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

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