Post-synthetic efficient functionalization of polyaniline with phosphorus-containing groups. Effect of phosphorus on electrochemical properties

Quílez‐Bermejo, Javier; Ghisolfi, Alessio; Grau-Marín, Daniel; San‐Fabián, Emilio; Morallón, Emilia; Cazorla‐Amorós, Diego

doi:10.1016/j.eurpolymj.2019.07.048

Cited by 23 publications

(19 citation statements)

References 64 publications

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“…The redox processes observed with a high reversibility are in agreement with the formation of polyaniline-based oligomers. In polyaniline, redox processes, related with the change of the oxidation states from leucoemeraldine to emeraldine and emeraldine to pernigraniline in the polymer chain, appear at around 0.3 and 0.7 V vs. RHE in acid conditions, respectively [39,40]. However, the high reversibility and symmetry of the redox processes suggest that covalently bound redox species may also exist.…”

Section: Electrochemical Characterization Of Swcnt Functionalized Witmentioning

confidence: 99%

Electrochemical functionalization of single wall carbon nanotubes with phosphorus and nitrogen species

Quintero-Jaime

Cazorla‐Amorós

Morallón

2020

Electrochimica Acta

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Single Wall Carbon Nanotubes (SWCNTs) have been successfully functionalized by electrochemical oxidation in presence of 4-aminophenyl phosphonic acid (4-APPA).Electrochemical modification has been performed by cyclic voltammetry using different upper potential limits, producing the incorporation of N and P functionalities on SWCNT through polymerization reactions, although some covalent attachment cannot be discarded. Electrochemical oxidation in presence of CNT produces polymerization of 4-APPA, what has been related to the interaction between monomer and the CNT surface.The voltammograms of the functionalized SWCNT show different well-defined redox processes that are maintained at high pH. Raman spectroscopy shows that the structure of the SWCNT is maintained even at high potentials suggesting that oxidation selectively occurs in the 4-APPA monomer favoring polymer chain growth. The degree of modification of SWCNT can be easily controlled by selecting the electrochemical conditions.

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Section: Electrochemical Characterization Of Swcnt Functionalized Witmentioning

confidence: 99%

Electrochemical functionalization of single wall carbon nanotubes with phosphorus and nitrogen species

Quintero-Jaime

Cazorla‐Amorós

Morallón

2020

Electrochimica Acta

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“…Nonetheless, few works can be found regarding phosphonated polyanilines, and most of them use chemical routes to achieve functionalization, either on the rings or on secondary nitrogen atoms. It was reported that the chemical post-modification of polyaniline could be attained by direct phosphonation under specific experimental conditions [30][31][32][33]. Alternatively, the chemical oxidation of phosphonated methoxy-or benzyl-aniline monomers yielded polyaniline-derived structures showing additional functionalities to the phosphonic group [34,35].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Phosphorus-Containing Polyanilines by Electrochemical Copolymerization

et al. 2020

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In this study, the phosphonation of a polyaniline (PANI) backbone was achieved in an acid medium by electrochemical methods using aminophenylphosphonic (APPA) monomers. This was done through the electrochemical copolymerization of aniline with either 2- or 4-aminophenylphosphonic acid. Stable, electroactive polymers were obtained after the oxidation of the monomers up to 1.35 V (reversible hydrogen electrode, RHE). X-ray photoelectron spectroscopy (XPS) results revealed that the position of the phosphonic group in the aromatic ring of the monomer affected the amount of phosphorus incorporated into the copolymer. In addition, the redox transitions of the copolymers were examined by in situ Fourier-transform infrared (FTIR) spectroscopy, and it was concluded that their electroactive structures were analogous to those of PANI. From the APPA monomers it was possible to synthesize, in a controlled manner, polymeric materials with significant amounts of phosphorus in their structure through copolymerization with PANI.

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“…C1s and O1s spectra of all materials are included in Figures S3–S8 in the Supplementary Materials . G/Si-PANI-X and G/Ti-PANI-X samples show two peaks in the N1s spectra, which are associated with polyaniline [ 40 , 41 , 42 ]: (i) neutral amine groups at 399.5 eV and (ii) positively charged nitrogen atoms at approximately 401.7 eV. Table 2 shows the ratio between positively charged nitrogen atoms and total nitrogen content and the total nitrogen atomic content.…”

Section: Resultsmentioning

confidence: 99%

Polyaniline-Derived N-Doped Ordered Mesoporous Carbon Thin Films: Efficient Catalysts towards Oxygen Reduction Reaction

2020

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One of the most challenging targets in oxygen reduction reaction (ORR) electrocatalysts based on N-doped carbon materials is the control of the pore structure and obtaining nanostructured thin films that can easily be incorporated on the current collector. The carbonization of nitrogen-containing polymers and the heat treatment of a mixture of carbon materials and nitrogen precursor are the most common methods for obtaining N-doped carbon materials. However, in this synthetic protocols, the surface area and pore distribution are not controlled. This work enables the preparation of 2D-ordered N-doped carbon materials through the carbonization of 2D polyaniline. For that purpose, aniline has been electropolymerized within the porous structure of two different templates (ordered mesoporous Silica and ordered mesoporous Titania thin films). Thus, aniline has been impregnated into the porous structure and subsequently electropolymerized by means of chronoamperometry at constant potential. The resultant samples were heat-treated at 900 °C with the aim of obtaining 2D N-doped carbon materials within the template structures. Polyaniline and polyaniline-derived carbon materials have been analyzed via XPS and TEM and characterized by electrochemical measurements. It is worth noting that the obtained 2D-ordered mesoporous N-doped carbon materials have proved to be highly active electrocatalysts for the ORR because of the formation of quaternary nitrogen species during the heat treatment.

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Post-synthetic efficient functionalization of polyaniline with phosphorus-containing groups. Effect of phosphorus on electrochemical properties

Cited by 23 publications

References 64 publications

Electrochemical functionalization of single wall carbon nanotubes with phosphorus and nitrogen species

Electrochemical functionalization of single wall carbon nanotubes with phosphorus and nitrogen species

Synthesis of Phosphorus-Containing Polyanilines by Electrochemical Copolymerization

Polyaniline-Derived N-Doped Ordered Mesoporous Carbon Thin Films: Efficient Catalysts towards Oxygen Reduction Reaction

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