13 C CP/MAS NMR spectroscopic analysis. After hydrogenation, the chemical shift of the labelled nitrile at 124 ppm, was converted to a new chemical shift at 47 ppm corresponding to the α-carbon of the expected primary amine product. To test the general applicability of the hydrogenation protocol, a series of consumer acrylonitrile-based polymers were tested, including NBR, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), and acrylic textile (TEX) (Fig. 2). Common to these types of acrylonitrile polymers is the general lack of efficient recycling technologies 30−35 . Hydrogenation of the selected NBR, ABS, and SAN substrates showed full conversion of the nitrile to the corresponding amine as evident from IR− and 13 C CP/MAS NMR analysis. However, different conditions were needed to achieve conversion of the nitrile groups in acrylic textiles, since these materials were both insoluble and hard to swell. RuMACHO® ( RuC1 , Fig. 2) proved ineffective for the reduction of the textile substrates. Here another Ru-catalyst ( RuC6 , Fig. 2) previously reported by Beller and co-workers for small molecule nitrile hydrogenation 36 proved active although restricting the reaction towards only surface hydrogenation and a higher degree of secondary amine formation compared to non-TEX substrates (visible by 13 C CP/MAS NMR, see the SI pp. S152−S174). The developed nickel-catalysed hydrocyanation-hydrogenation reaction sequence was examined for NBR2 , ABS1 , SBR1 , and SBR2 , providing the corresponding primary amine-based polymers as evidenced from IR− and 13 C CP/MAS NMR analysis (see Fig. 2 and pp. S169−S217). In addition, poly(amine) derivatives were synthesised with increased amine contents from the reaction of H-NBR2 , H-ABS2 , or H-SAN2 , with Boc-protected aziridine, followed by deprotection, to evaluate the effect of this post-modification on CO 2 -adsorption (see the SI, pp. S218−S241). Besides single polymeric materials, the option of reacting mixed polymer batches was explored, such as MIX1 , which is a combination of ABS1 , ABS2 , SAN1 , and SAN2 in equal amounts yielding a mixed-polymer derived adsorbent, H-MIX1 . Furthermore, from studying the solubility of acrylic fibres, it was found that the biobased γ-valerolactone (GVL) 37 was ideal for isolating acrylic polymers by dissolution, thus rendering it possible to extract this type of polymer from a larger mixed textile waste fraction. To mimic this idea, a mixture of seven different fabrics composed of wool, viscose, poly(propylene), poly(ethylene terephthalate), poly(amide), cotton, elastane, and acrylic fibres, was subjected to stirring in GVL while heated to 150 °C for 15 min. These conditions provided a grey powder ( MIX2 ) after precipitation in H 2 O, with identical 1 H−NMR-spectroscopic features compared to an acrylic textile ( TEX1 ), thus demonstrating the efficacy of the dissolution protocol. MIX2 was hydrogenated with similar efficacy to textile substrates TEX1 and TEX2 (see the SI, pp. S145−S165). To further validate the scalability of the hydrogenation reaction, a 10 g reaction using ABS1 as the substrate was carried out (Fig. 3a). The reaction was successful even without having to crush the building blocks into smaller pieces. After being subjected to the hydrogenation conditions for 24 h, the material was effectively converted into a suspended poly(amine) slurry, which upon work-up and washing showed full conversion of nitrile to the corresponding amine polymer H-ABS1 with a 67% weight recovery. The affinity of CO 2 towards the prepared adsorbents was established by TGA using either pure CO 2 , or 10% CO 2 balanced by N 2 at temperatures of either 25 °C, 50 °C, or 90 °C, over 5 hours adsorption (Fig. 3b−3e). Prior to analysis, all amine polymers were ball-milled under cryogenic conditions to provide a high surface area for CO 2 -adsorption. To directly compare measured adsorption capacities, a commercially available benchmark material, Lewatit VP OC 1065 (“Lewatit” from hereon), was analysed as well. This adsorbent is similar to the material used by the DAC-company, Climeworks 38 , and reports have demonstrated its potential for both DAC- and CCS-applications, such as a 1-ton CO 2 /day pilot plant for flue gas capture 8,39 . For almost all the analysed adsorbents, higher CO 2 -capacities and N-efficiencies (CO 2 /N) were observed at lower temperature vs. higher temperature (Fig. 3b−3e). However, this was not the trend for the H-NBR1 adsorbent, showing an average adsorption capacity of 2.98 mmol/g at 90 °C, while the highest average capacity for H-NBR2 was 2.03 mmol/g at 25 °C, although some H-NBR2 samples showed higher adsorption capacity at 90 °C. It was found that nitrile rubber-derived adsorbents give highest capacity at 25 °C as small particles (-140 +500 mesh), whereas they display a higher capacity at 90 °C with larger particle sizes. Possibly these adsorbents display higher gas-permeability at this temperature (see the SI, pp. S107−S108), which explain the variation in CO 2 -capacity due to difference in particle sizes. For adsorbents derived from ABS or SAN consumer plastics, the highest CO 2 -capacities were measured at 25 °C, ranging from 1.34−2.08 mmol/g. For these materials, one can observe N-efficiencies ranging from 0.43−0.49 (CO 2 /N), which is not far from the value of Lewatit (N-efficiency of 0.56 CO 2 /N). Textile hydrogenation products show highest capacities at 25 °C between 0.90−1.81 mmol/g, although with low N-efficiencies (0.09−0.14 CO 2 /N) likely due to a lower degree of nitrile reduction under the hydrogenation conditions. Our hydrocyanation-hydrogenation protocol rendered SBR-materials active for CO 2 -adsorption with highest capacities at 25 °C between 1.66−1.68 mmol/g. Another highlight of this two-step procedure was the increased CO 2 -capacity for HCN*-NBR2 compared to H-NBR2 by +0.77 mmol/g at 25 °C due to the increased amine content. Furthermore, the CO 2 -capacity of H-NBR2 could be increased by +0.48 mmol/g at 25 °C by the aziridine-modification protocol ( Az-HNBR2 ), although it was not beneficial for H-ABS2 and H-SAN2 . Considering desorption, analysis of three representative adsorbents, H-NBR2 , H-ABS2 , and H-SAN2 , led to a 96−100% desorption at just 80 °C when using helium as a sweep gas (see the SI, pp. S288−S290). On the other hand, in order to maintain a non-diluted CO 2 -product, it can be sensible to apply pure CO 2 as the sweep gas, which for the same adsorbents required 150 °C to enable 96−100% desorption (see the SI, pp. S291−S293) 40 . Compared to the adsorption capacity of Lewatit at 25 °C (average of 3.18 mmol/g), all synthesised adsorbents show lower values and adsorption rates likely due to being non-porous as observed from N 2 -physisorption analysis (see the SI, p. S6). Nevertheless, flue gas temperatures can vary significantly depending on the individual plant, commonly ranging 60−550 °C 41 . In China, where 64% of the electricity generation originated from coal-fired power plants in 2018 and 2019, the flue gas is generally cooled to 90 °C 42 . In that context, we observed impressive CO 2 -capacities and adsorption rates at 90 °C for nitrile rubber-derived products, H-NBR1 , H-NBR2 , and HCN*-NBR2 , when compared to Lewatit (Fig. 4a). Although they are non-porous materials, this lack can be overcome by the higher gas permeability at 90 °C. Adsorption was conducted for 15 minutes with a 10% CO 2 -concentration, representing a typical CO 2 -concentration in flue gas from a coal-fired plant 43 , while desorption was carried out at 150 °C for 15 minutes under pure CO 2 to prevent dilution 40 . When compared to Lewatit, the CO 2 -working capacity for the NBR-derived adsorbents was close to, or higher, under this short adsorption-desorption cycle, displaying working capacities up to 0.95 mmol/g. Nonetheless, after conducting 40 sorption cycles with these conditions, Lewatit was still the more stable adsorbent, portraying the highest working capacity of 0.47 mmol/g in cycle 40. FT-IR spectroscopic analysis indicated urea formation as the reason for loss in CO 2 -capacity (see the SI, pp. S242−S244), although this deactivation is most prominent with dry rather than humid gas, of which the latter is more relevant for flue gas carbon capture 44,45 . To better assess the thermal and chemical stability of NBR-, ABS-, and SAN-derived adsorbents, a series of stress tests were carried out with H-NBR2 , H-ABS2 , H-SAN2 , and Lewatit, by measuring CO 2 -capacities before and after specific conditions. As elevated temperatures are employed during desorption, CO 2 -capacities were measured before and after being exposed to heating at 150 °C for 10 hours under helium, CO 2 , or air, respectively. While high-capacity retentions were observed with both helium (95−100%) and CO 2 (89−97%), lower capacities were observed with air due to oxidative degradation (4−15%) compared to Lewatit (41%). Hydrolytic stability was examined by boiling the adsorbents in water for 7 days, showing excellent capacity retention for H-ABS2 and H-SAN2 (83−93%) vs. Lewatit (92%), although a lower value for H-NBR2 (12%), which visibly decomposed. The presence of NO 2 and SO 2 in flue gas also poses a major challenge to stability, thus capacity retentions were evaluated after subjecting the adsorbents to 10 hours of either NO 2 (203 ppm in N 2 ) or SO 2 (206 ppm in N 2 ) at 25 °C. Excellent capacity retentions were observed for the three consumer-plastic derived adsorbents after NO 2 (85−98%) and SO 2 (93−100%), when compared to Lewatit (41% and 50%, respectively), likely due to the more exposed amines in the macro-porous Lewatit. Finally, complementing the 40-cycle experiment with NBR-derived adsorbents of Fig. 4a, the working capacities of H-NBR2 , H-ABS2 , and H-SAN2 , were evaluated over 40 sorption cycles using similar flue gas relevant conditions (50 °C adsorption in 10% CO 2 /N 2 , and 150 °C desorption in CO 2 ). Although Lewatit displayed the highest capacity retention after the 40 cycles (93%), the consumer plastic-derived adsorbents retained capacities of 75−84% of which the first 10 cycles account for the most deactivation (9−21% loss of capacity) compared to the latter 30 cycles (4−6% loss of capacity). Our results demonstrate a proof-of-concept for mitigating the global problem with plastic, rubber, and textile waste, while potentially leading to a feedstock available on the million-ton scale for producing solid CO 2 -adsorbents. While the current catalytic system for the nitrile reduction based on ruthenium will need further refinement to become scalable, the findings that acrylonitrile consumer plastics can be converted into their amine derivatives for CO 2 -adsorption by a single catalytic modification, could represent a steppingstone towards large-scale sustainable adsorbent production. Declarations Author Contributions S.P. and T.S. designed the project. S.P. optimised the hydrogenation of NBR and acrylic textiles. S.P. and C.K. investigated the scope of NBR, ABS, SAN, and TEX hydrogenation. S.P. optimised the hydrocyanation-hydrogenation sequence with butadiene-based polymers, while S.P. and C.K. investigated the scope of hydrocyanation-hydrogenation. C.K. optimised and investigated the scope of Boc-aziridine modification reactions. S.P. and R.E. investigated the regioselectivity of the hydrocyanation reaction with small molecule model compounds. M.H. conducted initial TGA-analysis for the investigation of CO 2 -adsorption on hydrogenated NBR and aided with elemental analysis. S. P., C.K., R.E. and T.B. conducted elemental-, IR-, TGA/DSC-, and solution-state NMR analysis and cryogenic milling of polymer starting materials and products. C.K. conducted SEM-analysis. S.P., T.B., and R.E. investigated CO 2 -adsorption by TGA. D.J., S.P., and R.E. conducted 13 C−CP/MAS. N.C.N. directed the solid-state NMR experiments. S.P., C.K., and T.S. wrote the manuscript, with comments from all co-authors. Acknowledgements We are deeply grateful to Bjarke Donslund for assisting with the TGA/DSC- and cryogenic milling setups. We thank Rebekka Klemmt for SEM-training and initial measurements. Furthermore, we thank Marcel Ceccato, and associate professor Nina Lock, for N 2 -physisorption measurements. Funding We are immensely grateful for the financial support by the Novo Nordisk Foundation CO 2 Research Center (grant no. NNF21SA0072700, CORC publication no. CORC_24_44), the Danish National Research Foundation (Grant No. DNRF118), and Aarhus University. Access to facilities at the Danish Center for Ultrahigh-Field NMR Spectroscopy funded by the Danish Ministry of Higher Education and Science (Grant no. AU-2010-612-181) and the Novo Nordisk Foundation (Grant no. NNF220C0075797) is acknowledged. Access to a high-vacuum physisorption analyser was supported by the Carlsberg Foundation (Grant no: CF14-0506). SEM was funded by the Carlsberg Foundation (Grant no: CF20-0364) and the Aarhus University Centre for Integrated Materials Research (iMAT). Notes The authors declare competing financial interests: T.S. is co-owner of SyTracks a/s, which commercialises the two-chamber reactor, COware ® . References Intergovernmental Panel on Climate Change (IPCC), Climate Change 2021: The Physical Science Basis , IPCC Sixth Assessment Report https://www.ipcc.ch/report/ar6/wg1/#FullReport (2021). Global Carbon Budget https://globalcarbonatlas.org/budgets/carbon-budget/ (2023). Hamdy, L. B., Goel, C., Rudd, J. A., Barron, A. R. & Andreoli, E. The application of amine-based materials for carbon capture and utilization: an overarching view. Mater. Adv. 2 , 5843−5880 (2021). Varghese, A. M. & Karanikolos, G. N. CO 2 capture adsorbent functionalized by amine – bearing polymer: A review. Int. J. Greenh. Gas Con. 96 , 103005 (2020). Dziejarski, B., Serafin, J., Andersson, K. & Krzyzynska, R. 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Heydari-Gorji, A. & Sayari, A. Thermal, Oxidative, and CO 2 -Induced Degradation of Supported Polyethyleneimine Adsorbents. Ind. Eng. Chem. Res. 51 , 6887−6894 (2012). Sayari, A., Heydari-Gorji, A. & Yang, Y. CO 2 -induced Degradation of Amine-Containing Adsorbents: Reaction Products and Pathways. J. Am. Chem. Soc. 134 , 13834−13842 (2012). Additional Declarations Yes there is potential Competing Interest. Troels Skrydstrup is co-owner of SyTracks a/s, which commercialises the two-chamber reactor, COware®. Supplementary Files SISkrydstrup.pdf Supplementary Information Cite Share Download PDF Status: Posted Version 1 posted 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-5626417","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Physical Sciences - Article","associatedPublications":[],"authors":[{"id":398944629,"identity":"09eb5274-140d-46b7-93b1-83fc90fca807","order_by":0,"name":"Troels Skrydstrup","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAApElEQVRIiWNgGAWjYFAC5gPMMKZkAzEaeBjYEkjWwmNAohZ7/jMfPxdUbGPgn5HAeHMGUbZI5G6WnnHmNoPEjQRmyw3EaeHdxszbdpuB4UYCm+QDorTwn3nGzPvvNoM88VoYctiYeRtuMxiAtBDnsBtpxtI8x27zGJ552GxJlPfZ+w8//MxTc1tO7njywZs9xGhBOJCBsYEUDaNgFIyCUTAK8AEAjeQuKJljxtYAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0001-8090-5050","institution":"Aarhus University","correspondingAuthor":true,"prefix":"","firstName":"Troels","middleName":"","lastName":"Skrydstrup","suffix":""},{"id":398944630,"identity":"cf380de3-ad69-437e-899b-29b0ca1b561a","order_by":1,"name":"Simon Pedersen","email":"","orcid":"","institution":"Aarhus University","correspondingAuthor":false,"prefix":"","firstName":"Simon","middleName":"","lastName":"Pedersen","suffix":""},{"id":398944631,"identity":"69385ac0-2d68-4c8f-ab44-26a6b99edab0","order_by":2,"name":"Clemens Kaussler","email":"","orcid":"https://orcid.org/0000-0001-7722-7914","institution":"Aarhus University","correspondingAuthor":false,"prefix":"","firstName":"Clemens","middleName":"","lastName":"Kaussler","suffix":""},{"id":398944632,"identity":"e8fb7450-dca1-4ccd-ac17-48d327f6e551","order_by":3,"name":"Ruth Ebenbauer","email":"","orcid":"","institution":"Aarhus University","correspondingAuthor":false,"prefix":"","firstName":"Ruth","middleName":"","lastName":"Ebenbauer","suffix":""},{"id":398944633,"identity":"6de47ff0-d84d-48ab-9a94-08685ecca283","order_by":4,"name":"Thomas Bech","email":"","orcid":"","institution":"Aarhus University","correspondingAuthor":false,"prefix":"","firstName":"Thomas","middleName":"","lastName":"Bech","suffix":""},{"id":398944634,"identity":"92fced6c-0583-4760-96e1-6f9bfd61c849","order_by":5,"name":"Riccardo Giovanelli","email":"","orcid":"","institution":"Aarhus University","correspondingAuthor":false,"prefix":"","firstName":"Riccardo","middleName":"","lastName":"Giovanelli","suffix":""},{"id":398944635,"identity":"95eb288a-c717-46aa-95cd-dd86ca92c519","order_by":6,"name":"Martin Lahn","email":"","orcid":"","institution":"Aarhus University","correspondingAuthor":false,"prefix":"","firstName":"Martin","middleName":"","lastName":"Lahn","suffix":""},{"id":398944636,"identity":"3f8bffd5-d590-4c11-83fe-85ba11eeef1a","order_by":7,"name":"Dennis Juhl","email":"","orcid":"","institution":"Aarhus University","correspondingAuthor":false,"prefix":"","firstName":"Dennis","middleName":"","lastName":"Juhl","suffix":""},{"id":398944637,"identity":"e3518fe9-aa76-4d0b-b414-d7abcb94d1bf","order_by":8,"name":"Niels Christian Nielsen","email":"","orcid":"","institution":"Aarhus University","correspondingAuthor":false,"prefix":"","firstName":"Niels","middleName":"Christian","lastName":"Nielsen","suffix":""}],"badges":[],"createdAt":"2024-12-11 17:55:29","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5626417/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5626417/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":73309047,"identity":"a99d89e1-614e-42fb-940a-a35617626ce6","added_by":"auto","created_at":"2025-01-08 17:47:45","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":1015094,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea. \u003c/strong\u003eConversion of nitrile-based consumer polymers to poly(amines) for CO\u003csub\u003e2\u003c/sub\u003e-adsorption. \u003cstrong\u003eb. \u003c/strong\u003eConversion of \u003cstrong\u003eNBR1\u003c/strong\u003e to \u003cstrong\u003eH-NBR1\u003c/strong\u003e through Ru-catalysed hydrogenation. \u003cstrong\u003ec. \u003c/strong\u003eFT−IR spectroscopic analysis of \u003cstrong\u003eNBR1\u003c/strong\u003e and \u003cstrong\u003eH-NBR1\u003c/strong\u003e. \u003cstrong\u003ed.\u003c/strong\u003e \u003csup\u003e13\u003c/sup\u003eC CP/MAS NMR spectroscopic analysis of \u003cstrong\u003eNBR1\u003c/strong\u003e, \u003cstrong\u003eH-NBR1\u003c/strong\u003e, and \u003cstrong\u003eH-NBR1\u003c/strong\u003e exposed to \u003csup\u003e13\u003c/sup\u003eCO\u003csub\u003e2\u003c/sub\u003e. \u003cstrong\u003ee.\u003c/strong\u003e CO\u003csub\u003e2\u003c/sub\u003e-adsorption by thermogravimetric analysis showing adsorption with \u003cstrong\u003eH-NBR1 \u003c/strong\u003e(curves are averages from measuring duplicate products batches two times each). \u003cstrong\u003ef.\u003c/strong\u003e 2-Step hydrocyanation-hydrogenation of styrene butadiene rubber (\u003cstrong\u003eSBR1\u003c/strong\u003e), also showing conversion by \u003csup\u003e13\u003c/sup\u003eC CP/MAS NMR using a partly \u003csup\u003e13\u003c/sup\u003eC−labelled polymer. \u003csup\u003ea\u003c/sup\u003eConversion was determined by elemental analysis. \u003csup\u003eb\u003c/sup\u003eSpecific conditions were used for preparing the \u003csup\u003e13\u003c/sup\u003eC−labelled polymers (see the SI, pp. S166−S181). BD = Butadiene.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5626417/v1/4b46252ecfd3b3a559183993.png"},{"id":73309542,"identity":"a8ec3519-1abc-4a7d-ac9d-2c4df83c0bb5","added_by":"auto","created_at":"2025-01-08 17:55:45","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1482096,"visible":true,"origin":"","legend":"\u003cp\u003eScope of consumer polymers. Pictures show substrates and representative particles used in the reactions. AN% = weight percentage of acrylonitrile repeating unit in the polymer as determined from elemental analysis. The prefix \u003cstrong\u003eH-\u003c/strong\u003e signifies a hydrogenated polymer, while \u003cstrong\u003eHCN*-\u003c/strong\u003e signifies a hydrocyanated and hydrogenated polymer. \u003csup\u003ea\u003c/sup\u003eSee the SI for the specific conditions used for individual substrates. Butadiene-contents of individual substrates besides \u003cstrong\u003eSBR1\u003c/strong\u003e are not known. \u003csup\u003eb\u003c/sup\u003eAcrylic textiles consist mainly of poly(acrylonitrile) but also other co-monomers. \u003csup\u003ec\u003c/sup\u003eAN% is higher than the actual value due to additional N-content from the poly(amide) co-polymer. \u003csup\u003ed\u003c/sup\u003eThe grey acrylic powder, \u003cstrong\u003eMIX2\u003c/strong\u003e (lower-right corner), was obtained from selective dissolution from a mixed textile polymer batch (the depicted textiles), see also the SI, pp. S63−S67.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5626417/v1/ed7245d3b8078c076e82a968.png"},{"id":73309045,"identity":"d8ead628-3f99-4d71-834e-c3b565961145","added_by":"auto","created_at":"2025-01-08 17:47:45","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1054180,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea.\u003c/strong\u003e 10 g scale hydrogenation of \u003cstrong\u003eABS1\u003c/strong\u003e to \u003cstrong\u003eH-ABS1\u003c/strong\u003e. Conditions: \u003cstrong\u003eRuC1\u003c/strong\u003e (2 wt%), KO\u003cem\u003et\u003c/em\u003e-Bu (4 wt%), H\u003csub\u003e2\u003c/sub\u003e (30 bar), \u003cem\u003ei\u003c/em\u003e-PrOH (100 mL), 80 °C, 24 h. \u003cstrong\u003eb.\u003c/strong\u003e CO\u003csub\u003e2\u003c/sub\u003e-capacities (100% CO\u003csub\u003e2\u003c/sub\u003e, 5 h, 25 °C, 50 °C, and 90 °C). \u003cstrong\u003ec.\u003c/strong\u003e CO\u003csub\u003e2\u003c/sub\u003e-capacities (10% CO\u003csub\u003e2\u003c/sub\u003e, 5 h, 25 °C, 50 °C, and 90 °C). \u003cstrong\u003ed. \u003c/strong\u003eN-Efficiencies (100% CO\u003csub\u003e2\u003c/sub\u003e, 5 h, 25 °C, 50 °C, and 90 °C) based on N-contents derived from elemental analysis. \u003cstrong\u003ee. \u003c/strong\u003eN-Efficiencies (10% CO\u003csub\u003e2\u003c/sub\u003e, 5 h, 25 °C, 50 °C, and 90 °C) based on N-contents derived from elemental analysis. Uncertainties are given as the range of capacities or N-efficiencies measured over all product batches.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5626417/v1/c0a031dc4981b2b6996a0cb6.png"},{"id":73309044,"identity":"039642c4-ad46-4ade-b979-3b6f85c72558","added_by":"auto","created_at":"2025-01-08 17:47:45","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":538492,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eRetention of CO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e-capacity after stress tests. a.\u003c/strong\u003e Simulated flue gas capture for best-performing adsorbents, \u003cstrong\u003eH-NBR1\u003c/strong\u003e, \u003cstrong\u003eH-NBR2\u003c/strong\u003e, \u003cstrong\u003eHCN*-NBR2\u003c/strong\u003e, and the benchmark material Lewatit, showing both the adsorption in the first cycle and the effects on working capacity over 40 cycles of 15 min. adsorption and 15 min. desorption. Rounded pictures show the substrates used to prepare the adsorbents.\u003cstrong\u003e b.\u003c/strong\u003e Retention of CO\u003csub\u003e2\u003c/sub\u003e-capacity after: \u003cstrong\u003e1\u003c/strong\u003e: He, 150 °C, 10 h. \u003cstrong\u003e2\u003c/strong\u003e: Air, 150 °C, 10 h. \u003cstrong\u003e3\u003c/strong\u003e: CO\u003csub\u003e2\u003c/sub\u003e (100%), 150 °C, 10 h. \u003cstrong\u003e4\u003c/strong\u003e: Boiled in H\u003csub\u003e2\u003c/sub\u003eO (7 days). \u003cstrong\u003e5\u003c/strong\u003e: NO\u003csub\u003e2\u003c/sub\u003e (203 ppm), 25 °C, 10 h. \u003cstrong\u003e6\u003c/strong\u003e: SO\u003csub\u003e2\u003c/sub\u003e (206 ppm), 25 °C, 10 h. \u003cstrong\u003e7\u003c/strong\u003e: Retention of working capacity after 40 cycles of adsorption (10% CO\u003csub\u003e2\u003c/sub\u003e, 50 °C, 15 min.) and desorption (100% CO\u003csub\u003e2\u003c/sub\u003e, 150 °C, 15 min.).\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5626417/v1/82b34b4f37c863fe2b3abf21.png"},{"id":76316181,"identity":"cd8c3bfe-fc7c-4356-9d4e-961c67a4d59b","added_by":"auto","created_at":"2025-02-14 16:54:44","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4769437,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5626417/v1/58608187-3694-4786-bc67-8a06b38ad630.pdf"},{"id":73309048,"identity":"de32db87-3e4b-46eb-9db3-9e18b8af2ac1","added_by":"auto","created_at":"2025-01-08 17:47:46","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":48042581,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"SISkrydstrup.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5626417/v1/3ace3b366fd08d0c48490e65.pdf"}],"financialInterests":"\u003cb\u003eYes\u003c/b\u003e there is potential Competing Interest.\nTroels Skrydstrup is co-owner of SyTracks a/s, which commercialises the two-chamber reactor, COware®.","formattedTitle":"\u003cp\u003eCO\u003csub\u003e2\u003c/sub\u003e capture with post-modified consumer acrylonitrile plastics\u003c/p\u003e","fulltext":[{"header":"Full Text","content":"\u003cp\u003eFor mitigating global warming to the 1.5\u0026minus;2.0 \u0026deg;C target of the Paris Agreement, the Intergovernmental Panel on Climate Change (IPCC) estimates a yearly requirement of 5\u0026minus;16 Gt carbon dioxide removal (CDR) by 2050. CCS-technologies such as bioenergy carbon capture and storage (BECCS) and direct air capture (DAC) are key for achieving this goal\u003csup\u003e1,9\u003c/sup\u003e. These gigaton-scale targets are far from the current yearly capture capacities of CCS, BECCS, and DAC, consisting of 50 M, 2 Mt, and 0.047 Mt, respectively\u003csup\u003e10\u0026minus;13\u003c/sup\u003e. Today, point source carbon capture technologies operating at industrial capacity rely on aqueous solutions of small-molecule amines, e.g. monoethanolamine (MEA), but suffer from sorbent leaching, corrosion, decomposition, and a high energy penalty for sorbent regeneration\u003csup\u003e3\u003c/sup\u003e. Next-generation solid adsorbents including amine-grafted or -impregnated supported materials, metal-organic frameworks (MOFs), or self-supported poly(amines), abate the problems of conventional carbon capture\u003csup\u003e3\u003c/sup\u003e. However, today only the liquid absorbents, such as MEA, have reached a commercial scale technology readiness level (TRL) of 9\u003csup\u003e14\u003c/sup\u003e. One unifying trait for most liquid- and solid amine sorbents, is their synthetic dependency on fossil-based resources for production. Attaining the multi-gigaton per-year CCS- and CDR-targets will require significant scaling of adsorbent production to the million-ton level, leading to further environmental challenges unless a switch to sustainable resources is made.\u003c/p\u003e\n\u003cp\u003eConcurrent with global warming, there are growing concerns about\u0026nbsp;the adverse impact of accumulating plastic waste on the environment and human health\u003csup\u003e15\u003c/sup\u003e. In 2022, the total combined production capacity of plastics reached a staggering 400 million tons, of which only 9% corresponded to recycled polymeric materials\u003csup\u003e16\u003c/sup\u003e. Landfilling and incineration remain the most common means of disposal of end-of-life consumer plastic-, rubber-, and textile products. Polymers comprised of nitrogen-containing functionalities could ideally be converted through catalytic processes into solid amine adsorbents for use in CCS, thus in effect solving one problem with the other\u003csup\u003e17\u003c/sup\u003e. Undeniably, this is challenging due to multiple factors as these materials were originally not designed for carbon capture purposes. While different consumer plastics may be composed of the same monomers, other factors such as thermosetting, co-monomers, and additives complicate their use as one uniform feedstock, in strong contrast to fossil fuel derived base chemicals. Despite these challenges, consumer products made from acrylonitrile monomers were identified as promising raw materials for accessing polymers structurally similar to the CO\u003csub\u003e2\u003c/sub\u003e-adsorbing poly(allylamine) (PAA) (Fig. 1a)\u003csup\u003e18\u003c/sup\u003e. These acrylonitrile-based materials, which had a combined yearly output of 14.2 million tons in 2022\u003csup\u003e19\u0026minus;21\u003c/sup\u003e, could be upcycled to the corresponding poly(amine) CO\u003csub\u003e2\u003c/sub\u003e-adsorbent through a single catalytic hydrogenation step.\u003c/p\u003e\n\u003cp\u003eCatalytic nitrile hydrogenation has to date been confined to small molecule substrates besides one recent example for non-vulcanised and soluble nitrile butadiene rubber (NBR)\u003csup\u003e22\u0026minus;24\u003c/sup\u003e. Through a screening, we found that the hydrogenation conditions developed by Beller et al. using catalytic RuMACHO\u003csup\u003e\u0026reg;\u003c/sup\u003e (\u003cstrong\u003eRuC1\u003c/strong\u003e) were effective for the conversion of an NBR sample (\u003cstrong\u003eNBR1\u003c/strong\u003e, Fig. 1b)\u003csup\u003e25\u003c/sup\u003e. The desired poly(amine) structure (\u003cstrong\u003eH-NBR1\u003c/strong\u003e) was confirmed by infrared- (IR) and \u003csup\u003e13\u003c/sup\u003eC\u0026nbsp;cross polarisation magic angle spinning nuclear magnetic resonance (\u003csup\u003e13\u003c/sup\u003eC CP/MAS NMR) spectroscopic analysis (Fig. 1c and 1d, see full characterisation of \u003cstrong\u003eH-NBR1\u003c/strong\u003e, pp. S88\u0026minus;97 of the SI), while formation of the \u003csup\u003e13\u003c/sup\u003eC-labelled carbamate was determined by the appearance of a chemical shift at 165 ppm from exposing cryogenically milled \u003cstrong\u003eH-NBR1\u003c/strong\u003e to \u003csup\u003e13\u003c/sup\u003eCO\u003csub\u003e2\u003c/sub\u003e. Although not visible by IR- or \u003csup\u003e13\u003c/sup\u003eC CP/MAS NMR analysis for \u003cstrong\u003eH-NBR1\u003c/strong\u003e, the formation of secondary and/or tertiary amines, leading to a thermoset material occurs to a minor degree through a previously reported amine-imine crosslinking side-reaction\u003csup\u003e25\u003c/sup\u003e. The production of a basic gas phase was observed after the reaction, indicating ammonia evolution (see the SI, Fig. S7). The affinity of \u003cstrong\u003eH-NBR1\u003c/strong\u003e towards CO\u003csub\u003e2\u003c/sub\u003e was confirmed by thermogravimetric analysis (TGA) using a flow of CO\u003csub\u003e2\u003c/sub\u003e at temperatures of 25 \u0026deg;C, 50 \u0026deg;C, and 90 \u0026deg;C, showing up to an average 2.98 mmol/g CO\u003csub\u003e2\u003c/sub\u003e-capacity (Fig. 1e). To further complement this nitrile hydrogenation strategy towards poly(amines), a nickel-catalysed hydrocyanation protocol\u003csup\u003e26\u0026minus;28\u003c/sup\u003e was adapted to introduce nitriles to styrene-butadiene rubber (SBR) using ex situ-generated HCN gas within a two-chamber reactor system\u003csup\u003e29\u003c/sup\u003e. This protocol displayed an average conversion of 44% of butadiene to alkyl nitriles for an SBR-sample (\u003cstrong\u003eSBR1\u003c/strong\u003e, see the SI, pp. S81\u0026minus;S83 and Fig. 1f). The hydrocyanated polymer could then be hydrogenated to the corresponding poly(amine) applying similar conditions to the NBR-reduction. In one example, \u003cstrong\u003eSBR1\u003c/strong\u003e was reacted with a mixture of H\u003csup\u003e13\u003c/sup\u003eCN/H\u003csup\u003e12\u003c/sup\u003eCN in a 1:4 ratio, thus generating a partially labelled \u003cstrong\u003eH\u003csup\u003e12/13\u003c/sup\u003eCN-SBR1\u003c/strong\u003e product which allowed tracking of the \u003csup\u003e13\u003c/sup\u003eC-enriched chemical shift by \u003csup\u003e13\u003c/sup\u003eC CP/MAS NMR spectroscopic analysis. After hydrogenation, the chemical shift of the labelled nitrile at 124 ppm, was converted to a new chemical shift at 47 ppm corresponding to the \u0026alpha;-carbon of the expected primary amine product.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTo test the general applicability of the hydrogenation protocol, a series of consumer \u0026nbsp;acrylonitrile-based polymers were tested, including NBR, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), and acrylic textile (TEX) (Fig. 2). Common to these types of acrylonitrile polymers is the general lack of efficient recycling technologies\u003csup\u003e30\u0026minus;35\u003c/sup\u003e. Hydrogenation of the selected NBR, ABS, and SAN substrates showed full conversion of the nitrile to the corresponding amine as evident from IR\u0026minus; and \u003csup\u003e13\u003c/sup\u003eC CP/MAS NMR analysis. However, different conditions were needed to achieve conversion of the nitrile groups in acrylic textiles, since these materials were both insoluble and hard to swell. RuMACHO\u0026reg; (\u003cstrong\u003eRuC1\u003c/strong\u003e, Fig. 2) proved ineffective for the reduction of the textile substrates. Here another Ru-catalyst (\u003cstrong\u003eRuC6\u003c/strong\u003e, Fig. 2) previously reported by Beller and co-workers for small molecule nitrile hydrogenation\u003csup\u003e36\u003c/sup\u003e proved active although restricting the reaction towards only surface hydrogenation and a higher degree of secondary amine formation compared to non-TEX substrates (visible by \u003csup\u003e13\u003c/sup\u003eC CP/MAS NMR, see the SI pp. S152\u0026minus;S174). The developed nickel-catalysed hydrocyanation-hydrogenation reaction sequence was examined for \u003cstrong\u003eNBR2\u003c/strong\u003e, \u003cstrong\u003eABS1\u003c/strong\u003e, \u003cstrong\u003eSBR1\u003c/strong\u003e, and \u003cstrong\u003eSBR2\u003c/strong\u003e, providing the corresponding primary amine-based polymers as evidenced from IR\u0026minus; and \u003csup\u003e13\u003c/sup\u003eC CP/MAS NMR analysis (see Fig. 2 and pp. S169\u0026minus;S217). In addition, poly(amine) derivatives were synthesised with increased amine contents from the reaction of \u003cstrong\u003eH-NBR2\u003c/strong\u003e, \u003cstrong\u003eH-ABS2\u003c/strong\u003e, or \u003cstrong\u003eH-SAN2\u003c/strong\u003e, with Boc-protected aziridine, followed by deprotection, to evaluate the effect of this post-modification on CO\u003csub\u003e2\u003c/sub\u003e-adsorption (see the SI, pp. S218\u0026minus;S241).\u003c/p\u003e\n\u003cp\u003eBesides single polymeric materials, the option of reacting mixed polymer batches was explored, such as \u003cstrong\u003eMIX1\u003c/strong\u003e, which is a combination of \u003cstrong\u003eABS1\u003c/strong\u003e, \u003cstrong\u003eABS2\u003c/strong\u003e, \u003cstrong\u003eSAN1\u003c/strong\u003e, and \u003cstrong\u003eSAN2\u003c/strong\u003e in equal amounts yielding a mixed-polymer derived adsorbent, \u003cstrong\u003eH-MIX1\u003c/strong\u003e. Furthermore, from studying the solubility of acrylic fibres, it was found that the biobased \u0026gamma;-valerolactone (GVL)\u003csup\u003e37\u003c/sup\u003e was ideal for isolating acrylic polymers by dissolution, thus rendering it possible to extract this type of polymer from a larger mixed textile waste fraction. To mimic this idea, a mixture of seven different fabrics composed of wool, viscose, poly(propylene), poly(ethylene terephthalate), poly(amide), cotton, elastane, and acrylic fibres, was subjected to stirring in GVL while heated to 150 \u0026deg;C for 15 min. These conditions provided a grey powder (\u003cstrong\u003eMIX2\u003c/strong\u003e) after precipitation in H\u003csub\u003e2\u003c/sub\u003eO, with identical \u003csup\u003e1\u003c/sup\u003eH\u0026minus;NMR-spectroscopic features compared to an acrylic textile (\u003cstrong\u003eTEX1\u003c/strong\u003e), thus demonstrating the efficacy of the dissolution protocol. \u003cstrong\u003eMIX2\u003c/strong\u003e was hydrogenated with similar efficacy to textile substrates \u003cstrong\u003eTEX1\u003c/strong\u003e and \u003cstrong\u003eTEX2\u003c/strong\u003e (see the SI, pp. S145\u0026minus;S165).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTo further validate the scalability of the hydrogenation reaction, a 10 g reaction using \u003cstrong\u003eABS1\u003c/strong\u003e as the substrate was carried out (Fig. 3a). The reaction was successful even without having to crush the building blocks into smaller pieces. After being subjected to the hydrogenation conditions for 24 h, the material was effectively converted into a suspended poly(amine) slurry, which upon work-up and washing showed full conversion of nitrile to the corresponding amine polymer \u003cstrong\u003eH-ABS1\u0026nbsp;\u003c/strong\u003ewith a 67% weight recovery.\u003c/p\u003e\n\u003cp\u003eThe affinity of CO\u003csub\u003e2\u003c/sub\u003e towards the prepared adsorbents was established by TGA using either pure CO\u003csub\u003e2\u003c/sub\u003e, or 10% CO\u003csub\u003e2\u003c/sub\u003e balanced by N\u003csub\u003e2\u003c/sub\u003e at temperatures of either 25 \u0026deg;C, 50 \u0026deg;C, or 90 \u0026deg;C, over 5 hours adsorption (Fig. 3b\u0026minus;3e). Prior to analysis, all amine polymers were ball-milled under cryogenic conditions to provide a high surface area for CO\u003csub\u003e2\u003c/sub\u003e-adsorption. To directly compare measured adsorption capacities, a commercially available benchmark material, Lewatit VP OC 1065 (\u0026ldquo;Lewatit\u0026rdquo; from hereon), was analysed as well. This adsorbent is similar to the material used by the DAC-company, Climeworks\u003csup\u003e38\u003c/sup\u003e, and reports have demonstrated its potential for both DAC- and CCS-applications, such as a 1-ton CO\u003csub\u003e2\u003c/sub\u003e/day pilot plant for flue gas capture\u003csup\u003e8,39\u003c/sup\u003e. For almost all the analysed adsorbents, higher CO\u003csub\u003e2\u003c/sub\u003e-capacities and N-efficiencies (CO\u003csub\u003e2\u003c/sub\u003e/N) were observed at lower temperature vs. higher temperature (Fig. 3b\u0026minus;3e). However, this was not the trend for the \u003cstrong\u003eH-NBR1\u0026nbsp;\u003c/strong\u003eadsorbent, showing an average adsorption capacity of 2.98 mmol/g at 90 \u0026deg;C, while the highest average capacity for \u003cstrong\u003eH-NBR2\u003c/strong\u003e was 2.03 mmol/g at 25 \u0026deg;C, although some \u003cstrong\u003eH-NBR2\u003c/strong\u003e samples showed higher adsorption capacity at 90 \u0026deg;C. It was found that nitrile rubber-derived adsorbents give highest capacity at 25 \u0026deg;C as small particles (-140 +500 mesh), whereas they display a higher capacity at 90 \u0026deg;C with larger particle sizes. Possibly these adsorbents display higher gas-permeability at this temperature (see the SI, pp. S107\u0026minus;S108), which explain the variation in CO\u003csub\u003e2\u003c/sub\u003e-capacity due to difference in particle sizes. For adsorbents derived from ABS or SAN consumer plastics, the highest CO\u003csub\u003e2\u003c/sub\u003e-capacities were measured at 25 \u0026deg;C, ranging from 1.34\u0026minus;2.08 mmol/g. For these materials, one can observe N-efficiencies ranging from 0.43\u0026minus;0.49 (CO\u003csub\u003e2\u003c/sub\u003e/N), which is not far from the value of Lewatit (N-efficiency of 0.56 CO\u003csub\u003e2\u003c/sub\u003e/N). Textile hydrogenation products show highest capacities at 25 \u0026deg;C between 0.90\u0026minus;1.81 mmol/g, although with low N-efficiencies (0.09\u0026minus;0.14 CO\u003csub\u003e2\u003c/sub\u003e/N) likely due to a lower degree of nitrile reduction under the hydrogenation conditions. Our hydrocyanation-hydrogenation protocol rendered SBR-materials active for CO\u003csub\u003e2\u003c/sub\u003e-adsorption with highest capacities at 25 \u0026deg;C between 1.66\u0026minus;1.68 mmol/g. Another highlight of this two-step procedure was the increased CO\u003csub\u003e2\u003c/sub\u003e-capacity for \u003cstrong\u003eHCN*-NBR2\u003c/strong\u003e compared to \u003cstrong\u003eH-NBR2\u003c/strong\u003e by +0.77 mmol/g at 25 \u0026deg;C due to the increased amine content. \u0026nbsp;Furthermore, the CO\u003csub\u003e2\u003c/sub\u003e-capacity of \u003cstrong\u003eH-NBR2\u003c/strong\u003e could be increased by +0.48 mmol/g at 25 \u0026deg;C by the aziridine-modification protocol (\u003cstrong\u003eAz-HNBR2\u003c/strong\u003e), although it was not beneficial for \u003cstrong\u003eH-ABS2\u003c/strong\u003e and \u003cstrong\u003eH-SAN2\u003c/strong\u003e. Considering desorption, analysis of three representative adsorbents, \u003cstrong\u003eH-NBR2\u003c/strong\u003e, \u003cstrong\u003eH-ABS2\u003c/strong\u003e, and \u003cstrong\u003eH-SAN2\u003c/strong\u003e, led to a 96\u0026minus;100% desorption at just 80 \u0026deg;C when using helium as a sweep gas (see the SI, pp. S288\u0026minus;S290). On the other hand, in order to maintain a non-diluted CO\u003csub\u003e2\u003c/sub\u003e-product, it can be sensible to apply pure CO\u003csub\u003e2\u003c/sub\u003e as the sweep gas, which for the same adsorbents required 150 \u0026deg;C to enable 96\u0026minus;100% desorption (see the SI, pp. S291\u0026minus;S293)\u003csup\u003e40\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eCompared to the adsorption capacity of Lewatit at 25 \u0026deg;C (average of 3.18 mmol/g), all synthesised adsorbents show lower values and adsorption rates likely due to being non-porous as observed from N\u003csub\u003e2\u003c/sub\u003e-physisorption analysis (see the SI, p. S6). Nevertheless, flue gas temperatures can vary significantly depending on the individual plant, commonly ranging 60\u0026minus;550 \u0026deg;C\u003csup\u003e41\u003c/sup\u003e. In China, where 64% of the electricity generation originated from coal-fired power plants in 2018 and 2019, the flue gas is generally cooled to 90 \u0026deg;C\u003csup\u003e42\u003c/sup\u003e. In that context, we observed impressive CO\u003csub\u003e2\u003c/sub\u003e-capacities and adsorption rates at 90 \u0026deg;C for nitrile rubber-derived products, \u003cstrong\u003eH-NBR1\u003c/strong\u003e, \u003cstrong\u003eH-NBR2\u003c/strong\u003e, and \u003cstrong\u003eHCN*-NBR2\u003c/strong\u003e, when compared to Lewatit (Fig. 4a). Although they are non-porous materials, this lack can be overcome by the higher gas permeability at 90 \u0026deg;C. Adsorption was conducted for 15 minutes with a 10% CO\u003csub\u003e2\u003c/sub\u003e-concentration, representing a typical CO\u003csub\u003e2\u003c/sub\u003e-concentration in flue gas from a coal-fired plant\u003csup\u003e43\u003c/sup\u003e, while desorption was carried out at 150 \u0026deg;C for 15 minutes under pure CO\u003csub\u003e2\u003c/sub\u003e to prevent dilution\u003csup\u003e40\u003c/sup\u003e. When compared to Lewatit, the CO\u003csub\u003e2\u003c/sub\u003e-working capacity for the NBR-derived adsorbents was close to, or higher, under this short adsorption-desorption cycle, displaying working capacities up to 0.95 mmol/g. Nonetheless, after conducting 40 sorption cycles with these conditions, Lewatit was still the more stable adsorbent, portraying the highest working capacity of 0.47 mmol/g in cycle 40. FT-IR spectroscopic analysis indicated urea formation as the reason for loss in CO\u003csub\u003e2\u003c/sub\u003e-capacity (see the SI, pp. S242\u0026minus;S244), although this deactivation is most prominent with dry rather than humid gas, of which the latter is more relevant for flue gas carbon capture\u003csup\u003e44,45\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eTo better assess the thermal and chemical stability of NBR-, ABS-, and SAN-derived adsorbents, a series of stress tests were carried out with \u003cstrong\u003eH-NBR2\u003c/strong\u003e, \u003cstrong\u003eH-ABS2\u003c/strong\u003e, \u003cstrong\u003eH-SAN2\u003c/strong\u003e, and Lewatit, by measuring CO\u003csub\u003e2\u003c/sub\u003e-capacities before and after specific conditions. As elevated temperatures are employed during desorption, CO\u003csub\u003e2\u003c/sub\u003e-capacities were measured before and after being exposed to heating at 150 \u0026deg;C for 10 hours under helium, CO\u003csub\u003e2\u003c/sub\u003e, or air, respectively. While high-capacity retentions were observed with both helium (95\u0026minus;100%) and CO\u003csub\u003e2\u003c/sub\u003e (89\u0026minus;97%), lower capacities were observed with air due to oxidative degradation (4\u0026minus;15%) compared to Lewatit (41%). Hydrolytic stability was examined by boiling the adsorbents in water for 7 days, showing excellent capacity retention for \u003cstrong\u003eH-ABS2\u003c/strong\u003e and \u003cstrong\u003eH-SAN2\u0026nbsp;\u003c/strong\u003e(83\u0026minus;93%) vs. Lewatit (92%), although a lower value for \u003cstrong\u003eH-NBR2\u003c/strong\u003e (12%), which visibly decomposed. The presence of NO\u003csub\u003e2\u003c/sub\u003e and SO\u003csub\u003e2\u003c/sub\u003e in flue gas also poses a major challenge to stability, thus capacity retentions were evaluated after subjecting the adsorbents to 10 hours of either NO\u003csub\u003e2\u003c/sub\u003e (203 ppm in N\u003csub\u003e2\u003c/sub\u003e) or SO\u003csub\u003e2\u003c/sub\u003e (206 ppm in N\u003csub\u003e2\u003c/sub\u003e) at 25 \u0026deg;C. Excellent capacity retentions were observed for the three consumer-plastic derived adsorbents after NO\u003csub\u003e2\u003c/sub\u003e (85\u0026minus;98%) and SO\u003csub\u003e2\u003c/sub\u003e (93\u0026minus;100%), when compared to Lewatit (41% and 50%, respectively), likely due to the more exposed amines in the macro-porous Lewatit. Finally, complementing the 40-cycle experiment with NBR-derived adsorbents of Fig. 4a, the working capacities of \u003cstrong\u003eH-NBR2\u003c/strong\u003e, \u003cstrong\u003eH-ABS2\u003c/strong\u003e, and \u003cstrong\u003eH-SAN2\u003c/strong\u003e, were evaluated over 40 sorption cycles using similar flue gas relevant conditions (50 \u0026deg;C adsorption in 10% CO\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e, and 150 \u0026deg;C desorption in CO\u003csub\u003e2\u003c/sub\u003e). Although Lewatit displayed the highest capacity retention after the 40 cycles (93%), the consumer plastic-derived adsorbents retained capacities of 75\u0026minus;84% of which the first 10 cycles account for the most deactivation (9\u0026minus;21% loss of capacity) compared to the latter 30 cycles (4\u0026minus;6% loss of capacity).\u003c/p\u003e\n\u003cp\u003eOur results demonstrate a proof-of-concept for mitigating the global problem with plastic, rubber, and textile waste, while potentially leading to a feedstock available on the million-ton scale for producing solid CO\u003csub\u003e2\u003c/sub\u003e-adsorbents. While the current catalytic system for the nitrile reduction based on ruthenium will need further refinement to become scalable, the findings that acrylonitrile consumer plastics can be converted into their amine derivatives for CO\u003csub\u003e2\u003c/sub\u003e-adsorption by a single catalytic modification, could represent a steppingstone towards large-scale sustainable adsorbent production.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor Contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eS.P. and T.S. designed the project. S.P. optimised the hydrogenation of NBR and acrylic textiles. S.P. and C.K. investigated the scope of NBR, ABS, SAN, and TEX hydrogenation. S.P. optimised the hydrocyanation-hydrogenation sequence with butadiene-based polymers, while S.P. and C.K. investigated the scope of hydrocyanation-hydrogenation. C.K. optimised and investigated the scope of Boc-aziridine modification reactions. S.P. and R.E. investigated the regioselectivity of the hydrocyanation reaction with small molecule model compounds. M.H. conducted initial TGA-analysis for the investigation of CO\u003csub\u003e2\u003c/sub\u003e-adsorption on hydrogenated NBR and aided with elemental analysis. S. P., C.K., R.E. and T.B. conducted elemental-, IR-, TGA/DSC-, and solution-state NMR analysis and cryogenic milling of polymer starting materials and products. C.K. conducted SEM-analysis. S.P., T.B., and R.E. investigated CO\u003csub\u003e2\u003c/sub\u003e-adsorption by TGA. D.J., S.P., and R.E. conducted \u003csup\u003e13\u003c/sup\u003eC\u0026minus;CP/MAS. N.C.N. directed the solid-state NMR experiments. S.P., C.K., and T.S. wrote the manuscript, with comments from all co-authors.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe are deeply grateful to Bjarke Donslund for assisting with the TGA/DSC- and cryogenic milling setups. We thank Rebekka Klemmt for SEM-training and initial measurements. Furthermore, we thank Marcel Ceccato, and associate professor Nina Lock, for N\u003csub\u003e2\u003c/sub\u003e-physisorption measurements.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe are immensely grateful for the financial support by the Novo Nordisk Foundation CO\u003csub\u003e2\u003c/sub\u003e Research Center (grant no. NNF21SA0072700, CORC publication no. CORC_24_44), the Danish National Research Foundation (Grant No. DNRF118), and Aarhus University. Access to facilities at the Danish Center for Ultrahigh-Field NMR Spectroscopy funded by the Danish Ministry of Higher Education and Science (Grant no. AU-2010-612-181) and the Novo Nordisk Foundation (Grant no. NNF220C0075797) is acknowledged. Access to a high-vacuum physisorption analyser was supported by the Carlsberg Foundation (Grant no: CF14-0506).\u0026nbsp;SEM was funded by the Carlsberg Foundation (Grant no: CF20-0364) and the Aarhus University Centre for Integrated Materials Research (iMAT).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eNotes\u003cbr\u003e\u003c/strong\u003eThe authors declare competing financial interests: T.S. is co-owner of SyTracks a/s, which commercialises the two-chamber reactor, COware\u003csup\u003e\u0026reg;\u003c/sup\u003e.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eIntergovernmental Panel on Climate Change (IPCC), \u003cem\u003eClimate Change 2021: The Physical Science Basis\u003c/em\u003e, IPCC Sixth Assessment Report https://www.ipcc.ch/report/ar6/wg1/#FullReport (2021).\u003c/li\u003e\n\u003cli\u003eGlobal Carbon Budget https://globalcarbonatlas.org/budgets/carbon-budget/ (2023).\u003c/li\u003e\n\u003cli\u003eHamdy, L. B., Goel, C., Rudd, J. 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Soc. \u003c/em\u003e\u003cstrong\u003e134\u003c/strong\u003e, 13834\u0026minus;13842 (2012).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-5626417/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5626417/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Carbon capture and storage (CCS) is considered an indispensable tool for abating climate change caused by human activity. With annual CO2-emissions exceeding 37 gigatons, there is an urgent need for accessing sorbents on a million-ton production scale. Solid amine-based CO2-adsorbents are advantageous compared to conventional aqueous absorbents due to an energetically more facile regeneration and greater stability. However, synthesis of solid adsorbents is still comparatively costly and of lower production capacity. Here we report the transition metal catalysed hydrogenation or combined hydrocyanation/hydrogenation of abundant but difficult-to-recycle consumer nitrile plastics, rubbers, and textiles, to generate solid amine adsorbents that capture and release CO2 by thermal swing adsorption. The protocol is showcased with nitrile gloves, LEGO® bricks, kitchenware plastic, and acrylic textiles, taking advantage of the nitrogen already present in these polymers. These amine materials display CO2-capacities up to an average of 2.98 mmol/g, while some can match or even surpass the working capacity of a commercial benchmark adsorbent, Lewatit VP OC 1065, when subjected to simulated flue gas at 90 °C. Furthermore, excellent adsorbent stabilities towards harmful NO2 and SO2 flue gas components are observed. We anticipate our work will provide a potential pathway forward to rapidly accessing new solid adsorbents from consumer plastics for managing CO2-emissions.","manuscriptTitle":"CO2 capture with post-modified consumer acrylonitrile plastics","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-08 17:47:41","doi":"10.21203/rs.3.rs-5626417/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"bf689040-c8e9-457f-96d3-36320be3cb6f","owner":[],"postedDate":"January 8th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":42534390,"name":"Physical sciences/Chemistry/Catalysis/Homogeneous catalysis"},{"id":42534391,"name":"Physical sciences/Chemistry/Polymer chemistry"},{"id":42534392,"name":"Physical sciences/Chemistry/Environmental chemistry/Pollution remediation"},{"id":42534393,"name":"Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology"},{"id":42534394,"name":"Physical sciences/Chemistry/Green chemistry/Sustainability"}],"tags":[],"updatedAt":"2025-02-14T16:46:36+00:00","versionOfRecord":[],"versionCreatedAt":"2025-01-08 17:47:41","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5626417","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5626417","identity":"rs-5626417","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}