Autors: Popova M., Theochari G., Mihaylov M., Chakarova K., Hadjiivanov K., Boycheva, S. V., Szegedi A., Marinkov N., Karashanova D., Kovacheva D., Velinov N.
Title: Waste-derived hierarchical zeolite/silica composites for CO₂ capture: Integrating phase composition and 3D printing for enhanced adsorption
Keywords: 3D printing, CO2 capture, Coal fly ash, Rice husk waste, Zeolite/mesoporous silica composites

Abstract: Waste-derived zeolite/mesoporous silica composites containing FAU, LTA, and sodalite phases in different proportions were synthesized from coal fly ash and rice husk-derived silica, providing a sustainable route for converting industrial and agricultural residues into functional CO2 adsorbents. The composites were characterized by X-ray powder diffraction (XRD), N2 physisorption, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) in TEM, X-ray fluorescence (XRF), Mössbauer spectroscopy, and Fourier transform infrared (FTIR) spectroscopy using NO, CO, and CO2 as probe molecules. The results showed that varying the silica content in the synthesis mixture strongly affects the zeolite phase composition, leading to FAU/LTA-containing composites at lower silica contents and to FAU/sodalite-containing phase assemblage at higher silica content. All samples exhibited hierarchical micro/mesoporosity. It was found that the CO2 adsorption was governed mainly by the zeolite phase composition, zeolite/ silica ratio and accessibility of extra-framework Na⁺ adsorption sites. The best performance was achieved for FA-Si-2, which exhibited both the highest CO2 uptake under static (4.0 mmol g⁻¹) and dynamic (3.9 mmol g⁻¹) conditions. FTIR results showed that CO2 adsorption is dominated by molecular adsorption on Na⁺-containing sites, mainly in bridged configurations, whereas carbonate-like species represent only a minor secondary population. The cycling experiments confirmed effective regeneration at 100 °C, with a capacity loss ≤ 10% over 15 adsorption–desorption cycles. A 3D-printed adsorbent based on FA-Si-1 exhibited slightly enhanced CO2 uptake compared with the powdered material, highlighting the potential of additive manufacturing to improve accessibility and mass transfer, making the material more suitable for practical applications.

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Journal of Environmental Chemical Engineering, vol. 14, pp. 123710, 2026, Netherlands, https://doi.org/10.1016/j.jece.2026.123710

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