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The development of the basic understanding of the charge storage mechanisms in electrodes for energy storage applications needs deep characterization of the electrode/electrolyte interface. In this work, we studied the charge of the double layer capacitance at single layer graphene (SLG) electrode used as a model material, in neat (EMIm-TFSI) and solvated (with acetonitrile) ionic liquid electrodes. The combination of electrochemical impedance spectroscopy and gravimetric electrochemical quartz crystal microbalance (EQCM) measurements evidence that the presence of solvent drastically increases the charge carrier density at the SLG/ionic liquid interface. The capacitance is thus governed not only by the electronic properties of the graphene, but also by the specific organization of the electrolyte side at the SLG surface originating from the strong interactions existing between the EMIm+ cations and SLG surface. EQCM measurements also show that the carbon structure, with the presence of sp2 carbons, affects the charge storage mechanism by favoring counter-ion adsorption on SLG electrode versus ion exchange mechanism in amorphous porous carbons.
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The solid electrolyte interphase (SEI) remains a central challenge to lithium-ion battery durability, in part due to poor understanding of the basic chemistry responsible for its formation and evolution. In this study, the SEI on a non-intercalating tungsten anode is measured by operando neutron reflectometry and quartz crystal microbalance. A dual-layer SEI is observed, with a 3.7 nm thick inner layer and a 15.4 nm thick outer layer. Such structures have been proposed in the literature, but have not been definitively observed via neutron reflectometry. The SEI mass per area was 1207.2 ng/cm2, and QCM provides insight into the SEI formation dynamics during a negative-going voltage sweep and its evolution over multiple cycles. Monte Carlo simulations identify SEI chemical compositions consistent with the combined measurements. The results are consistent with a primarily inorganic, dense inner layer and a primarily organic, porous outer layer, directly confirming structures proposed in the literature. Further refinement of techniques presented herein, coupled with additional complementary measurements and simulations, can give quantitative insight into SEI formation and evolution as a function of battery materials and cycling conditions. This, in turn, will enable scientifically-guided design of durable, conductive SEI layers for Li-ion batteries for a range of applications.
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A molecularly imprinted electrochemical quartz crystal microbalance (EQCM) sensor is fabricated here for taurine, a ß-amino acid significant for functioning of almost all vital organs. The polymeric film of l-methionine was electrochemically deposited on gold-coated EQCM electrode. Experimental parameters were optimized for controlling the performance of molecularly imprinted polymer (MIP)-modified sensor such as ratio of monomer and template, number of electropolymerization cycles, mass deposited in each cycle, and pH. Thus, fabricated MIP-EQCM sensor was successfully applied for estimation of taurine in solutions with varying matrices, such as aqueous, human blood plasma, milk from cow, buffalo, and milk powder. Under optimized parameters, response of MIP sensor to taurine was linearly proportional to its concentration with limit of detection as 0.12µM. Hence, a highly sensitive and selective piezoelectric sensor for taurine has been reported here via imprinting approach.
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Eletroquímica , Impressão Molecular/métodos , Polimerização , Taurina/química , Animais , Calibragem , Carbono/química , Eletrodos , Vidro/química , Ouro/química , Humanos , Concentração de Íons de Hidrogênio , Microscopia de Força Atômica , Modelos Moleculares , Técnicas de Microbalança de Cristal de Quartzo , Reprodutibilidade dos Testes , Taurina/sangue , TermodinâmicaRESUMO
Degradation of cathode materials in lithium-ion batteries results in the presence of transition metal ions in the electrolyte, and these ions are known to play a major role in capacity fade and cell failure. Yet, while it is known that transition metal ions migrate from the metal oxide cathode and deposit on the graphite anode, their specific influence on anode reactions and structures, such as the solid electrolyte interphase (SEI), is still quite poorly understood due to the complexity in studying this interface in operational cells. In this work we combine operando electrochemical atomic force microscopy (EC-AFM), electrochemical quartz crystal microbalance (EQCM), and electrochemical impedance spectroscopy (EIS) measurements to probe the influence of a range of transition metal ions on the morphological, mechanical, chemical, and electrical properties of the SEI. By adding representative concentrations of Ni2+, Mn2+, and Co2+ ions into a commercially relevant battery electrolyte, the impacts of each on the formation and stability of the anode interface layer is revealed; all are shown to pose a threat to battery performance and stability. Mn2+, in particular, is shown to induce a thick, soft, and unstable SEI layer, which is known to cause severe degradation of batteries, while Co2+ and Ni2+ significantly impact interfacial conductivity. When transition metal ions are mixed, SEI degradation is amplified, suggesting a synergistic effect on the cell stability. Hence, by uncovering the roles these cathode degradation products play in operational batteries, we have provided a foundation upon which strategies to mitigate or eliminate these degradation products can be developed.
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Zinc-ion batteries, in which zinc ions and protons do intercalation and de-intercalation during battery cycling with various proposed mechanisms under debate, have been studied. Recently, electrolytic zinc-manganese batteries, exhibiting the pure dissolution-deposition behavior with a large charge capacity, have been accomplished through using electrolytes with Lewis acid. However, the complicated chemical environment and mixed products hinder the investigation though it is crucial to understand the detailed mechanism. Here, cyclic voltammetry coupled electrochemical quartz crystal microbalance (EQCM) and ultraviolet-visible spectrophotometry (UV-Vis) are respectively, for the very first time, used to study the transition from zinc-ion batteries to zinc electrolytic batteries by the continuous addition of acetate ions. These complementary techniques operando trace the mass and the composition evolution. The observed formation and dissolution of zinc hydroxide sulfate (ZHS) and manganese oxides evince the effect of acetate ions on zinc-manganese batteries from an alternative perspective. Both the amount of acetate and the pH value have large impacts on the capacity and Coulombic efficiency of the MnO2 electrode, and thus they should be optimized when constructing a full zinc-manganese battery with high rate capability and reversibility.
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Manganês , Zinco , Compostos de Manganês , Técnicas de Microbalança de Cristal de Quartzo , Óxidos , Espectrofotometria Ultravioleta , AcetatosRESUMO
Research into extracellular vesicles (EVs) has grown significantly over the last few decades with EVs being widely regarded as a source of biomarkers for human health and disease with massive clinical potential. Secreted by every cell type in the body, EVs report on the internal cellular conditions across all tissue types. Their presence in readily accessible biofluids makes the potential of EV biosensing highly attractive as a noninvasive diagnostic platform via liquid biopsies. However, their small size (50-250 nm), inherent heterogeneity, and the complexity of the native biofluids introduce challenges for effective characterization, thus, limiting their clinical utility. This has led to a surge in the development of various novel EV biosensing techniques, with capabilities beyond those of conventional methods that have been directly transferred from cell biology. In this review, key detection principles used for EV biosensing are summarized, with a focus on some of the most recent and fundamental developments in the field over the last 5 years. This article is categorized under: Diagnostic Tools > Biosensing Diagnostic Tools > In Vitro Nanoparticle-Based Sensing.
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Técnicas Biossensoriais , Exossomos , Vesículas Extracelulares , Humanos , Exossomos/metabolismo , Vesículas Extracelulares/metabolismo , BiomarcadoresRESUMO
The quartz crystal microbalance (QCM) measurement technique is utilized in a broad variety of scientific fields and applications, where surface and interfacial processes are relevant. However, the costs of purchasing QCMs is typically high, which has limited its employment in education as well as by scientists in developing countries. In this article, we present an open-source QCM, built on the OpenQCM project, and using an impedance-based measurement technique (QCM-I), which can be built for <200 euro. Our QCM allows for simultaneous monitoring of the frequency change and dissipation, such that both soft and rigid materials can be characterized. In addition, our QCM measurements can be combined with simultaneous electrochemical measurement techniques (EQCM-I). We demonstrate the validity of our system by characterizing the electrodeposition of a rigid metallic film (Cu) and by the electropolymerization of aniline. Finally, we discuss potential improvements to our system.
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Rechargeable batteries employing aqueous electrolytes are more reliable and cost-effective as well as possess high ionic conductivity compared to the flammable organic electrolyte solutions. Among these types of batteries, aqueous batteries with multivalent ions attract more attention in terms of providing high energy density. Herein, electrochemical behavior of an organic electrode based on a highly aromatic polymer containing 2,3-diaminophenazine repeating unit, namely poly(ortho-phenylenediamine) (PoPD), is tested in two different multivalent ions (Zn2+ and Al3+) containing aqueous electrolytes, that is, in zinc sulfate and aluminum chloride solutions. PoPD is synthesized via electropolymerization, and its ion transport and storage mechanism are comprehensively investigated by structural and electrochemical analyses. The electrochemical quartz crystal microbalance, time-dependent Fourier transform infrared, and electrochemical impedance spectroscopy analyses as well as ex situ X-ray diffraction observations established that along with the Zn2+ or Al3+ ions, reversible proton insertion/extraction also takes place. Contrary to the most of the organic electrodes that requires the use of conductive carbon additives, the electrodeposited PoPD electrode is intrinsically electrically conductive enough, resulting in a binder and additive free electrode assembly. In addition, its discharge products do not dissolve in aqueous medium. As a whole, the resulting PoPD electrode delivers excellent rate performances with prolonged cycle life in which discharge capacities of â¼110 mAh g-1 in 0.25 M AlCl3 and â¼93 mAh g-1 in 1 M ZnSO4 aqueous electrolyte after 1000 cycles at a current density of 5C have been achieved.
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Formation and evolution of the microscopic solid electrolyte interphase (SEI) at the Mg electrolyte/electrode interface are less reported and need to be completely understood to overcome the compatibility challenges at the Mg anode-electrolyte. In this paper, SEI evolution at the Mg electrolyte/electrode interface is investigated via an in situ electrochemical quartz crystal microbalance with dissipation mode (EQCM-D), electrochemical impedance spectroscopy (EIS), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), and Fourier transform infrared spectrometry (FTIR). Results reveal remarkably different interfacial evolutions for the two Mg electrolyte systems that are studied, a non-halogen Mg(TFSI)2 electrolyte in THF with DMA as a cosolvent (nhMg-DMA electrolyte) versus a halogen-containing all-phenyl complex (APC) electrolyte. The nhMg-DMA electrolyte reports a minuscule SEI formation along with a significant Coulomb loss at the initial electrochemical cycles owing to an electrolyte reconstruction process. Interestingly, a more complicated SEI growth is observed at the later electrochemical cycles accompanied by an improved reversible Mg deposition attributed to the newly formed coordination environment with Mg2+ and ultimately leads to a more homogeneous morphology for the electrochemically deposited Mg0, which maintains a MgF2-rich interface. In contrast, the APC electrolyte shows an extensive SEI formation at its initial electrochemical cycles, followed by a SEI dissolution process upon electrochemical cycling accompanied by an improved coulombic efficiency with trace water and chloride species removed. Therefore, it leads to SEI stabilization progression upon further electrochemical cycling, resulting in elevated charge transport kinetics and superior purity of the electrochemically deposited Mg0. These outstanding findings augment the understanding of the SEI formation and evolution on the Mg interface and pave a way for a future Mg-ion battery design.
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Electrochemical quartz crystal microbalance (EQCM) and AC-electrogravimetry methods were employed to study ion dynamics in carbon nanotube base electrodes in NaCl aqueous electrolyte. Two types of carbon nanotubes, Double Wall Carbon Nanotube (DWCNT) and Multi Wall Carbon Nanotube (MWCNT), were chosen due to their variable morphology of pores and structure properties. The effect of pore morphology/structure on the capacitive charge storage mechanisms demonstrated that DWCNT base electrodes are the best candidates for energy storage applications in terms of current variation and specific surface area. Furthermore, the mass change obtained via EQCM showed that DWCNT films is 1.5 times greater than MWCNT films in the same potential range. In this way, the permselectivity of DWCNT films showed cation exchange preference at cathode potentials while MWCNT films showed anion exchange preference at anode potentials. The relative concentration obtained from AC-electrogravimetry confirm that DWCNT base electrodes are the best candidates for charge storage capacity electrodes, since they can accommodate higher concentration of charged species than MWCNT base electrodes.
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The anion exchange and water dynamics of a phosphonium-based alkaline anion exchange membrane (AAEM) during the methanol oxidation process have been studied with the electrochemical quartz crystal microbalance (EQCM). The viscoelastic effects of the phosphonium-based AAEM in water and the optimal film thickness for EQCM analysis were identified by acoustic impedance analysis. The phosphonium-based AAEM exhibited stronger mechanical toughness in water when compared to a quaternary-ammonium-based membrane that was studied previously. From the simultaneous measurement of the electrochemical response and the frequency changes of the quartz crystal oscillator, water ingress/egress to/from the AAEM film was found to accompany the hydrogen adsorption/desorption, Pt oxidation process, and methanol oxidation process. The in situ study of AAEM films helps illustrate the critical role that water transport plays in electrochemical processes during the operation of anion exchange membrane fuel cells. The generated CO32- and HCOO-, during methanol oxidation, were absorbed into the AAEM film, replacing the OH- in the film, as shown by the decrease in frequency after one potential cycle. The exchange of OH- by CO32- and HCOO- was found to be reversible. These results provide insights into the anion exchange processes in membranes and emphasize the importance of characterizing the hydrated membranes under electrochemical conditions.
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HYPOTHESIS: Dimensionally stable electroactive films displaying spatially addressed redox sites is still a challenging goal due to gel-like structure. Polyelectrolyte and surfactants can yield highly mesostructured films using simple buildup strategies as layer-by-layer. The use of redox modified surfactants is expected to introduce order and an electroactive response in thin films. EXPERIMENTS: The assembly of polyacrylic acid and different combinations of redox-modified and unmodified hexadecyltrimethylammonium bromide yields highly structured and electroactive thin films. The growth, viscoelastic properties, mass, and electron transport of these films were studied by combining electrochemical and quartz crystal balance with dissipation experiments. FINDINGS: Our results show that the films are highly rigid and poorly hydrated. The mass and charge transport reveal that the ingress (egress) of the counter ions during the electrochemical oxidation (reduction) is accompanied with a small amount of water, which is close to their hydration sphere. Thus, the generated mesostructured films present an efficient charge transport with negligible changes in their structures during the electron transfer process. The control over the meso-organization and its stability represents a promising tool in the construction of devices where the vectorial transfer of electrons, or ions, is required.
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Microliter volumes are used in electrochemical detection and preconcentration of radionuclides to reduce the dose received by researchers and equipment. Unfortunately, there is a lack of analysis of radionuclides with coupled electrochemical techniques and microliter volume reactors. The goals of this work are 1) to develop a miniaturized micro-electrochemical quartz crystal microbalance (µeQCM) reactor for use in small volume (50-200 µL) electrogravimetric experiments and 2) to use this reactor to characterize the preconcentration of neptunium on carbon electrodes via electroprecipitation. We successfully deposited neptunium in the new µeQCM reactor and verified its operation. We found that preconcentration of neptunium on carbon coated electrodes was possible by chronoamperometry at -1.6 VAg/AgCl. The mass shift of the resulting precipitate was indicative of the amount of neptunium on the electrode, although the correlation between the mass increase and activity of the preconcentrated material was not linear. Neptunium precipitate reduced electron transfer to the solution as evidenced by the increase in charge transfer resistance compared to bare electrodes.
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Electroprecipitation can be used to preconcentrate lanthanum on carbon electrode surfaces. The use of complexing ligands is expected to improve the electroprecipitation of lanthanum by protecting La ions in solution from the alkaline region near the electrode surface. However, the electroprecipitation mechanism of La in the presence of a complexing ligand is not known. The goal of this work is to 1) determine the effect of the complexing ligand, α-hydroxy isobutyric acid (HIBA), on the electroprecipitation of La onto the gold electrodes, and 2) identify the changes in the mechanism of accumulation when preconcentrating in the presence of HIBA. We used an electrochemical quartz crystal microbalance (eQCM) and needle type pH microelectrodes to determine pH near the electrode surface in combination with cyclic voltammetry to understand the electroprecipitation mechanism. We used the bi-dentate ligand HIBA as a ligand and found that lanthanum electroprecipitation is hindered in the presence of HIBA. The presence of HIBA also delayed the onset of film formation during a cyclic voltammetric experiment by ~100 mV compared to experiments performed without HIBA. The shift in onset potential is attributed to the buffering action of HIBA (pKa = 3.7) since the shift is not present in subsequent scans. The precipitated film was characterized by scanning electron microscopy, X-ray photoelectron spectrometry, and Auger nanoprobe spectrometry. While we found that La(OH)3 was the predominant chemical state of the film on electrodes in the absence of HIBA, La2O3 was found for films created in the presence of HIBA. Our finding demonstrates that La(OH)3 can be electrodeposited at room temperature.
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One of the intended applications for the modification of ion exchange membranes with polyaniline (PAni) is to use it as a matrix to include chemical species that confer a special property such as resistance to fouling or ion selectivity. In particular, the inclusion of polyelectrolyte molecules into the PAni matrix appears to be the way to modulate these properties of selective membranes. Therefore, it must be clearly understood how the polyelectrolyte is incorporated into the matrix of polyaniline. Among the results obtained in this paper using poly(sodium 4-styrenesulfonate) (PSS) and an electrochemical quartz crystal microbalance, the amount of polyelectrolyte incorporated into PAni is found to be proportional to the PSS concentration in solution if its value is between 0 and 20 mM, while it reaches a maximum value when the PSS in solution is greater than 20 mM. When the anion exchange membranes are modified with these composite deposits, the transport number of chloride was found to decrease progressively (when the PSS concentration in solution is between 0 and 20 mM) to reach a practically constant value when a concentration of PSS greater than 20 mM was used.
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Studying the electrogravimetric behavior of Mg/Fe-layered double hydroxide (LDH) nanoparticles with an electrochemical quartz crystal microbalance demonstrates its pseudocapacitance properties of mix cation and anion exchanger. The electrochemical control of the oxidation state of iron constituting the layered sheets allowed anion intercalation/deintercalation into the LDH interlayer space. Concomitantly, in agreement with the pH of zero point of net charge of the Mg/Fe-LDH, the interfacial pH increase via catalyzed hydrogen evolution reaction allows cation electroadsorption onto the external surfaces of the nanoplatelets.
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The paper presents three datasets obtained by electrochemical quartz microbalance technique which was applied to studies of conducting polymer film in contact with non-aqueous electrolyte solution. The first dataset describes the calibration procedure of gold-coated quartz crystal, immersed in acetonitrile silver ion-containing electrolyte, by means of silver layer electrodeposition. On the basis of experimentally measured dependence of the resonance frequency on the varying electrode mass in the course of electrochemical silver deposition/dissolution, the calibration coefficient was found to be equal to 13.6 ng/Hz. The second dataset has been collected when thus calibrated EQCM cell was used for determination of the mass change due to the polypyrrole film growth during anodic oxidation of pyrrole monomer from its acetonitrile solution. Its treatment reveals the proportionality between the mass change and the charge spent for pyrrole electrooxidation, the proportionality coefficient being 53.5 g per mole of electrons. The third dataset contains EQCM measurement data during repetitive charge-discharge treatment of the deposited polypyrrole film (cyclic voltammetry, CV) in monomer-free electrolyte. Collected data shows that continuous cycling of the polymer film leads to progressive increase of the cation-exchange contribution to the total ion flux which maintains the film's electroneutrality during variation of its redox state. These findings might be useful both for a qualitative consideration of the cycling stability of polypyrrole in non-aqueous medium and for a quantitative mathematical modelling of polypyrrole electropolymerization and its redox transformations.
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Uric acid-imprinted polypyrrole-based (MIP(UA)-Ppy) electrochemical quartz crystal microbalance sensor (EQCM) was developed. Experiments and theoretical calculations were focused on molecular interactions between uric acid molecule and: i) polypyrrole imprinted by uric acid (MIP(UA)-Ppy) ii) polypyrrole film without any molecular imprints (NIP-Ppy). Resonant frequency differences during electrochemical deposition of MIP(UA)-Ppy and NIP-Ppy films were observed and were attributed to the phenomenon of molecule capture within formed Ppy matrix. EQCM-resonators modified by MIP-Ppy showed the following advantages: selectivity, qualitative response, cost-effectiveness, and simple procedure. The selectivity of MIP(UA)-Ppy was tested by the replacement of uric acid in the PBS solution with several different concentrations of caffeine and glucose. Langmuir isotherm based molecular adsorption model was applied to evaluate the interaction of MIP(UA)-Ppy with uric acid. From experimental results calculated the standard Gibbs free energy of association (ΔGa) of uric acid with MIP(UA)-Ppy is -16.4 ± 2.05 kJ/mol and with NIP-Ppy is -13.3 ± 8.56 kJ/mol ΔG values illustrate that the formation of uric acid complex with MIP(UA)-Ppy is thermodynamically more favourable than that for complexation with NIP-Ppy.
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In this work the impact of molecular inter-linker size on gold nanoparticle (AuNP) mono-/multilayer structural properties, density and homogeneity has been investigated. These characteristics are of great importance for functional binding of biomolecules. Positively charged high or low molecular weight inter-linkers, poly-L-lysine (PLL) or N-(6-mercapto)hexylpyridinium (MHP), were used to attach negatively charged AuNPs on a planar gold surface as well as to further interlink into a multilayer structure via layer-by-layer deposition. The inter-particle interaction within the assembled AuNP films was adjusted by the ionic strength in the AuNPs dispersions. The AuNP layer density and structural/viscoelastic properties were evaluated by the quartz crystal microbalance with dissipation (QCM-D) technique. The validity of the commercial Voigt model, specifically developed for quantitative QCM-D data analysis of homogeneous viscoelastic films, was evaluated by a model independent analysis when comparing the assembled AuNP films with a homogeneous layer of a mucin from bovine submaxillary glands. Both AuNP mono- and multilayers, attached/interlinked via long flexible PLL molecules assembled to denser and more soft/viscous structures compared to those interlinked by short MHP compounds. Thus, PLL-interlinked AuNP mono-/multilayer structures were further investigated as a platform for laccase enzyme functional adsorption via qualitative assessment of bioelectrochemical characteristics of the enzyme.
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Ouro/química , Nanopartículas Metálicas/química , Mucinas/química , Polilisina/química , Compostos de Piridínio/química , Animais , Sítios de Ligação , Bovinos , Físico-Química , Peso Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
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 ClO4- 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, LuPc2. 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.