Simultaneous electrochemical and mössbauer measurements on polymeric iron phthalocyanine oxygen electrodes

Blomquist, J.; Helgeson, U.; Moberg, L.C.; Johansson, Lennart; Larsson, Ragnar

doi:10.1016/0013-4686(82)80037-6

Cited by 19 publications

(9 citation statements)

References 12 publications

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“…Not only should catalyst activity be maintained over the device lifetime, but selectivity should also (section ). However, several catalysts with promising beginning-of-life performance, such as porphyrins, , degrade over time. Our current insight in this area is rather limited.…”

Section: Discussionmentioning

confidence: 99%

“…On the other hand, the stability of porphyrin and porphyrin-like structures tends to be low. 86,87 High temperature annealing in an inert atmosphere results in a significantly increased stability; however, the heat treatment tends to decrease the selectivity toward H 2 O 2 . 87,88…”

Section: Electrochemical H 2 O 2 Productionmentioning

confidence: 99%

“…The latter is of particular interest because the activity is among the highest in Figure a. On the other hand, the stability of porphyrin and porphyrin-like structures tends to be low. , High temperature annealing in an inert atmosphere results in a significantly increased stability; however, the heat treatment tends to decrease the selectivity toward H 2 O 2 . , …”

Section: Tailoring the Electrode: Fundamental Aspects Of The 2-electr...mentioning

confidence: 99%

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Toward the Decentralized Electrochemical Production of H₂O₂: A Focus on the Catalysis

Yang

Verdaguer‐Casadevall²,

et al. 2018

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H2O2 is a valuable, environmentally friendly oxidizing agent, with a wide range of uses, from the provision of clean water to the synthesis of valuable chemicals. The on-site electrolytic production of H2O2 would bring the chemical to applications beyond its present reach. The successful commercialization of electrochemical H2O2 production requires cathode catalysts with high activity, selectivity and stability. In this Perspective, we highlight our current understanding of the factors that control the cathode performance. We review the influence of catalyst material, electrolyte and the structure of the interface at the mesoscopic scale. We provide original theoretical data on the role of the geometry of the active site and its influence on activity and selectivity. We have also conducted a series of original experiments on (i) the effect of pH on H2O2 production on glassy carbon, pure metals, and metal-mercury alloys, and (ii) the influence of cell geometry and mass transport in liquid half-cells in comparison to membrane electrode assemblies.

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Section: Discussionmentioning

confidence: 99%

Section: Electrochemical H 2 O 2 Productionmentioning

confidence: 99%

Section: Tailoring the Electrode: Fundamental Aspects Of The 2-electr...mentioning

confidence: 99%

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Toward the Decentralized Electrochemical Production of H₂O₂: A Focus on the Catalysis

Yang

Verdaguer‐Casadevall²,

et al. 2018

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“…Information was obtained on the magnetic orientation of several different electrodes. Blomquist et al (31,32) studied polymeric iron with phthalocyanine oxygen electrodes. The electrocatalytic activity was investigated as a function of various methods for the preparation of these electrodes.…”

Section: Miscellaneous Applicationsmentioning

confidence: 99%

Moessbauer spectroscopy

Stevens¹,

Bowen²

1984

Anal. Chem.

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“…Many mononuclear metal porphyrins act as electrocatalysts (1-21) but the work of Collman and Anson (22)(23)(24)(25)(26)(27)(28) and has revealed that certain binuclear porphyrins are much more effective. Similarly, mononuclear phthalocyanines of iron and cobalt are effective (36)(37)(38)(39)(40)(41)(42)(43)(44)(45)(46)(47)(48)(49)(50), but some ill-characterised "dimeric" and polymeric phthalocyanines appear more effective (51)(52)(53)(54)(55)(56)(57)(58)(59)(60)(61)(62). Savy and co-workers (54)(55)(56) performed ESCA, esr, Mijssbauer and optical spectroscopic studies to establish correlations between the spectroscopic properties of polymeric and monomeric iron phthalocyanines and the electrocatalytic activity of these species towards oxygen reduction.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic reduction of molecular oxygen by mononuclear and binuclear cobalt phthalocyanines

Hempstead¹,

Lever²,

Leznoff³

1987

Can. J. Chem.

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Investigations of the electrocatalytic activity of mononuclear and binuclear cobalt phthalocyanines for the reduction of molecularoxygen established that the latter compounds are more effective catalysts than the corresponding mononuclear species.A correlation between the half-bandwidths for the Q band of these species and their catalytic efficiency, expressed as a kinetically-limited current, suggests that the increase in activity may be attributed to electronic coupling between the phthalocyanine rings.Mrcnner R. Her*apstpnp, A. B. P. Leven et Cllppotto C. LtzNopr. Can. J. Chem. 65,2671Chem. 65, (1987 (22)(23)(24)(25)(26)(27)(28) and Chang and co-workers (29)(30)(31)(32)(33)(34)(35) has revealed that certain binuclear porphyrins are much more effective. Similarly, mononuclear phthalocyanines of iron and cobalt are effective (36-50), but some ill-characterised "dimeric" and polymeric phthalocyanines appear more effective (51)(52)(53)(54)(55)(56)(57)(58)(59)(60)(61)(62). Savy and co-workers (54-56) performed ESCA, esr, Mdssbauer and optical spectroscopic sfudies to establish correlations between the spectroscopic properties of polymeric and monomeric iron phthalocyanines and the eiectrocatalytic activity of these species towards oxygen reduction. We consider here a correlation between the optical spectra of a series of well-characterized mono-and binuciear cobalt phthalocyanines and their electrocatalytic activity. for about an hour before scanning the working electrode at a rate of 100 mV/s over the range 0.00 to *1.00 V versus the silver wire.Adsorbed layers on OPG or SAPG electrodes were obtained by cycling until the anodic and cathodic peak currents associated with the adsorbed species remained constant over 5 min ofcontinuous scanning. When this condition was satisfied, the adsorbed layer was assumed to have reached a steady coverage. Scans at various rates were then recorded to determine the surface coverage (vide infra).The catalytic efficiency of the various phthalocyanine compounds was investigated with the adsorbed species on the OPG electrode. This modified electrode was removed from the phthalocyanine solution, washed with ethanol, then with water, and finally placed in the cell for the aqueous studies. The 0.l0 M NaOH solution in this cell had been purged with oxygen for several hours to ensure saturation. The electrode was then scanned over the range 0.00 to -1.00 V versus sce at a rate of l0 mV/s for rotation rates ranging from 400 to l0 0O0 rpm.After each scan. the electrode was held at 0.00 V for I min to oermit the rotation rate to be changed for the next scan. The theory of intramolecular coupling in these binuclear phthalocyanines has been presented elsewhere (66). In solution, these binuclear species are expected to exist in a dynamic equilibrium between various conformations, dependent upon the nature of the bridge since, in some cases, steric effects may provide barriers to free rotation. Therefore, the electronic absorption spectrum of a solution of one of these binuclear species wo...

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Simultaneous electrochemical and mössbauer measurements on polymeric iron phthalocyanine oxygen electrodes

Cited by 19 publications

References 12 publications

Toward the Decentralized Electrochemical Production of H₂O₂: A Focus on the Catalysis

Toward the Decentralized Electrochemical Production of H₂O₂: A Focus on the Catalysis

Moessbauer spectroscopy

Electrocatalytic reduction of molecular oxygen by mononuclear and binuclear cobalt phthalocyanines

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Simultaneous electrochemical and mössbauer measurements on polymeric iron phthalocyanine oxygen electrodes

Cited by 19 publications

References 12 publications

Toward the Decentralized Electrochemical Production of H2O2: A Focus on the Catalysis

Toward the Decentralized Electrochemical Production of H2O2: A Focus on the Catalysis

Moessbauer spectroscopy

Electrocatalytic reduction of molecular oxygen by mononuclear and binuclear cobalt phthalocyanines

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Product

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Toward the Decentralized Electrochemical Production of H₂O₂: A Focus on the Catalysis

Toward the Decentralized Electrochemical Production of H₂O₂: A Focus on the Catalysis