Mechanism of H(2)O(2) Decomposition by Triphenylphosphine Oxide

[Image: see text] A decomposition mechanism of H(2)O(2) by triphenylphosphine oxide (TPPO) is presented. TPPO is often incorporated in proton-exchange membrane electrolytes as a moiety to inhibit the H(2)O(2)-induced degradation of the membranes. However, it has not been revealed how TPPO decreases the concentration of free H(2)O(2) in the membranes. Following the experimental X-ray structures, the TPPO dimer capturing two H(2)O(2) molecules was used as the calculation model. The vibrational spectrum calculations for various hydration numbers show that this model correctly reproduces the spectral peaks of TPPO capturing H(2)O(2). On the basis of this model, the H(2)O(2) decomposition mechanism by the TPPO dimer was searched. It was consequently found that this reaction proceeds through three steps: (1) Hydrogen transfer from H(2)O(2) to the P=O bond of TPPO, (2) Hydrogen transfer from the −OOH group to the −OH group, and (3) O–O bond formation between O(2) groups. The calculated vibrational spectra for the reactants and intermediates indicated that the first and second steps are activated by vibrational excitations. Moreover, the third step giving low barrier heights is considered to proceed through two reaction paths: directly producing the O(2) molecule or going through an HOOOH intermediate. Interestingly, this reaction mechanism was found to use the violation of the octet rule for the P=O double bond, resulting in the strong H(2)O(2) binding of TPPO.