Structural Study of Poly-Molybdate Ions in Acid Mo–Ni Aqueuous Solutions

Abstract

Structures of poly-molybdate ions in acid Ni-Mo aqueous solutions have been investigated by the anomalous x-ray scattering (AXS), EXAFS and small angle x-ray scattering (SAXS) methods. In a solution containing only molybdenum ions, molybdenum ions form a poly-molybdate ion consisting of seven edge-sharing MoO6 octahedra. In a solution containing both Mo and Ni ions, there exists another poly-molybdate ion consisting of 6 edge-sharing MoO6 surrounding a Ni ion. The coordination number of Mo-Mo pairs decreases by half by adding citric ions. This indicates that the large poly-molybdate ion is decomposed to smaller molybdate ions due to formation of citric complexes. This is also confirmed by the SAXS measurement. Since molybdenum-nickel alloys are not electrodeposited from the solutions without citric ions, we expect that the decomposition of large poly-molybdate ions in the solution is closely related with the mechanism of the induced codeposition of molybdenum and nickel alloy.