Cobalt phthalocyanine tetracarboxylic acid modified reduced graphene oxide: a sensitive matrix for the electrocatalytic detection of peroxynitrite and hydrogen peroxide

Hosu, Ioana Silvia; Wang, Qian; Vasilescu, Alina; Peteu, Serban F.; Rădiţoiu, Valentin; Railian, Svetlana; Zaitsev, Vladimir; Turcheniuk, Kostiantyn; Wang, Qi; Li, Musen; Boukherroub, Rabah; Szunerits, Sabine

doi:10.1039/c4ra09781e

Cited by 74 publications

(39 citation statements)

References 71 publications

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“…Recent studies have suggested that CoPc aggregation occurs when CoPc is adsorbed to carbon surfaces at high loadings 39,51,52 and that this aggregation limits the number of exposed active sites and, therefore, the measured per-CoPc TOFs 39 . To explore whether aggregation influences the results of our mechanistic studies, we explored the loading dependence on CO 2 RR activity by CoPc both physisorbed onto EPG and within the P4VP films over four orders of magnitude of loading between 2.19 × 10 −11 mol cm −2 and 2.19 × 10 −7 mol cm −2 (results are summarized in Supplementary Figs.…”

Section: Resultsmentioning

confidence: 99%

Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation

2019

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The selective and efficient electrochemical reduction of CO 2 to single products is crucial for solar fuels development. Encapsulating molecular catalysts such as cobalt phthalocyanine within coordination polymers such as poly-4-vinylpyridine leads to dramatically increased activity and selectivity for CO 2 reduction. In this study, we use a combination of kinetic isotope effect and proton inventory studies to explain the observed increase in activity and selectivity upon polymer encapsulation. We provide evidence that axial-coordination from the pyridyl moieties in poly-4-vinylpyridine to the cobalt phthalocyanine complex changes the rate-determining step in the CO 2 reduction mechanism accounting for the increased activity in the catalyst-polymer composite. Moreover, we show that proton delivery to cobalt centers within the polymer is controlled by a proton relay mechanism that inhibits competitive hydrogen evolution. These mechanistic findings provide design strategies for selective CO 2 reduction electrocatalysts and serve as a model for understanding the catalytic mechanism of related heterogeneous systems.

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Section: Resultsmentioning

confidence: 99%

Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation

2019

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“…Interestingly, transition metal porphyrins and similar molecular complexes are known to self‐assemble on coinage metal supports . Several studies have been devoted towards understanding the molecule‐support interaction of transition metal–porphyrins or pthalocyanines on supports such as gold, silver, copper, platinum or even non‐metal surfaces such as graphene,, graphene oxide,, and carbon nanotubes ,,. Depending on the strength/nature of the interaction between metal surface and organometallic homogeneous catalyst, the charge, spin, or magnetism of the adsorbed molecular catalyst can be modified which in turn may influence its catalytic properties …”

Section: Introductionmentioning

confidence: 99%

Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes

Siahrostami

Nørskov

2018

ChemCatChem

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It has been a long‐standing goal to find alternative, cost effective catalysts for oxygen reduction reaction (ORR) in fuel cells. Molecular complexes capable of efficiently catalyzing ORR, when supported on a conducting solid surface could provide interesting hybrid materials combining the best of homogeneous and heterogeneous catalysis. We use density functional theory to study the ORR activity of molecular (unsupported) and gold supported 3d metal (II)‐porphycenes (MPc). All the 3d metal‐porphycenes adsorb strongly on the Au(111) support with negative free energy of formation ranging from 1.0–3.0 eV while solvation lowers the energy of molecular MPc by only 0.5 eV compared to the gas phase. These indicate that the 3d MPc are stable and anchored firmly to the gold surface under ORR conditions. Based on our analysis, the gold support enhances the ORR activity in some of the examined MPc systems. We find that the molecular MnPc and FePc are the best ORR electrocatalysts with theoretical overpotentials of 0.44 V and 0.36 V. This work highlights the important role of the support in preserving/increasing the activity of molecular catalyst.

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“…Studies of the biochemical roles of the PON precursors, nitric oxide and superoxide anion, have been performed using electrochemical detection methods for real-time, label-free and direct measurement of these reactive species [17–19]. There are some reports of the direct detection of PON by electroanalytical techniques reported in the literature [14–28]. Amatore and co-workers studied the electrochemical oxidation of PON by steady-state and transient voltammetry with platinized carbon microelectrodes [15–18].…”

Section: Introductionmentioning

confidence: 99%

“…Chemically-modified platinum microelectrodes coated with manganese tetraaminophthalocyanine films were utilized for PON detection in alkaline solution (pH 10.2) where it is more stable [21]. More recently, it was shown that improved catalytic PON activity could be achieved by depositing nanostructured metalloporphyrin or metallophtalocyanine films onto glassy carbon or carbon fiber electrodes [25-28]. …”

Section: Introductionmentioning

confidence: 99%

Electrochemical detection of peroxynitrite using hemin–PEDOT functionalized boron-doped diamond microelectrode

Peteu

Whitman

Galligan

et al. 2016

Analyst

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Peroxynitrite is a potent nitroxidation agent and highly reactive metabolite, clinically correlated with a rich pathophysiology. Its sensitive and selective detection is challenging due to its high reactivity and short sub-second lifetime. Boron-doped diamond (BDD) microelectrodes have attracted interest because of their outstanding electroanalytical properties that include a wide working potential window and enhanced signal-to-noise ratio. Herein, we report on the modification of a BDD microelectrode with an electro-polymerized film of hemin and polyethylenedioxythiophene (PEDOT) for the purpose of selectively quantifying peroxynitrite. The nanostructured modified polymer layer was characterized by Raman spectroscopy and scanning electron microscopy (SEM). The electrochemical response to peroxynitrite was studied by voltammetry and time-based amperometry. The measured detection limit was 10 ± 0.5 nM (S/N=3), the sensitivity was 4.5 ± 0.5 nA/nM and the response time was 3.5 ± 1 s. The hemin-PEDOT BDD sensors exhibited a response variability of 5% or less (RSD). The stability of the sensors after a 20-day storage in 0.1 M PB (pH 7.4) at 4 °C was excellent as at least 93% of the initial response to 50 nM PON was maintained. The presence of PEDOT was correlated with a sensitivity increase.

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Cobalt phthalocyanine tetracarboxylic acid modified reduced graphene oxide: a sensitive matrix for the electrocatalytic detection of peroxynitrite and hydrogen peroxide

Abstract: The electrocatalytic properties of cobalt phthalocyanine modified reduced graphene oxide for peroxynitrite and hydrogen peroxide are investigated.

Cited by 74 publications

References 71 publications

Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation

Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation

Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes

Electrochemical detection of peroxynitrite using hemin–PEDOT functionalized boron-doped diamond microelectrode

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