Preparation of Ag(I) and Cu(II) exchanged α-zirconium phosphate by using molten nitrate salts and their electric characterization

Fully exchanged anhydrous silver form, Zr(AgPO4)2 and partially exchanged Cu form of α-ZrP were prepared by treating molten state of AgNO3 and Cu(NO3)2 with crystalline α-ZrP and semicrystalline ZrP gel. Conductivity measurement was carried out at 10∼300°C using pulse and de methods to separate ionic and electronic contribution of the total conductivity. Ag ion exchanged ZrP showed ionic conductivity mainly, because low coordination number and covalent bonding of the Ag ion causes weak coulombic interaction with oxygen anions around the cation. The conductivities were in the range of 10−7 to 10−4ω−1 • cm−1. The crystallinity in this system did not influence the conductivity much. On the other hand, Cu ion exchanged ZrP had electronic conductivity mainly in the range of 10−7 to 10−5ω−1 • cm−1. The electronic conducting was different depending on the extent of Cu ion exchange. The semiconducting property of Cu form of α-ZrP can be explained by d-p-d orbital overlap in CuOCu bonding.