Selective electro-oxidation of carbon monoxide with carbon-supported Rh- and Ir-porphyrins at low potentials in acid electrolyte

Baar, J.F. van; Veen, J.A.R. van; Wit, N. de

doi:10.1016/0013-4686(82)80059-5

Cited by 38 publications

(29 citation statements)

References 14 publications

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“…--The fact that CO oxidation takes place at iridium porphyrins in the same potential range as that in which oxygen reduction occurs [1], taking into account that this reaction starts with the adsorption of CO on an Ir(III) single site [18,19], mitigates against the assumption that a dimer should be the active species. Furthermore, it is noted that aged porphyrins (IrOEP and IrTPP) drop drastically in oxygen reduction activity and produce only hydrogen peroxide, even when supported on carbon.…”

Section: Discussionmentioning

confidence: 99%

An in-situ Raman study of the effect of the support for adsorbed iridium-chelates in catalysing oxygen reduction

Bouwkamp-Wijnoltz

Pałys

Visscher

et al. 1996

Journal of Electroanalytical Chemistry

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Section: Discussionmentioning

confidence: 99%

An in-situ Raman study of the effect of the support for adsorbed iridium-chelates in catalysing oxygen reduction

Bouwkamp-Wijnoltz

Pałys

Visscher

et al. 1996

Journal of Electroanalytical Chemistry

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“…In the earlier studies, most of the work was focused on the reduction of molecular O 2 but was later shown over the years that they catalyze a myriad of reactions. Some phthalocyanines and related macrocyclic complexes catalyze (i) the electrooxidation of formic acid [8,30], CO [8,[29][30][31][32][33], SO 2 [34][35][36], oxalic acid [37][38][39][40][41][42][43][44][45][46][47][48], glucose [49][50][51][52][53][54][55][56][57][58][59][60][61][62][63], molecular hydrogen [64][65][66][67][68], H 2 O 2 [67][68][69], hydrazine [8,30,47,…”

Section: Introductionmentioning

confidence: 99%

Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions

Zagal¹,

Griveau²,

Silva³

et al. 2010

Coordination Chemistry Reviews

548

415

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“…1,3 From this context, we have paid special attention to Rh porphyrins-based CO oxidation catalysts. [4][5][6] We have demonstrated that the CO oxidation activity strongly depends on the structures of porphyrin ligands and found a carbon-supported Rh tetrakis͑4-carboxyphenylporphyrin͒ ͓Rh͑TCPP͒/C, Fig. 1͔ that can oxidize CO at a high rate below 0.1 V ͓vs a reversible hydrogen electrode ͑RHE͔͒ at 60°C.…”

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confidence: 98%

CO Electro-oxidation by Rh Disulfo-deuteroporphyrin, and Its Mitigation Effect on CO Poisoning of PEMFC Anode

Yamazaki

Yao

Takeda

et al. 2011

Electrochem. Solid-State Lett.

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A catalyst that uses Rh deuteroporphyrin 2,4-disulfonic acid was demonstrated to catalyze electrochemical CO oxidation at low overpotentials. The catalytic activity was enhanced by the improvement of the adsorption method. The onset potential of the improved catalyst was less than 0.05 V ͑vs a reversible hydrogen electrode, at 60°C͒. This onset potential is lower than that for other Rh porphyrin-based catalysts reported previously. The CO poisoning of a Pt electrode was mitigated by the addition of this Rh porphyrin complex into the electrolyte solution. The Pt anode of a proton exchange membrane fuel cell ͑PEMFC͒ is sensitive to CO. Electrochemical CO oxidation might be a key reaction to counteract CO poisoning. © 2010 The Electrochemical Society. ͓DOI: 10.1149/1.3516636͔ All rights reserved.Manuscript submitted July 7, 2010; revised manuscript received October 11, 2010. Published November 22, 2010 In the development of a proton exchange membrane fuel cell ͑PEMFC͒, CO poisoning of the Pt anode has been a severe problem. Many CO-tolerant anode catalysts, such as Pt-Ru anode catalysts, have been developed to overcome this problem.1,2 The CO-tolerance of these catalysts is derived from the electronic properties that weaken CO adsorption. 2If CO is oxidized electrochemically during the operation of a PEMFC, the problem of CO poisoning could be significantly counteracted. Unfortunately, conventional CO-tolerant electrocatalysts cannot oxidize CO at lower overpotentials under conditions of the anode at which a PEMFC operates. 1,3 From this context, we have paid special attention to Rh porphyrins-based CO oxidation catalysts. [4][5][6] We have demonstrated that the CO oxidation activity strongly depends on the structures of porphyrin ligands and found a carbon-supported Rh tetrakis͑4-carboxyphenylporphyrin͒ ͓Rh͑TCPP͒/C, Fig. 1͔ that can oxidize CO at a high rate below 0.1 V ͓vs a reversible hydrogen electrode ͑RHE͔͒ at 60°C. 6 These potential regions are considerably lower than those with Pt-based electrocatalysts. However, because the anode overpotential is almost zero in a PEMFC, the onset potential for CO electrooxidation by catalysts also has to be decreased close to 0 V before they can be applied to a PEMFC.In this work, we first tried to decrease the overpotential for CO oxidation by Rh porphyrin catalysts based on the relationship between structure and activity obtained in the previous study 6 and found that carbon-supported Rh deuteroporphyrin 2,4-disulfonic acid ͓Rh͑DPDS͒/C, Fig. 1͔ can catalyze electrochemical CO oxidation at a lower potential than that required for Rh͑TCPP͒/C. At 60°C, the catalyst can oxidize CO below 0.05 V vs RHE.Furthermore, we tried to mitigate the CO poisoning of Pt-based electrodes using this Rh porphyrin complex. It was known that certain kind of additives or cocatalysts improved the CO-tolerance of Pt catalysts.7-10 Because Rh porphyrin complexes can reduce CO concentration by the electrochemical oxidation at low potentials, they are promising candidates as effective additives. In t...

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Selective electro-oxidation of carbon monoxide with carbon-supported Rh- and Ir-porphyrins at low potentials in acid electrolyte

Cited by 38 publications

References 14 publications

An in-situ Raman study of the effect of the support for adsorbed iridium-chelates in catalysing oxygen reduction

An in-situ Raman study of the effect of the support for adsorbed iridium-chelates in catalysing oxygen reduction

Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions

CO Electro-oxidation by Rh Disulfo-deuteroporphyrin, and Its Mitigation Effect on CO Poisoning of PEMFC Anode

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