DOE OSTI2020
A systematic investigation of uranyl borates under different synthetic conditions resulted in five new 2D compounds, namely, (H 3 O)[(UO 2 )(BO 3 )], Li[(UO 2 )(BO 3 )] · (H 2 O), α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ], β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] and K 2.5 [(UO 2 ) 5 (BO 3 ) 2 O 2.5 (OH) 1.5 ] · (H 2 O) 2.5 . (H 3 O)[(UO 2 )(BO 3 )] and Li[(UO 2 )(BO 3 )] · (H 2 O) were obtained from hydrothermal reactions at 220 °C using the same mineralizer. Both materials possess the uranophane sheet topology with different symmetry of the unit cells. In the structure of (H 3 O)[(UO 2 )(BO 3 )] and Li[(UO 2 )(BO 3 )] · (H 2 O), UO 7 pentagonal bipyramids share edges and vertexes with four BO 3 planar triangles. α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] and β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] are polytypes. α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] was synthesized from a high-temperature solid-state reaction under ambient pressure; whereas β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] was obtained from a high-temperature/high-pressure (HT/HP) reaction. Both structures have an identical anion topology, but β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] crystallizes in space group with higher symmetry. In K 2.5 [(UO 2 ) 5 (BO 3 ) 2 O 2.5 (OH) 1.5 ] · (H 2 O) 2.5 , which was obtained from a hydrothermal reaction, UO 7 polyhedra share vertexes and edges with two independent BO 3 triangles, forming the most complex uranyl borate layers among all five compounds. The different synthetic routes, novel topologies, thermal behavior and Raman spectra are discussed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗