Compounds containing electrically conducting macromolecules bear interesting properties as functional materials in various fields. As for catalytic applications, however, principles are scarcely, if at all, understood. Here we describe a systematic investigation of the relationship between the structure of a new type of conducting polymer supported metal catalyst and the catalystʼs oxidation activity. We have found that nanoclusters of unusual β-PtO2 (d = (1.9 ± 0.5) nm) could be deposited on polyaniline, and the resulting catalyst exhibits exceptionally low light-off temperatures in carbon monoxide oxidation even in the presence of other environmental pollutants. Characterizing the working state of the active catalyst by combining in situ/operando techniques (EPR, DRIFTS, and EXAFS), we visualized a distinctly increased charge carrier density within the support. Our results suggest that the intensive contact between an electron-conducting polymer support and up-grown nanoparticles affords a charge exchange between redox centers, thereby boosting catalytic activity dramatically.

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