Remote detection of gaseous ammonia using the near infrared transmission properties of polyaniline

Ammonia is a key component of many industrial processes where it is used in very high concentrations. The applications range from high quality steel production and fertiliser manufacture, to the refrigeration of food products and ice ring leisure facilities. Ammonia escapes have been identified as a large and serious problem by both government and industry. Simple and robust ammonia sensors for remote monitoring applications remain an area of continuous interest.

Polyaniline is a conducting polymer used in ‘electronic nose’ instrumentation and has been shown to be electronically sensitive to ammonia. In this paper, we report on the application of electrochemically-prepared polyaniline films for the measurement of gaseous ammonia at 1300 nm. This wavelength corresponds to a region of high optical transmission for optical fibres and is also compatible with telecom devices and technology. A simple and robust measurement system based on a standard telecom 1300 nm LED is described and remote sensing using 100 m of duplex multimode fibre is demonstrated.

Typically, the transmission of the polyaniline films at 1300 nm increases by approximately 1% in response to gaseous ammonia levels of 6 ppm in 50% RH. This represents the lower limit of detection in our study. Although initially the sensors react to the presence of ammonia very fast it takes over several hours for the output to reach the equilibrium. Clearly this is impractical however, it is possible to differentiate between different concentrations of ammonia by taking two readings at fixed intervals. A calibration curve for the sensors was obtained using two readings 15 s apart. The response time of the polyanaline films was found to be insensitive to the humidity variations in the range of 30–70% RH, however, over the 10–90% variation the changes were of the same order of magnitude as those induced by 6 ppm of ammonia.     

The effect of transition metal ions (M2+=Mn2+, Ni2+, Co2+, Cu2+) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells

The effect of transition metal ions(M~(2+)=Mn~(2+),Ni~(2+),Co~(2+),Cu~(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I~-/I_3~-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn~(2+),Ni~(2+),Co~(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu~(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu~(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni~(2+), PANI-Co~(2+),PANI-Mn~(2+) and PANI-Cu~(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M~(2+)=Mn~(2+),Ni~(2+),Co~(2+),Cu~(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.     

Polyaniline sensitized Pt@TiO2 for visible-light-driven H2 generation

Polyaniline is a typical conducting polymer with high migration electron rate, good stability, eco-friendly properties, and high absorption coefficients for visible light. In the present study, polyaniline decorated Pt@TiO₂ for visible light-driven H₂ generation is reported for the first time. The above-mentioned nanocomposite is prepared through a simple oxidative-polymerization and characterized by infrared spectroscopy, transmission electron microscopy, X–ray diffraction, thermogravimetric analysis, and ultraviolet–visible diffuse reflectance spectra. Polyaniline modification improves the absorption of the nanocomposite in visible light region via a photosensitization effect similar to dye–sensitization but does not influence the crystal structure and size of Pt@TiO₂. The polyaniline modified Pt@TiO₂ exhibits a remarkable visible light activity (61.8 μmol h⁻¹ g⁻¹) and good stability for H₂ generation (with an average apparent quantum yield of 10.1%) with thioglycolic acid as an electron donor. This work provides new insights into using conducting polymers, including polyaniline, as a sensitizer to modify Pt@TiO₂ for visible-light hydrogen generation.     

Conducting polymers inducing catalysis: Enhanced formic acid electro-oxidation at a Pt/polyaniline nanocatalyst

Research is moving rapidly to sustain convenient energy resources fulfilling the global climate legislations. Herein, a novel catalyst of platinum nanoparticles (PtNPs) dispersed onto polyaniline (PANi) is recommended for formic acid electro-oxidation (FAO); the fundamental anodic reaction in direct formic acid fuel cells (DFAFCs). The catalyst's preparation scheme allows a sequential electrodeposition of fibril PANi and spherical PtNPs (ca. 65 nm in size) on a glassy carbon (GC) substrate and permits a precise control over the deposition sequence and loading. Interestingly, incorporation of PANi into the catalyst's ingredients can significantly (ca. 16 times) improve the catalytic activity of the catalyst towards FAO by shifting the mechanism towards the desirable dehydrogenation pathway and mitigating the undesirable poisoning dehydration pathway. The catalytic efficiency is tuned by manipulating the deposition order and loading of different catalyst's ingredients. Several techniques are employed to confirm the successful deposition of the catalyst and to evaluate its morphology, composition and crystal structure. While PtNPs are essential for FA adsorption, PANi improves the dispersion of PtNPs and mediates FAO to facilitate the charge transfer and mitigate CO poisoning. A promising catalytic stability is achieved in a long continuous (150 CVs) electrolysis experiment.     

Electrochemical synthesis of polymer based on 4-(2-furyl) benzenamine: Electrochemical properties,characterization and applications

4-(2-Furyl) benzenamine (FBA), was successfully synthesized by a simple method including substitution of furan on p-nitroaniline followed by reduction of nitro group. Structure of the synthesized monomer was verified using IR, ¹H NMR and GC–MS techniques. Corresponding poly(4-(2-furyl) benzenamine) (PFBA) was electrochemically synthesized in acidic aqueous and organic solutions by cyclic potential sweep method. Characterization of the resulting polymer was performed by cyclic voltammetry (CV), IR, UV–vis spectroscopy, and scanning electron microscopy (SEM). Effect of solvent on the electroactivity of the polymer modified electrode was investigated. The HOMO, LUMO levels and band gap energies of the doped and undoped form of the PFBA were calculated using UV–vis and CV data. The electrochromic properties and corrosion behavior of PFBA were studied. The electrochromic properties of the copolymer film, electrochemically coated on transparent conductive oxide, corroborate multi-color electrochromic behavior of the polymer whenever the applied potential was switched from reducing (yellow) to oxidizing status (green). The FBA polymer was found to exhibit enhanced corrosion protection effect on steel electrode in comparison with corresponding polyaniline (PANI) and polyfuran (PFu) homopolymers based on series of electrochemical measurements in 3.5 wt% NaCl electrolyte solutions.     

Green synthesis of polyaniline/clay/iron ternary nanocomposite by the one step solid state intercalation method

The incorporation of two or more active components into clay layered structure with uniform distribution is expected to facilitate wider applications of the material. In this study, nanocomposite composed of clay, polyaniline and iron nanoparticles was synthesized by a facile and environmentally friendly strategy for the first time. Local smectite clay from Tunisia was exchanged with Fe³⁺ then it was subjected to fine grinding with anilinium chloride using mortar grinder and the mixture has been allowed for ageing at ambient air until the change of color to dark green. Both interlayer Fe³⁺ cations and atmospheric oxygen act as oxidant for aniline polymerization. In addition, the presence of interlayer Fe³⁺ and Fe²⁺ cations (the result of the reduction of Fe³⁺) at the same time favors the formation of iron nanoparticles phase. Electrical and dielectric properties have studied using spectroscopy impedance. The ac conduction shows a regime of constant dc conductivity at low frequencies and a crossover to a frequency-dependent regime of the type Aω^S at high frequencies. The material shows high dielectric constant, resulting from the presence of iron nanoparticles, indicating its improved ability to store electric energy and to be used as capacitor.     

Simultaneous degradation of RhB and reduction of Cr(VI) by MIL-53(Fe)/Polyaniline (PANI) with the mediation of organic acid

MIL-53(Fe)/polyaniline (PANI) composite was prepared by in situ depositing PANI on the surface of MIL-53(Fe) and their catalytic performances on the simultaneous removal of RhB and Cr(VI) were investigated. The elimination efficiency of both RhB and Cr(VI) reached more than 98% under pH=2 where hydrochloric acid and citric acid were used to adjust the pH. The results indicated that MIL-53(Fe)/PANI revealed an obvious pH response to the degradation of RhB, while citric acid promoted the Cr(VI) photoreduction. UV-Vis spectra, EIS, and photocurrent response experiments showed that MIL-53(Fe)/PANI had a better light response and carrier migration ability than MIL-53(Fe). The transient absorption spectra also exhibited that the lifetimes of photo-generated carriers were prolonged after the conductive polymer deposition on the MIL-53(Fe) surface. Scavenger experiments demonstrated that the main active species were ·O₂^- and OH. Combined with activity evaluation results, and the possible photocatalytic mechanism of MIL-53(Fe)/PANI on RhB oxidation and Cr(VI) reduction was proposed. The addition of conductive polymer can effectively improve the light response of the catalyst under acidic conditions, and meanwhile citric acid also provided a new mediation for the synergistic degradation of multiple pollutants. Good activity and stability of the catalysts made the scale-up purification of acid water feasible under UV-Vis light.     

Preparation and performance of PANI–PVA composite film doped with HCl

The polyaniline (PANI)–poly (vinyl alcohol) (PVA) composite film doped with HCl was prepared by adopting PVA as matrix. Effects of PVA content and film drying temperature on properties of HCl–PANI–PVA composite film were studied. A comparison was made for tensile strength, elasticity, conductivity and thermal stability of PVA, HCl–PANI or HCl–PANI–PVA. PVA film presented the highest tensile strength and elasticity (150.8?MPa and 300.0%), but its conductivity was the lowest. The conductivity of HCl–PANI–PVA was the highest (1500?S?m^?1), and tensile strength and elasticity of HCl–PANI–PVA were higher than those of HCl–PANI. The order of their thermal stability is PVA?>?HCl–PANI?>?HCl–PANI–PVA before 260°C, and the order of their thermal stability is HCl–PANI?>?HCl–PANI–PVA?>?PVA after 260°C. At the same time, the structure and conductive mechanism of composite materials were characterised and analysed through infrared and scanning electron microscopy (SEM).     

Synthesis of graphene/vitamin C template-controlled polyaniline nanotubes composite for high performance supercapacitor electrode

A graphene nanosheet/polyaniline nanotube (GPNT) composite is prepared for the first time by in-situ chemical oxidative polymerization of aniline using vitamin C as a structure directing agent. The vitamin C molecules lead to the synthesis of polyaniline (PANI) nanotubes through the development of rod-like assembly by H-bonding in an aqueous medium. The initially synthesized graphene oxide/polyaniline nanotubes composite is reduced to graphene using hydrazine monohydrate followed by re-oxidation and protonation of the PANI to produce the GPNT nanocomposite. This novel composite showed a high specific capacitance of 534.37 F/g and an excellent energy density of 74.27 Wh/kg at a constant current of 0.5 mA. Besides, the GPNT composite exhibited excellent cycle life with 91.4% specific capacitance retained after 500 charge-discharge cycles. The excellent performance is due to the synergistic combination of graphene which provides good electrical conductivity and mechanical stability, and PANI nanofiber which deals with good redox activity.