Structure-performance relationship of additive-incorporated tetraethylenepentamine-functionalized SiO₂ in direct air capture of CO₂

Abstract

Direct air capture (DAC) using amine-functionalized solid adsorbents holds promise for achieving negative carbon emissions. In this study, a series of additive-incorporated tetraethylenepentamine-functionalized SiO₂ adsorbents with varying tetraethylenepentamine and additive contents were prepared via a simple impregnation method, characterized by various techniques, and applied in the DAC process. The structure-performance relationship of these adsorbents in DAC was investigated, revealing that the quantity of active amine sites (or the tetraethylenepentamine content in the exposed layer), as determined by CO₂-TPD measurement, was an important factor affecting the adsorbent performance. This factor, which varied with the tetraethylenepentamine content, additive type, and additive content, showed a positive correlation with the CO₂ adsorption capacity of the adsorbents. The optimal adsorbent, 40TEPA-10PEG/SiO₂ containing 40 wt % tetraethylenepentamine and 10 wt % polyethylene glycol (Mn = 200), exhibited a stable CO₂ capacity of 2.1 mmol·g^–1 and amine efficiency of 0.22 over 20 adsorption–desorption cycles (adsorption at 400 ppm CO₂/N₂ and 30 °C for 60 min, and desorption at pure N₂ and 90 °C for 20 min). Moreover, even after deliberate accelerated oxidation treatment (pretreated in air at 100 °C for 10 h), the CO₂ capacity of 40TEPA-10PEG/SiO₂ remained at 2.0 mmol·g^–1. The superior thermal and oxidative stability of 40TEPA-10PEG/SiO₂ makes it a promising adsorbent for DAC applications.

Graphical abstract

Keywords

tetraethylenepentamine-functionalized adsorbent / direct air capture / active amine sites / CO₂ adsorption capacity / thermal and oxidative stability

References

[1] InternationalEnergy Agency (IEA). CO₂ Emissions in 2023. IEA Website, 2024

[2] LindseyR. Climate Change: Atmospheric Carbon Dioxide. NOAA Climate Website, 2024

[3] LacknerK SZiockH JGrimesP. Carbon dioxide extraction from air: is it an option? Proceedings of the 24th International Conference on Coal Utilization & Fuel Systems. Clearwater, Florida, March 8–11, 1999

[4] BouckaertSPalesA FMcGladeCRemmeUWannerBVarroLD’AmbrosioDSpencerT. Net Zero by 2050: A Roadmap for the Global Energy Sector. Paris: IEA Publications, 2021

[5] Sodiq A , Abdullatif Y , Aissa B , Ostovar A , Nassar N , El-Naas M , Amhamed A . A review on progress made in direct air capture of CO₂. Environmental Technology & Innovation, 2023, 29: 102991

[6] Zhang C , Sun S , He S , Wu C . Direct air capture of CO₂ by KOH-activated bamboo biochar. Journal of the Energy Institute, 2022, 105: 399–405

[7] Tao Z , Tian Y , Ou S Y , Gu Q , Shang J . Direct air capture of CO₂ by metal cation-exchanged LTA zeolites: effect of the charge-to-size ratio of cations. AIChE Journal. American Institute of Chemical Engineers, 2023, 69(8): e18139

[8] BoseSSenguptaDRayderT MWangXKirlikovaliK OSekizkardesA KIslamogluTFarhaO K. Challenges and opportunities: metal-organic frameworks for direct air capture. Advanced Functional Materials, 2023, 2307478

[9] Wadi B , Golmakani A , Manovic V , Nabavi S A . Evaluation of moderately grafted primary, diamine, and triamine sorbents for CO₂ adsorption from ambient air: balancing kinetics and capacity under humid conditions. Industrial & Engineering Chemistry Research, 2021, 60(36): 13309–13317

[10] Anyanwu J T , Wang Y , Yang R T . CO₂ capture (including direct air capture) and natural gas desulfurization of amine-grafted hierarchical bimodal silica. Chemical Engineering Journal, 2022, 427: 131561

[11] Sun J , Zhao M , Huang L , Zhang T , Wang Q . Recent progress on direct air capture of carbon dioxide. Current Opinion in Green and Sustainable Chemistry, 2023, 40: 100752

[12] Liu F , Wang T , Dong H , Liu W . Modified metal-organic framework by a novel coordinatively unsaturated amine grafting mechanism for direct air capture of CO₂. Chemical Engineering Journal, 2023, 454: 140431

[13] Kumar R , Bandyopadhyay M , Pandey M , Tsunoji N . Amine-impregnated nanoarchitectonics of mesoporous silica for capturing dry and humid 400 ppm carbon dioxide: a comparative study. Microporous and Mesoporous Materials, 2022, 338: 111956

[14] Goeppert A , Zhang H , Sen R , Dang H , Prakash G K S . Oxidation-resistant, cost-effective epoxide-modified polyamine adsorbents for CO₂ capture from various sources including air. ChemSusChem, 2019, 12(8): 1712–1723

[15] Qi L , Han Y , Bai G , Liu Q , Fei Z , Chen X , Zhang Z , Tang J , Cui M , Qiao X . Role of brush-like additives in CO₂ adsorbents for the enhancement of amine efficiency. Journal of Environmental Chemical Engineering, 2021, 9(6): 106709

[16] Rim G , Kong F , Song M , Rosu C , Priyadarshini P , Lively R P , Jones C W . Sub-ambient temperature direct air capture of CO₂ using amine-impregnated MIL-101(Cr) enables ambient temperature CO₂ recovery. JACS Au, 2022, 2(2): 380–393

[17] Wijesiri R P , Knowles G P , Yeasmin H , Hoadley A F A , Chaffee A L . CO₂ capture from air using pelletized polyethylenimine impregnated MCF silica. Industrial & Engineering Chemistry Research, 2019, 58(8): 3293–3303

[18] Rosu C , Pang S H , Sujan A R , Sakwa-Novak M A , Ping E W , Jones C W . Effect of extended aging and oxidation on linear poly(propylenimine)-mesoporous silica composites for CO₂ capture from simulated air and flue gas streams. ACS Applied Materials & Interfaces, 2020, 12(34): 38085–38097

[19] Chaikittisilp W , Khunsupat R , Chen T T , Jones C W . Poly (allylamine)-mesoporous silica composite materials for CO₂ capture from simulated flue gas or ambient air. Industrial & Engineering Chemistry Research, 2011, 50(24): 14203–14210

[20] Kim C , Ha Y , Choi M . Design of amine-containing nanoporous materials for postcombustion CO₂ capture from engineering perspectives. Accounts of Chemical Research, 2023, 56(21): 2887–2897

[21] Wang J , Long D , Zhou H , Chen Q , Liu X , Ling L . Surfactant promoted solid amine sorbents for CO₂ capture. Energy & Environmental Science, 2012, 5(2): 5742–5749

[22] Wang L , Al-Aufi M , Pacheco C N , Xie L , Rioux R M . Polyethylene glycol (PEG) addition to polyethylenimine (PEI)-impregnated silica increases amine accessibility during CO₂ sorption. ACS Sustainable Chemistry & Engineering, 2019, 7(17): 14785–14795

[23] Chen Y , Zhang J , Liu H , Wang X , Chen S . A surfactant modified solid amine adsorbent to enhance CO₂ adsorption performance. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 677: 132323

[24] Samaddoost L , Soltani M , Fatehifar E , Abbasi Asl E . Design of amine-functionalized resin via a facial method with efficient CO₂ capture from air. Process Safety and Environmental Protection, 2023, 171: 18–27

[25] He Z , Wang Y , Miao Y , Wang H , Zhu X , Li J . Mixed polyamines promotes CO₂ adsorption from air. Journal of Environmental Chemical Engineering, 2022, 10(2): 107239

[26] Wang Y , Miao Y , Ge B , He Z , Zhu X , Liu S , Li J , Yu L . Additives enhancing supported amines performance in CO₂ capture from air. SusMat, 2023, 3(3): 416–430

[27] Zhang J , Zuo J , Ai W , Zhang J , Zhu D , Miao S , Wei C . Preparation of mesoporous coal-gasification fine slag adsorbent via amine modification and applications in CO₂ capture. Applied Surface Science, 2021, 537: 147938

[28] Yan H , Zhang G , Xu Y , Zhang Q , Liu J , Li G , Zhao Y , Wang Y , Zhang Y . High CO₂ adsorption on amine-functionalized improved macro-/mesoporous multimodal pore silica. Fuel, 2022, 315: 123195

[29] Yuan Y , Wei J , Geng L , Mei D , Liao L . An amine-bifunctionalization strategy with Beta/KIT-6 composite as a support for CO₂ adsorbent preparation. RSC Advances, 2020, 10(56): 34187–34196

[30] Viola V O , Aquino T F D , Estevam S T , Bonetti B , Riella H G , Soares C , Padoin N . Synthesis and application of two types of amine sorbents impregnated on silica from coal fly ash for CO₂ capture. Results in Engineering, 2023, 20: 101596

[31] Irani M , Jacobson A T , Gasem K A M , Fan M . Modified carbon nanotubes/ tetraethylenepentamine for CO₂ capture. Fuel, 2017, 206: 10–18

[32] Thommes M , Kaneko K , Neimark A V , Olivier J P , Rodriguez-Reinoso F , Rouquerol J , Sing K S W . Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure and Applied Chemistry, 2015, 87(9-10): 1051–1069

[33] Wang H , Yang Z , Zhou Y , Cui H , Cheng Z , Zhou Z . Direct air capture of CO₂ with metal nitrate-doped, tetraethylenepentamine-functionalized SBA-15 adsorbents. Industrial & Engineering Chemistry Research, 2023, 62(41): 16579–16588

[34] Kulkarni V , Panda D , Singh S K . Direct air capture of CO₂ over amine-modified hierarchical silica. Industrial & Engineering Chemistry Research, 2023, 62(8): 3800–3811

[35] Zhao Y , Zhu Y , Zhu T , Lin G , Huo J , Lv D , Wang H , Sun Y . Enhanced CO₂ adsorption over silica-supported tetraethylenepentamine sorbents doped with alkanolamines or alcohols. Industrial & Engineering Chemistry Research, 2019, 58(1): 156–164

[36] Zhao M , Xiao J , Gao W , Wang Q . Defect-rich Mg-Al MMOs supported TEPA with enhanced charge transfer for highly efficient and stable direct air capture. Journal of Energy Chemistry, 2022, 68: 401–410

[37] Goeppert A , Czaun M , May R B , Prakash G K S , Olah G A , Narayanan S R . Carbon dioxide capture from the air using a polyamine based regenerable solid adsorbent. Journal of the American Chemical Society, 2011, 133(50): 20164–20167

[38] Niu M , Yang H , Zhang X , Wang Y , Tang A . Amine-impregnated mesoporous silica nanotube as an emerging nanocomposite for CO₂ capture. ACS Applied Materials & Interfaces, 2016, 8(27): 17312–17320

[39] Guo Y , Luo L , Zheng Y , Zhu T . Optimization of CO₂ adsorption on solid-supported amines and thermal regeneration mode comparison. ACS Omega, 2020, 5(17): 9641–9648

[40] Chen Z , Deng S , Wei H , Wang B , Huang J , Yu G . Polyethylenimine-impregnated resin for high CO₂ adsorption: an efficient adsorbent for CO₂ capture from simulated flue gas and ambient air. ACS Applied Materials & Interfaces, 2013, 5(15): 6937–6945

[41] Kumar D R , Rosu C , Sujan A R , Sakwa-Novak M A , Ping E W , Jones C W . Alkyl-aryl amine-rich molecules for CO₂ removal via direct air capture. ACS Sustainable Chemistry & Engineering, 2020, 8(29): 10971–10982

[42] Wang X , Song C . Temperature-programmed desorption of CO₂ from polyethylenimine-loaded SBA-15 as molecular basket sorbents. Catalysis Today, 2012, 194(1): 44–52

[43] Guo Y , Liu X , Hu B . Adsorption oxidation desulfurization of model fuel by mesoporous SiO₂ supported deep eutectic solvents TBAB/PEG-200. New Journal of Chemistry, 2022, 46(46): 22143–22150

[44] Meth S , Goeppert A , Prakash G K S , Olah G A . Silica nanoparticles as supports for regenerable CO₂ sorbents. Energy & Fuels, 2012, 26(5): 3082–3090

[45] Sakwa-Novak M A , Tan S , Jones C W . Role of additives in composite PEI/oxide CO₂ adsorbents: enhancement in the amine efficiency of supported PEI by PEG in CO₂ capture from simulated ambient air. ACS Applied Materials & Interfaces, 2015, 7(44): 24748–24759

[46] Miller D D , Chuang S S C . Control of CO₂ adsorption and desorption using polyethylene glycol in a tetraethylenepentamine thin film: an in situ ATR and theoretical study. Journal of Physical Chemistry C, 2016, 120(44): 25489–25504

[47] Jin C , Sun T , Ampah J D , Liu X , Geng Z , Afrane S , Yusuf A A , Liu H . Comparative study on synthetic and biological surfactants’ role in phase behavior and fuel properties of marine heavy fuel oil-low carbon alcohol blends under different temperatures. Renewable Energy, 2022, 195: 841–852

[48] Liu Y , Ye Q , Shen M , Shi J , Chen J , Pan H , Shi Y . Carbon dioxide capture by functionalized solid amine sorbents with simulated flue gas conditions. Environmental Science & Technology, 2011, 45(13): 5710–5716

[49] Wang X , Guo Q , Kong T . Tetraethylenepentamine-modified MCM-41/silica gel with hierarchical mesoporous structure for CO₂ capture. Chemical Engineering Journal, 2015, 273: 472–480

[50] Ojeda M , Mazaj M , Garcia S , Xuan J , Maroto-Valer M M , Logar N Z . Novel amine-impregnated mesostructured silica materials for CO₂ capture. Energy Procedia, 2017, 114: 2252–2258

[51] Kapica-Kozar J , Michalkiewicz B , Wrobel R J , Mozia S , Piróg E , Kusiak-Nejman E , Serafin J , Morawski A W , Narkiewicz U . Adsorption of carbon dioxide on TEPA-modified TiO₂/titanate composite nanorods. New Journal of Chemistry, 2017, 41(16): 7870–7885

[52] DoD D. Adsorption Analysis: Equilibria and Kinetics. London: Imperial College Press, 1998

[53] Belmabkhout Y , Sayari A . Adsorption of CO₂ from dry gases on MCM-41 silica at ambient temperature and high pressure. 2: Adsorption of CO₂/N₂, CO₂/CH₄ and CO₂/H₂ binary mixtures. Chemical Engineering Science, 2009, 64(17): 3729–3735

[54] Balathanigaimani M , Shim W G , Lee J W , Moon H . Adsorption of methane on novel corn grain-based carbon monoliths. Microporous and Mesoporous Materials, 2009, 119(1-3): 47–52

[55] Bao Z , Yu L , Ren Q , Lu X , Deng S . Adsorption of CO₂ and CH₄ on a magnesium-based metal organic framework. Journal of Colloid and Interface Science, 2011, 353(2): 549–556

[56] Vellingiri K , Kumar P , Deep A , Kim K H . Metal-organic frameworks for the adsorption of gaseous toluene under ambient temperature and pressure. Chemical Engineering Journal, 2017, 307: 1116–1126

[57] Knöfel C , Martin C , Hornebecq V . Llewellyn P L Study of carbon dioxide adsorption on mesoporous aminopropylsilane-functionalized silica and titania combining microcalorimetry and in situ infrared spectroscopy. Journal of Physical Chemistry C, 2009, 113(52): 21726–21734

[58] Serna-Guerrero R , Belmabkhout Y , Sayari A . Modeling CO₂ adsorption on amine-functionalized mesoporous silica: 1. A semi-empirical equilibrium model. Chemical Engineering Journal, 2010, 161(1-2): 173–181

[59] Ahmadian Hosseini A , Jahandar Lashaki M . A comprehensive evaluation of amine-impregnated silica materials for direct air capture of carbon dioxide. Separation and Purification Technology, 2023, 325: 124580

[60] Bacsik Z , Atluri R , Garcia-Bennett A E , Hedin N . Temperature-induced uptake of CO₂ and formation of carbamates in mesocaged silica modified with n-propylamines. Langmuir, 2010, 26(12): 10013–10024

[61] Danon A , Stair P C , Weitz E . FTIR study of CO₂ adsorption on amine-grafted SBA-15: elucidation of adsorbed species. Journal of Physical Chemistry C, 2011, 115(23): 11540–11549

[62] Rim G , Priyadarshini P , Song M , Wang Y , Bai A , Realff M J , Lively R P , Jones C W . Support pore structure and composition strongly influence the direct air capture of CO₂ on supported amines. Journal of the American Chemical Society, 2023, 145(13): 7190–7204

[63] Hiyoshi N , Yogo K , Yashima T . Adsorption characteristics of carbon dioxide on organically functionalized SBA-15. Microporous and Mesoporous Materials, 2005, 84(1-3): 357–365

[64] Srikanth C S , Chuang S S C . Spectroscopic investigation into oxidative degradation of silica-supported amine sorbents for CO₂ capture. ChemSusChem, 2012, 5(8): 1435–1442

[65] Srikanth C S , Chuang S S C . Infrared study of strongly and weakly adsorbed CO₂ on fresh and oxidatively degraded amine sorbents. Journal of Physical Chemistry C, 2013, 117(18): 9196–9205

[66] Yoo C J , Park S J , Jones C W . CO₂ adsorption and oxidative degradation of silica-supported branched and linear aminosilanes. Industrial & Engineering Chemistry Research, 2020, 59(15): 7061–7071

[67] Tanthana J , Chuang S S C . In situ infrared study of the role of PEG in stabilizing silica-supported amines for CO₂ capture. ChemSusChem, 2010, 3(8): 957–964

Competing interests

The authours declare that they have no competing interests.

Acknowledgements

Financial support from the National Natural Science Foundation of China (Grant No. 22278143) is gratefully acknowledged.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2512-3 and is accessible for authorized users.

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