The electrochemical polymerization of polyaniline (PANI) was studied using correlative measurements of electrochemistry and UV–vis spectroscopy, i.e., spectroelectrochemistry. The electropolymerization of PANI was performed in an acidic medium (1 M HCl) containing 0.1 M aniline with cyclic voltammetry (CV) in a potential window from −0.3 to 1 V and a 50 mV s−1 scan rate. At the same time, UV–vis absorbance spectra in the wavelength range from 200 to 900 nm were measured for every 10 mV change in the CV. The CV results show the oxidation of the monomer at a high positive potential (0.9 V vs Ag), the continuous growth of the PANI film and the transformation between the three best-known forms of PANI redox in the potential range between −0.3 V and 1 V. In parallel, the spectroscopic study confirmed the formation of PANI oxidation. The spectroscopic results showed the formation of the final conductive PANI product (emeraldine salt) due to the absorbance of the formed charge carriers (polarons, bipolarons) during the polymerization. The correlative electrochemical/spectroscopy study gave an additional dimension to the PANI polymerization mechanism, where not only was the oxidation the lead type of reaction, but the reduction was also found to play an important role.

Polyaniline (PANI) is a conducting polymer, widely used in gas-sensing applications. Due to its classification as a semiconductor, PANI is also used to detect reducing ammonia gas (NH3), which is a well-known and studied topic. However, easier, cheaper and more straightforward procedures for sensor fabrication are still the subject of much research. In the presented work, we describe a novel, more controllable, synthesis approach to creating NH3 PANI-based receptor elements. The PANI was electrochemically deposited via cyclic voltammetry (CV) on screen-printed electrodes (SPEs). The morphology, composition and surface of the deposited PANI layer on the Au electrode were characterised with electron microscopy, Fourier-transform infrared spectroscopy and profilometry. Prior to the gas-chamber measurement, the SPE was suitably modified by Au sputtering the individual connections between the three-electrode system, thus showing a feasible way of converting a conventional three-electrode electrochemical SPE system into a two-electrode NH3-gas detecting system. The feasibility of the gas measurements’ characterisation was improved using the gas analyser. The gas-sensing ability of the PANI-Au-SPE was studied in the range 32–1100 ppb of NH3, and the sensor performed well in terms of repeatability, reproducibility and sensitivity.

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