Exploring the Synthesis of Monolithic Metal-Organic Frameworks and their Composites for Advanced Water Management Solutions

Metal-organic frameworks (MOFs) represent an expansive and exciting class of coordination polymers that are formed when metal ions or oxide clusters crystallise by self-assembling with multi-dentate organic linkers. While these porous materials have achieved remarkable academic success, their practical applications have been limited due to their powdery nature, which hampers usability in various settings. Recently, however, a groundbreaking class of monolithic MOFs has emerged, breaking the mould of traditional formulations. These innovative monoliths merge the advantageous qualities of pelletized materials with the exceptional single-crystal density and porosity characteristics that theoretical MOFs promise. For example, the monolith referred to as monoHKUST-1, which consists of copper ions coordinated with benzene-1,3,5-tricarboxylate linkers, has established itself as a benchmark for natural gas storage, highlighting its efficiency and capacity. Similarly, monoZIF-8, made from zinc and 2-methyl imidazolate linkers, has exhibited the remarkable ability to host catalytic nanoparticles (NP@monoMOF), thereby facilitating effective and environmentally sustainable water purification processes. Additionally, monoUiO-66, composed of zirconium oxide and benzoic dicarboxylate linkers, has shown significant promise in the realm of carbon dioxide adsorption, contributing to the fight against climate change. Building on these encouraging findings, efforts have been made to synthesise novel monolithic MOFs. Specifically targeted were aluminium-based MOFs (Al-MOFs) due to their superior mechanical, chemical, and thermal stability, qualities that make them particularly suitable for a range of industrial applications. A novel synthetic process led to the development of two new monolithic materials: monoMOF-303, featuring the robust and porous structure of Al(OH)(1- H- pyrazole-3,5-dicarboxylate), and monoAl-fum, which is based on octahedral AlO6-fumarate. In addition, a new technique was introduced that enables fine-tuning of both bulk density and pore size distribution within these macroscopic monoliths by artificially incorporating non-crystalline mesoporosity. The remarkable potential of monolithic MOFs to serve as hosts for nanoparticles was further evaluated through meticulous studies examining how the surface functionality of nanoparticles affects doping levels in both monoZIF-8 and monoUiO-66. The immobilisation of CdSe-TiO2 nanoparticles within monoZIF-8 was specifically investigated for its potential to degrade ciprofloxacin when exposed to visible light. Moreover, the synthesis of SnO2@monoUiO-66 showcased the versatility of monolithic MOFs, demonstrating their capability to host nanoparticles for the effective and photochemical degradation of methylene blue. In summary, the synthesis and characterisation of new monoMOFs, alongside their composite forms featuring nanoparticle integration (NP@monoMOF), have been comprehensively evaluated, leading to the creation of innovative materials with promising industrial applications. These advancements not only highlight the adaptability and functionality of monolithic MOFs but also pave the way for their future utilisation in a variety of fields.

Name dc:type.qualificationname

Doctor of Philosophy (PhD)

Level dc:type.qualificationlevel

Doctoral

Grantor dc:publisher.institution

University of Cambridge

Year dc:date.issued

2025

Author dc:creator

• Alghamdi, Lana

Advisor dc:contributor.advisor

• Wheatley, Andrew

• Monolithic Metal-Organic Frameworks
• Water Management Solutions

Licence

• https://www.repository.cam.ac.uk/bitstreams/6cbc046a-fe77-4f3c-a078-4c1a652b4114/download
• http://purl.org/NET/rdflicense/allrightsreserved

Language dc:language

eng

Author Identifier

0009-0000-2806-3749

OAI identifier oai:identifier

oai:www.repository.cam.ac.uk:1810/390393