In situ degradation and radiation-responsive behavior of metal organic frameworks under high-energy irradiation: implications for sensing and shielding

Abstract

This review examines the promise and challenges of metal–organic frameworks (MOFs) in high-radiation environments, focusing on their sensing and shielding applications. In radiation detection, specific MOF architectures, such as Tb–Cu₄I₄ clusters, achieve high light yields of ∼29 400 photons MeV⁻¹ and spatial resolutions of 12.6 lp mm⁻¹, enabling low detection limits as sensitive as 23 nGy s⁻¹ in flexible composite screens. Conversely, for dosimetry, actinide-based systems like U-Cbdcp show linear luminescence quenching across a wide dynamic range from 10 to 4700 Gy (R² = 0.999). The structural resilience of MOFs under irradiation is a key differentiator. Frameworks such as MIL-100(Fe/Cr) retain crystallinity and over 95% of their original surface area after 1 MGy γ-dose, while thorium-based TOF-16 withstands doses up to 4 MGy. However, stability is not uniform; ZIF-8 suffers a ∼55% BET surface area loss at 1.75 MGy, highlighting a strong dependence on metal-node and linker chemistry. Despite these advances, critical knowledge gaps exist and could impede practical deployment. A systematic, mechanistic understanding of in situ degradation pathways, such as linker scission and defect accumulation, and their quantitative impact on functional performance is lacking. Furthermore, radiation shielding efficacy demands not only high attenuation but also mechanical integrity, a domain where MOF composites are underexplored. This review provides a design roadmap to address these challenges, advocating for linker engineering with radiation-resistant π-systems, post-synthetic defect healing, and the creation of hybrid MOF-composite architectures. By integrating advanced in situ characterization with predictive computational models, this review charts a course for engineering next-generation, radiation-hardened MOFs, transforming them from laboratory curiosities into robust materials for nuclear, medical, and aerospace applications.