Characterization and electrochromic properties of poly(2,3,5,6-tetrafluoroaniline): Progress towards a transparent conducting polymer

ACS Appl. Mater. Interfaces

Meunier‐Prest

Heintz

et al. 2018

In this work, we report for the first time on a comprehensive study of poly(2,3,5,6-tetrafluoroaniline) (PTFANI). Contrary to the nonfluorinated polyaniline (PANI) or its analogues bearing one fluorine atom, PTFANI is a poorly conductive material. We present a comprehensive study of the electrosynthesized PTFANI from its monomer in an acidic aqueous medium. PTFANI was fully characterized by a potential-pH diagram, spectroelectrochemistry, and electrochemical quartz crystal microbalance (EQCM) measurements, as well as by a morphological study. Combined with the X-ray photoelectron spectroscopy (XPS) analysis, it allowed us to understand the redox properties of this polymer compared to those of the unsubstituted PANI. At pH < 1.85, no proton transfer occurred during the electrochemical process, but the insertion of anions at the site of the protonated imines was demonstrated through the EQCM and XPS experiments. PTFANI showed a lower ratio of 1 ClO per 3 2,3,5,6-tetrafluoroaniline units compared to that of PANI. The behavior at pH > 1.85 was different; no anion upload was observed during the electron transfer, but 1 H per electron was involved during the transition between the leucoemeraldine and emeraldine base forms. It should also be noted that the oxidation of the emeraldine into the pernigraniline form was not accessible in PTFANI because of the electron-withdrawing effects of the fluorine atoms. However, we took advantage of the unique behavior of PTFANI to build heterojunctions, by combining with a highly conductive molecular material, namely lutetium bisphthalocyanine, LuPc. The obtained double-lateral heterojunction exhibited a particularly interesting sensitivity to ammonia, even under humid atmospheres, with a limit of detection of 450 ppb. This work paves the way for the use of PTFANI in other electronic devices and as a sensor not only in the field of air quality monitoring but also in the field of health diagnosis in measuring the human breath.

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Comprehensive Study of Poly(2,3,5,6-tetrafluoroaniline): From Electrosynthesis to Heterojunctions and Ammonia Sensing

ACS Appl. Mater. Interfaces

Meunier‐Prest

Heintz

et al. 2018

“…The electronic properties of polyaniline derivatives are highly dependent on the nature of the substituents on the aniline ring. Numerous studies have focused on the properties of monofluorinated derivatives [2,3], but only a few on the fully fluorinated polyaniline (PolyTetraFluoroAniline, PTFA) [4]. In this study, we present electrochemical and morphological properties of PTFA polymer electroplated on conductive substrates, in comparison with polyaniline already used as sensing material in NH3 sensors [5,6].…”

Section: Introductionmentioning

confidence: 99%

Electrochemical deposition of aniline derivatives for conductometric gas sensors

Materials Today: Proceedings

Prest

Suisse

et al. 2019

To cite this version:M. Mateos, R Meunier Prest, J. M. Suisse, M. Bouvet. Electrochemical deposition of aniline derivatives for conductometric gas sensors. AbstractPolymer film of poly(2,3,5,6-tetrafluoroaniline) (PTFA) were electroplated on ITO substrate from acidic medium by chronoamperometry. Electrochemical and morphological characterizations were performed and compared to polyaniline properties similarly coated. It seemed that PTFA film had an irreversible redox response with poor conductivity due to the absence of acid-base doping. This film were then incorporated in a patented device called MSDI heterojunction to perform ammonia sensing in humid atmosphere.

“…Numerous studies have focused on the properties of monofluorinated derivatives [2], but only a few on the fully fluorinated polyaniline (PolyTetraFluoroAniline PTFA). The first aim of our work was to carry out a complete study of the PTFA polymer, from its electrosynthesis to its use as an active material in gas sensors.…”

Section: Motivationmentioning

confidence: 99%

Conducting Polymers for Ammonia Sensing: Electrodeposition, Hybrid Materials and Heterojunctions

Bouvet

Proceedings of Eurosensors 2017, Paris, France, 3–6 September 2017

Meunier‐Prest

et al. 2017

Polyaniline (PANI) with electrodonating and electrowithdrawing substituents were electrodeposited and studied as sensing materials in resistors and heterojunctions. Whereas the dimethoxyaniline leads to a highly conductive material, the tetrafluoroaniline leads to a poor conducting polymer. However, this latter was used in heterojunctions, associated with a highly conductive material, the lutetium bisphthalocyanine LuPc2. Elsewhere, hybrid materials combining polypyrrole (PPy) with ionic macrocycles as counterions were also electrosynthesized and used as sensing material in resistors, for the detection of ammonia. They exhibit a higher sensitivity compared to PPy prepared with small counterions, with a stable response in a broad range of relative humidity.Keywords: conducting polymer; heterojunction; gas sensor; ammonia; humidity MotivationA strong demand exists for gas sensors operating at low temperature and prepared with low energy processes. Thus, molecular materials, including polymeric materials that can be deposited by solution processing, are good candidates. They can also be used to prepare hybrid materials when associated with carbonaceous or inorganic compounds. The properties of the obtained materials, e.g., morphology, roughness and specific surface, hydrophilicity or hydrophobicity and eventually their optical and electronic properties can thus be tuned to optimize their sensing properties. Among solution processing technologies, electrodeposition presents clear advantages, for example when different materials need to be deposited on different electrodes located on the same substrate.The electronic properties of polyaniline derivatives [1] are highly dependent on the nature of the substituents on the aniline ring. Numerous studies have focused on the properties of monofluorinated derivatives [2], but only a few on the fully fluorinated polyaniline (PolyTetraFluoroAniline PTFA). The first aim of our work was to carry out a complete study of the PTFA polymer, from its electrosynthesis to its use as an active material in gas sensors. The second one was to study the interest of incorporating macrocyclic counteranions on the properties of another conducting polymer, namely polypyrrole (PPy). We prepared PPy-metallophthalocyanine complexes hybrid materials by electrosynthesis and by the layer-by-layer technique.