inorganic chemistry - Reaction intermediates of MnO2 catalyzed H2O2 decomposition reaction

Manganese dioxide catalyzes the decomposition of hydrogen peroxide to water and oxygen gas.

But what are the intermediates in this catalyzed reaction?

Answer

As Watts et al. have shown, the decomposition products of this Fenton-like reaction strongly depend on the $\mathrm{pH}$ of the solution.¹

If performed in acidic conditions, the reaction generates mostly hydroxy radicals, but no reductants (which would be the hydroperoxide and superoxide anions). If, conversely, the reaction is held in neutral conditions, Watts et al. have shown that the reaction produces significantly more of the aforementioned reductants.

Do et al. have conducted further research into the reaction mechanism at $\mathrm{pH}=7$ and concluded that the observed reaction order may be approximated as a pseudo 1^st order reaction, where the ratio $\ce{[H2O2]}/\ce{[#MnO2]}$ is vital to the description of the decomposition rate.² They have further shown that reactive intermediates, such as superoxide and hydroperoxide anions are generated by the reaction. After slightly modifying the pH towards alkaline conditions, the production rates for the reactive anions increased drastically.

Do et al. have meticulously assembled a table with a proposed reaction pathway:

And finally, I quote one of their closing statements:²

The existence of hydroperoxide/superoxide anion implies that the suggested reaction mechanism could be explained by hydrogen peroxide being decomposed, not only directly on the surface of manganese oxide, but also through a propagation reaction involving intermediates such as hydroperoxide/superoxide anion in solution.

---

References

1. Watts, R., Sarasa, J., Loge, F., and Teel, A. Oxidative and Reductive Pathways in Manganese-Catalyzed Fenton’s Reactions. J. Environ. Eng., 131(1), 2005, 158–164, DOI link.


2. Si-Hyun Do, Bill Batchelor, Hong-Kyun Lee, Sung-Ho Kong. Hydrogen peroxide decomposition on manganese oxide (pyrolusite): Kinetics, intermediates, and mechanism. Chemosphere, Volume 75, Issue 1, March 2009, Pages 8-12, DOI link.