Unprecedented Radiation Resistant Thorium–Binaphthol Metal–Organic Framework

Abstract

A thorium–organic framework (TOF-16) containing hexameric secondary building units connected by functionalized binaphthol linkers was synthesized, characterized, and irradiated to probe its radiation resistance. Radiation stability was examined using γ-rays and 5 MeV He2+ ions to simulate α particles. γ-irradiation of TOF-16 to an unprecedented 4 MGy dose resulted in no apparent bulk structural damage visible by X-ray diffraction. To further probe radiation stability, we conducted the first He2+ ion irradiation study of a metal–organic framework (MOF). Diffraction data indicate onset of crystallinity loss upon approximately 15 MGy of irradiation and total loss of crystallinity upon exposure to approximately 25 MGy of He2+ ion irradiation. The high radiation resistance observed suggests MOFs can withstand radiation exposure at doses found in nuclear waste streams and highlights the need for a systematic approach to understand and eventually design frameworks with exceptional radiation resistance.

Capture of Gaseous Iodine in Isoreticular Zirconium‐Based UiO‐n Metal‐Organic Frameworks: Influence of Amino Functionalization, DFT Calculations, Raman and EPR Spectroscopic Investigation

“…Previous studies have thus shown a significant stability of MOF materials networks when irradiated under large doses of gamma rays. [7][8][9][10] Therefore, right after the events of Fukushima, the first studies about the capture of radionuclides in MOFs emerged in the literature. These species can be solubilized in water like actinides, technetium and cesium, [4,11] or gaseous noble gas like Xe, Kr [12] or iodine derivatives.…”

“…Furthermore, MOFs can show a great chemical resistance, as they can be stable in liquid water, in high‐temperature steam or under irradiation. Previous studies have thus shown a significant stability of MOF materials networks when irradiated under large doses of gamma rays [7–10] . Therefore, right after the events of Fukushima, the first studies about the capture of radionuclides in MOFs emerged in the literature.…”

Visible colorimetric dosimetry of UV and ionizing radiations by a dual-module photochromic nanocluster

“…9 ). Metal-organic frameworks (MOFs) featuring high radiation-resistance were known as exemplified by Th 6 O 4 (OH) 4 (H 2 O) 6 (C 22 O 6 H 12 ) 6 (TOF-16) (Supplementary Table 3 ) 43 . The investigation on radiation stability of cluster species has not been conducted and the only relevant case is an ultrastable [Hf 13 ] nanocluster, which is highly resistant to both concentrated acid and alkali 44 , 45 .…”

Visible Colorimetric Dosimetry of UV and Ionizing Radiations by a Dual-Module Photochromic Nanocluster

“…Metal-organic frameworks (MOFs) featuring high radioresistance were known and Th 6 O 4 (OH) 4 (H 2 O) 6 (C 22 O 6 H 12 ) 6 (TOF-16) represents the most radioresistant MOFs reported to date (Table S3). 43 The investigation on radiation stability of cluster species was conducted for the rst time in this work and the only relevant case is an ultrastable [Hf 13 ] nanocluster which is highly resistant to both concentrated acid and alkali. 44,45 Th-SINAP-100 represents the only reported radioresistant polynuclear cluster and one of the most radioresistant metal-organic materials in general.…”