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Issue 47, 2015
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Bimetallic porous porphyrin polymer-derived non-precious metal electrocatalysts for oxygen reduction reactions

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Abstract

The development of efficient and stable electrocatalysts on the basis of non-precious metals (Co, Fe) is considered as one of the most promising routes to replace expensive and susceptible platinum as the oxygen reduction reaction (ORR) catalyst. Here we report a synthetic strategy for the precursor controlled, template-free preparation of novel mono- (Fe; Co) and bimetallic (Fe/Co) nitrogen-doped porous carbons and their electrocatalytic performance towards the ORR. The precursors are composed of metal–porphyrin based conjugated microporous polymers (M-CMPs with M = Fe; Co; Fe/Co) derived from polymerization of metalloporphyrins by the Suzuki polycondensation reaction, which enables the synthesis of bimetallic polymers with alternating metal–porphyrin units for the preparation of carbon-based catalysts with homogenously distributed CoN4 and FeN4 centres. Subsequent pyrolysis of the networks reveals the key role of pre-morphology and network composition on the active sites. 57Fe-Mössbauer spectroscopy was conducted on iron catalysts (Fe; Fe/Co) to determine the coordination of Fe within the N-doped carbon matrix and the catalytic activity-enhancing shift in electron density. In acidic media the bimetallic catalyst demonstrates a synergetic effect for cobalt and iron active sites, mainly through a 4-electron transfer process, achieving an onset potential of 0.88 V (versus a reversible hydrogen electrode) and a half-wave potential of 0.78 V, which is only 0.06 V less than that of the state-of-the-art Pt/C catalyst.

Graphical abstract: Bimetallic porous porphyrin polymer-derived non-precious metal electrocatalysts for oxygen reduction reactions

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Publication details

The article was received on 11 Aug 2015, accepted on 20 Oct 2015 and first published on 20 Oct 2015


Article type: Paper
DOI: 10.1039/C5TA06309D
Citation: J. Mater. Chem. A, 2015,3, 23799-23808
  • Open access: Creative Commons BY-NC license
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    Bimetallic porous porphyrin polymer-derived non-precious metal electrocatalysts for oxygen reduction reactions

    S. Brüller, H. Liang, U. I. Kramm, J. W. Krumpfer, X. Feng and K. Müllen, J. Mater. Chem. A, 2015, 3, 23799
    DOI: 10.1039/C5TA06309D

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