Photocatalytic Application of 4f-5f Inorganic-Organic Frameworks: Influence of Lanthanide Contraction on the Structure and Functional Properties of a Series of Uranyl-Lanthanide Complexes

Abstract

A series of 4f-5f heteronuclear metallic complexes were synthesized by a hydrothermal route from mixtures of uranyl acetate, lanthanide nitrate, and 1,2,4,5-benzenetetracarboxylic acid (H4BTA) in an aqueous system. Single-crystal X-ray analysis revealed that the thirteen UO2-Ln-BTA complexes ([(UO2)1.5Ln(C10O8H2)1.5(H2O)x]y H2O; Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13); x=6 for 1-4, x=5 for 5-13; y=0 for 4, y=1 for 3, y=2 for 2, y=3 for 5, 9, 10, 12, 13, y=4 for 1, 6, 7, 8, 11) are isomorphous with three-dimensional structures. For the purpose of developing potential applications of the UO2-Ln-BTA complexes, we investigated their surface photovoltage and photocatalytic properties. In addition, the thermogravimetric analysis and photoluminescent properties of these complexes were also studied in detail.