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In-situ IR spectroscopic study of oxidation of NaH2PO2 on pt electrodes in acidic solutions

The mechanism of electrochemical oxidation of hypophosphite on a polycrystalline platinum electrode was studied by SNIFTIRS (i.e. Subtractively Normalized Interfacial FTIR Spectroscopy) as well as by cyclic voltammetry. The in-situ IR reflectance spectra were analyzed as a function of the Pt electrode potentials in 0.5 mol/L H 2SO 4 +0.1 mol/L NaH 2PO 2 solution. The in-situ IR band characteristics are those near 2 100, 1 250 and 1 110 cm -1, assigned as the presence of adsorbed hydrogen atom on Pt and non-adsorbed H 3PO 4 molecule or phosphate species, respectively. It was concluded that both hydrogen atoms and H 2PO 2 are the adsorbed species on Pt in the potential range where the oxidation occurs, and the final oxidation product was H 3PO 4 rather than phosphate, different from the oxidation of hypophosphite on Ni electrode. Accordingly, a new mechanism was proposed for the hypophosphite oxidation on Pt electrodes in acidic media, i.e. in the potential range lower than 0.8 V(vs. SCE) the adsorbed H 2PO 2 was directly oxidized to phosphate via phosphite, and in the potential range higher than 0.8 V the oxygen-adsorbed species on Pt participates in the oxidation of H 2PO 2 into phosphate.