Recent advances in the applications of thorium-based metal–organic frameworks and molecular clusters

Abstract

This perspective highlights the recent advances in the structural and practical aspects of thorium-based metal-organic frameworks (Th-MOFs) and molecular clusters. Thorium, as an underexplored actinide, features surprisingly rich coordination geometries...

Achieving High Photo/Thermocatalytic Product Selectivity and Conversion via Thorium Clusters with Switchable Functional Ligands

“…As relatively abundant actinides on earth, thorium and its derivatives have manifested critical applications in nuclear energy, medical, and industrial fields because of their radiation resistance, high temperature resistance, and high thermal conductivity. − However, the relatively low structural variability of these materials restricts their development to some extent in more potential applications. − The development of thorium-based coordination compounds provides more possibilities to overcome these restrictions, because more structural variations and functional modulations can be readily implemented through the diverse coordination numbers and intriguing coordination modes of thorium as well as coordination of different functional ligands . Particularly, thorium-based metal–organic frameworks (Th-MOFs) have been tuned for applications in gas adsorption, ion exchange, and radiation resistance through coordination modification with different organic ligands. − Nevertheless, the application of thorium-based functionalized materials (including thorium-based complexes) in the field of catalysis is still largely unexplored. − To date, a mere handful of Th-MOFs have been reported to be applied as heterogeneous catalysts for CO 2 cycloaddition and photocatalytic oxidation of 2-chloroethyl ethyl sulfide. − …”

Energetic Systematics of Metal–Organic Frameworks: A Case Study of Al(III)-Trimesate MOF Isomers

“…Combining with the above thermodynamic trends, this suggests that a higher metal coordination environment carries more enthalpic stability from the coordinated ligands. This suggests the following: (1) frameworks with higher metal coordination (e.g., lanthanide- − and actinide-MOFs − ) may have favorable enthalpies of formations, (2) defect-rich isomers (and other related MOFs) with missing linker defects are enthalpically destabilized by possessing higher (O 2– + OH – )/ligand ratios through charge substitution of linkers by hydroxides or modulating reagents, implying that the formation of defect-rich MOFs is less enthalpically favorable . This again underlines the significant effects of metals and their corresponding coordination geometries in promoting enthalpic stabilities of MOFs.…”

Structural transformation of metal oxo species within UiO-66 type metal–organic frameworks

“…Beyond the well-studied transition metal elements ubiquitous within MOF literature, recent reports of actinidecontaining MOF nodes have accelerated the understanding of the elements' unique coordination chemistry which is pertinent for the nuclear waste storage and nuclear energy applications. [6][7][8][9][10][11][12][13][14][15] In particular, limited knowledge exists about that solid-state structural chemistry of thorium due to the uncontrolled growth of polynuclear Th species in solution. 16,17 Recent interest has surfaced to better understanding the structural behavior of thorium given surging interest in developing a more sustainable nuclear fuel process based on the 233 U-232 Th fuel cycle as opposed to the U 235 fuel cycle.…”