Dissertation committee:
Μαργαρίτα Νίκη Ασημακοπούλου, Αναπληρώτρια Καθηγήτρια, Τμήμα Φυσικής, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών.
Ιωάννης Σ. Παπαευσταθίου, Καθηγητής, Τμήμα Χημείας, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών.
Ματθαίος Σανταμούρης, Καθηγητής, Arts,Design & Architecture, University of New South Wales.
Κωνσταντίνος Καρτάλης, Καθηγητής, Τμήμα Φυσικής, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών.
Παναγιώτης Νάστος, Καθηγητής, Τμήμα Γεωλογίας και Γεωπεριβάλλοντος, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών.
Πατρίνα Παρασκευοπούλου, Αναπληρώτρια Καθηγήτρια, Τμήμα Χημείας, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών.
Ελισάβετ Μποσιώλη, Επίκουρη Καθηγήτρια, Τμήμα Φυσικής, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών.
Summary:
The presented thesis delves into the development of composite materials designed for applications within the built environment, particularly focused on exhibiting the capacity to capture carbon dioxide. This research endeavor has culminated in the creation of composite materials, achieved through the amalgamation of conventional construction substances like cement, gypsum, and recycled ceramics in powdered configuration. These ingredients are adeptly combined through dry-mixing with microporous constituents hailing from the Metal Organic Framework (MOF) class, namely ZIF-8, UiO-66 and MIL-53 (Al), interconnected via suitable binding agents including Polyvinyl Alcohol, MethylCellulose, Ethanol, and water. Eighteen samples were prepared. This production methodology exhibits potential for upscaling through the utilization of additive 3D printing techniques, thereby enabling cost-effective fabrication of advanced monolithic structures.
One of the noteworthy aspects of these composite materials is their adsorption capacity for carbon dioxide. At a temperature of 273 K, composite material consisting of recycled ceramic, MIL-53(Al) (7.5% wt) and Methylcellulose can adsorb 9.42 cm3 of CO2 per gram of the material. Furthermore, even at a slightly higher temperature of 298 K, it maintains a substantial adsorption capacity, capturing 4.79 cm3 g-1. This property makes it a promising candidate for carbon capture applications within the built environment. In addition to the composite mentioned above, another composite material, composed of Gypsum, UiO-66, and PolyVinyl Alcohol, exhibits notable adsorption capabilities as well. At 273 K, this composite material adsorbs 5.65 cm3 g-1, and at 298 K, it captures 3.09 cm3 g-1. This demonstrates the versatility of the approach, as different combinations of building materials and MOFs can be tailored to meet specific requirements. The samples’ adsorption capacity at 273 K ranges from 1.72 cm3 g-1 up 9.42 cm3 g-1 while at 298 K from 0.72 cm3 g-1 up to 4.79 cm3 g-1 . Furthermore, thermal gravimetric analysis (TGA) results have indicated that all the composites are capable of withstanding temperatures higher than 200°C before experiencing structural collapse. Nevertheless, the materials containing gypsum exhibit a weight loss at around 150°C that is attributed in the dehydration of the CaSO4·2H2O. This resilience to elevated temperatures is crucial for ensuring the stability and durability of these composite materials when incorporated into various construction applications. Additionally, powder X-ray diffraction (PXRD) results have revealed that the MOFs maintain their crystallinity even after the mixing process with water and the other building materials, as well as during the formation of pellets. However this was not the case for the sample consisting of cement and UiO-66. This preservation of crystalline structure in the majority of the samples is an indication to the robustness of the composite manufacturing process, ensuring that the unique adsorption properties of the MOFs are retained in the final composite materials. Overall, these composite materials represent an advancement in sustainable construction practices, offering not only exceptional carbon capture capabilities but also the ability to withstand high temperatures, all while retaining the crystalline properties of the incorporated MOFs.
The introductory chapter of the thesis embarks on a comprehensive review, elucidating recent strides in the domain of shaping and producing MOF macro structures. This exploration extends to encompass binding materials, a facet that has remained relatively unexplored until now. However, this chapter illuminates their prospective role in catapulting MOFs toward heightened industrial applicability. The subsequent chapter delves into the intricate process of synthesizing the aforementioned composite materials. Integral to this exploration are measurements including Thermal Gravimetric Analysis (TGA) and Powder X-ray Diffraction (PXRD), both of which furnish insights into the material's structural and thermal attributes. Additionally, the chapter spotlights the results stemming from CO2 porosimetry, shedding light on the materials' efficacy in capturing carbon dioxide. In the third chapter, the thesis undertakes a rigorous life cycle assessment of a distinct MOFs, namely ZIF-8. This analytical investigation encompasses diverse synthetic pathways, critically evaluating their environmental implications and overall sustainability. By scrutinizing each facet of the life cycle, from production to disposal, this chapter provides a comprehensive understanding of the ecological footprint associated with the synthesized ZIF-8s.
Keywords:
Metal organic frameworks, construction materials, binders, monoliths, carbon dioxide capture, buildings
