Irreversible electrocatalytic reduction of V(V) to V(IV) using phosphomolybdic acid

Abstract

Although VO_22^+(aq) reduction is kinetically slow at glassy carbon and Pt electrodes, phosphomolybdic acid is shown to catalyze the electrochemical reduction of VO_2^+(aq) to VO_2^+(aq) in 1.0 M H_2SO_4(aq). A second-order rate constant of 33 M^(-1) s^(-1) was observed for this process. ^(31)P NMR spectra demonstrated that PMo_(11)VO_(40)^(4-) and PMo_(18)V_2O_(40)^(50-) were the dominant P-containing species under electrocatalytic conditions. The incorporation of V^V into the polyoxoanion led to a shift in potential from E^o(VO^(2+)(aq)/VO^(2+)(aq)) = +0.80 V vs Ag/AgCl for free V^V/V^(IV) to Eo' = +0.55 V vs Ag/AgCl for V^(V)/V^(Iv) bound in the heteropolyoxometalate (PMo_(11)VO_(40_^(4-)). This shift in formal potential corresponded to an equilibrium constant of 1.7 X 10^4 M^(-1) for preferential binding of V^V over V^(IV) by the heteropolyoxoanion. This negative shift in redox potential, combined with the slow electrochemical kinetics of free VO_2^+(aq) reduction and with the facile reaction of bound V^(IV) with free V^V in 1.0 M H_2SO_4(aq), resulted in the irreversible electrocatalytic reduction of VO_2^+(aq) to VO^(2+)(aq).