Investigations of Cu/Zn Oxalates from Aqueous Solution: Single-Phase Precursors and Beyond.

The existence of a limited solid-solution series in the Cu/Zn binary metal oxalate system is reported. Coprecipitation was applied for the preparation of a comprehensive set of mixed Cu/Zn oxalates. Rietveld refinement of the XRD data revealed the formation of mixed-metal oxalate single phases at the compositional peripheries. Accordingly, the isomorphous substitution of ZnII into CuII oxalate takes place at Zn contents of ≤6.6 and ≥79.1 atom %. Zn incorporation leads to a pronounced unit-cell contraction accompanied by Vegard-type trends for the lattice parameters. Morphologically, both solid solutions show close resemblance to the corresponding pure single-metal oxalates, and thus distinct differences are identified (SEM). The successful formation of solid solutions was further evidenced by thermal analysis. The decomposition temperature of the oxalate was taken as an approximation for ZnII incorporation into the CuII oxalate structure. Single decomposition events are observed within the stated compositional boundaries and shift to higher temperature with increasing Zn content, whereas multiple events are present near Cu/Zn parity. Moreover, these findings are supported by IR and Raman spectroscopic investigations. This study on the Cu/Zn mixed-metal oxalate system sheds light on the important prerequisites for solid-solution formation and identifies the structural limitations that predefine its application as catalyst precursor.