Accession Number:

ADA510206

Title:

Unraveling Oxygen Reduction Reaction Mechanisms on Carbon-Supported Fe-Phthalocyanine and Co-Phthalocyanine Catalysts in Alkaline Solutions

Descriptive Note:

Journal article

Corporate Author:

INDIANA UNIV-PURDUE UNIV AT INDIANAPOLIS

Report Date:

2009-01-01

Pagination or Media Count:

10.0

Abstract:

In this work, we combine electrochemical measurements, such as the rotating disk electrode RDE and the rotating ring-disk electrode RRDE techniques, and density functional theory DFT calculations to elucidate the mechanisms of the oxygen reduction reaction ORR on carbon-supported Fe-phthalocyanine FePcC and Co-phthalocyanine CoPcC catalysts in 0.1 M NaOH solutions. The onset potential for ORR on FePcC catalyst is found to be around 0.05 V vs. HgHgO in 0.1 M NaOH solutions, which is 100 mV more positive than that on CoPcC. RDE and RRDE measurements show that the ORR mechanism is via a 4e- pathway on the FePcC while it is through a 2e- pathway on the CoPcC catalyst. The catalyst stability tests reveal that FePc is much less stable than CoPc under fuel cell cathode working conditions. Moreover, DFT calculations were performed to study the adsorption of O2, H2O, OH, HOOH, and H2OO molecules on FePc and CoPc molecule catalysts. We conclude the following from our theoretical and experimental results for the ORR on FePcC and CoPcC catalysts 1 the lower the O2 adsorption energy, the higher the kinetics of the ORR will be 2 the ORR pathways, 2e- or 4e-, are mainly determined by the H2O2 adsorption configurations and 3 OH adsorption on the catalysts is considered to be an important factor to affect the catalyst stability.

Subject Categories:

  • Physical Chemistry

Distribution Statement:

APPROVED FOR PUBLIC RELEASE