Highly sensitive multicomponent materials designed for the recognition of hazardous compounds request control over interfacial chemistry. The latter is a key parameter in the construction of the sensing (macro) molecular architectures. In this work, multi-walled carbon nanotubes (CNTs) were deposited on diazonium-modified, flexible indium tin oxide (ITO) electrodes prior to the electropolymerization of pyrrole. This three-step process, including diazonium electroreduction, the deposition of CNTs and electropolymerization, provided adhesively-bonded, polypyrrole-wrapped CNT composite coatings on aminophenyl-modified flexible ITO sheets. The aminophenyl (AP) groups were attached to ITO by electroreduction of the in-situ generated aminobenzenediazonium compound in aqueous, acidic medium. For the first time, polypyrrole (PPy) was electrodeposited in the presence of both benzenesulfonic acid (dopant) and ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA), which acts as a chelator. The flexible electrodes were characterized by XPS, Raman and scanning electron microscopy (SEM), which provided strong supporting evidence for the wrapping of CNTs by the electrodeposited PPy. Indeed, the CNT average diameter increased from 18 ± 2.6 nm to 27 ± 4.8, 35.6 ± 5.9 and 175 ± 20.1 after 1, 5 and 10 of electropolymerization of pyrrole, respectively. The PPy/CNT/NH₂-ITO films generated by this strategy exhibit significantly improved stability and higher conductivity compared to a similar PPy coating without any embedded CNTs, as assessed by from electrochemical impedance spectroscopy measurements. The potentiometric response was linear in the 10⁻⁸–3 × 10⁻⁷ mol L⁻¹ Pb(II) concentration range, and the detection limit was 2.9 × 10⁻⁹ mol L⁻¹ at S/N = 3. The EGTA was found to drastically improve selectivity for Pb(II) over Cu(II). To account for this improvement, the density functional theory (DFT) was employed to calculate the EGTA–metal ion interaction energy, which was found to be −374.6 and −116.4 kJ/mol for Pb(II) and Cu(II), respectively, considering solvation effects. This work demonstrates the power of a subtle combination of diazonium coupling agent, CNTs, chelators and conductive polymers to design high-performance electrochemical sensors for environmental applications.

This review critically summarizes the knowledge of imprinted polymer-based electrochemical sensors for the detection of pesticides, metal ions and waterborne pathogenic bacteria, focusing on the last five years. MIP-based electrochemical sensors exhibit low limits of detection (LOD), high selectivity, high sensitivity and low cost. We put the emphasis on the design of imprinted polymers and their composites and coatings by radical polymerization, oxidative polymerization of conjugated monomers or sol-gel chemistry. Whilst most imprinted polymers are used in conjunction with differential pulse or square wave voltammetry for sensing organics and metal ions, electrochemical impedance spectroscopy (EIS) appears as the chief technique for detecting bacteria or their corresponding proteins. Interestingly, bacteria could also be probed via their quorum sensing signaling molecules or flagella proteins. If much has been developed in the past decade with glassy carbon or gold electrodes, it is clear that carbon paste electrodes of imprinted polymers are more and more investigated due to their versatility. Shortlisted case studies were critically reviewed and discussed; clearly, a plethora of tricky strategies of designing selective electrochemical sensors are offered to “Imprinters”. We anticipate that this review will be of interest to experts and newcomers in the field who are paying time and effort combining electrochemical sensors with MIP technology.

Adhesion of polymers to surfaces is of the upmost importance in timely applications such as protective coatings, biomaterials, sensors, new power sources and soft electronics. In this context, this work examines the role of molecular interactions in the adhesion of polypyrrole thin films to flexible Indium Tin Oxide (ITO) electrodes grafted with aryl layers from various diazonium salts, namely 4-carboxybenzenediazonium (ITO-CO₂H), 4-sulfonicbenzenediazonium (ITO-SO₃H), 4-N,N-dimethylbenzenediazonium (ITO-N(CH₃)₂), 4-aminobenzenediazonium (ITO-NH₂), 4-cyanobenzenediazonium (ITO-CN) and 4-N-phenylbenzenediazonium (ITO-NHPh). It was demonstrated that PPy thin layers were adherent to all aryl-modified surfaces, whereas adhesive failure was noted for bare ITO following simple solvent washing or sonication. Adhesion of polypyrrole was investigated in terms of hydrophilic/hydrophobic character of the underlying aryl layer as probed by contact angle measurements. It was found that sulfonic acid-doped polypyrrole (PPy-BSA) thin films were preferably deposited on the most hydrophobic surfaces. More importantly, the redox properties and electrochemical impedance of PPy were closely related to the hydrophobic character of the aryl layers. This work demonstrates that diazonium compounds are unique molecular glues for conductive polymers and permit to tune their interfacial properties. With robust, diazonium-based architectured interfaces, one can design high performance materials for e.g., sensors, printed soft electronics and flexible thermoelectrics.

In recent years, porous carbon-based materials have demonstrated their potential as electrode materials, particularly as supercapacitors for energy storage. The specific capacitance of a carbon-based material is strongly influenced by its porosity. Herein, activated biochar (BCA) from millet was prepared using ZnCl₂ as an activator at temperatures of 400, 700, and 900 °C. Activation was achieved through wet and dry impregnation of millet bran powder particles. The porosity of BCAs was assessed by determining the iodine and methylene blue numbers (N_I and N_MB, respectively), which provide information on microporosity and mesoporosity, respectively. Characterization of the BCAs was carried out using Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and cyclic voltammetry. The data show that the BCA prepared at 700 °C following dry impregnation, P700(p), has the highest N_I and the highest geometric mean value ($ñ=\sqrt{N_I\times N_{MB}}$), a descriptor we introduce to characterize the overall porosity of the biochars. P700(p) biochar exhibited remarkable electrochemical properties and a maximum specific capacitance of 440 F g⁻¹ at a current density of 0.5 A g⁻¹, in the three-electrode configuration. This value drops to 110 F g⁻¹, in the two-electrode configuration. The high specific capacitance is not due to ZnO, but essentially to the textural properties of the biochar (represented by ñ descriptor), and possibly but to a lesser extent to small amounts of Zn₂SiO₄ left over in the biochar. Moreover, the capacitance retention increases with cycling, up to 130%, thus suggesting electrochemical activation of the biochar during the galvanostatic charge-discharge process. To sum up, the combination of pyrolysis temperature and the method of impregnation permitted to obtaining of a porous biochar with excellent electrochemical properties, meeting the requirements of supercapacitors and batteries.