Thermochemistry of 3D and 2D Rare Earth Oxychlorides (REOCls).

The thermodynamic stability of rare earth (RE) materials plays a key role in the design of separation and recycling processes for RE elements. Thermodynamic stability is fundamentally influenced by the lanthanide contraction, as observed in the systematic reduction of unit cell volumes with increasing atomic number. RE materials are found in the form of solids having primary bonds in three dimensions (3D materials) as well as ones with primary bonds in two dimensions (2D materials) whose layers are held together by weak van der Waals (vdW) forces. While studies of synthesis, structure, and physical properties of 2D RE materials are numerous, no systematic research has compared their thermodynamic stability to that of 3D materials. In the present work, RE oxychlorides (REOCls), which display a structural transition from a 3D-polyhedral network (PbFCl-type) to a vdW-bonded layered one (SmSI-type) as the RE size decreases, were all synthesized by the flux method. High-temperature oxide melt solution calorimetry was used to determine their formation enthalpies to enable Born-Haber cycles to calculate lattice energies. Our results indicate that REOCl compounds are thermodynamically stable when compared to their binary oxides and chlorides. The lattice energies of 3D REOCls increase with decreasing RE size yet are insensitive to unit cell volumes for 2D REOCls. This is caused by interatomic interactions parallel and perpendicular to layers in the SmSI-type REOCls, causing a different structure response to the lanthanide contraction than 3D RE materials.