New oxide films have been electrodeposited from [P
2Mo
18O
62]
6− by potential cycling in mildly acidic aqueous media. To obtain an adherent and persistent film, it is necessary that more
than six electrons/molecule be fixed on the framework of the heteropolyanion. The film is then studied in pure supporting
electrolyte. In this medium, a remarkable current increase is observed during the potential cycling. Whether the film is deposited
on a glassy carbon electrode or on the gold electrode of an electrochemical quartz crystal microbalance (EQCM), exactly the
same steady current increase up to a maximum is obtained in cyclic voltammetric measurements. The EQCM reveals a steady mass
increase during the continuous cycling of the film in the supporting electrolyte. This behaviour is interpreted as featuring
an irreversible water and electrolyte intake into the film, up to a maximum, after which the phenomena observed during reduction
and oxidation processes are taken as featuring intercalation/deintercalation, respectively. This behaviour is much the same
as described in the literature for WO
3 and MoO
3 bronzes, except that the present films seem very stable and have shown no tendency to dissolve or deactivate.
Key words Heteropolyanion - Metal oxides - Intercalation/deintercalation - Electrochemical quartz crystal microbalance - Cyclic voltammetry
Received: 2 December 1998 / Accepted: 26 January 1999