Emeraldine Salt Research Articles

Molecular Dynamics Simulation Study on the Structural and Thermodynamic Analysis of Oxidized and Unoxidized Forms of Polyaniline.

The conducting polymer polyaniline (PANI) has shown significant interest for the development of electrified membranes (EMs) with superior antifouling characteristics. However, the blending and doping of PANI with other polymers and nanomaterials highly influence the properties of the membrane surface. PANI exists in two forms: oxidized, known as emeraldine salt (ES), and unoxidized, referred to as emeraldine base (EB). Therefore, understanding the different forms of PANI and the variations between the oxidized and unoxidized forms along the length of the polymer chain is intriguing. In this paper, we present the design of a novel copolymer consisting of EB and ES monomers with varying charge densities and different segmental arrangements. We present various intra- and intermolecular structural properties of the PANI chains using all-atom molecular dynamics (MD) simulations. Herein, we present a detailed conformational free energy analysis to understand the conformational transitions of the PANI chains. Our results show increased radius of gyration (Rg) values with increased charge density. Furthermore, we also present the H-bonding, free energy analysis, reduced density gradient (RDG), and solvent-accessible surface area (SASA) values for the observed conformational transitions of PANI. Therefore, these observations are crucial in understanding the complex behavior of chains for designing target-specific polymeric materials.

Enhancement of Conductivity and Productivity of Polyaniline Emeraldine Salt Using Diverse Treatment Solutions

Enhancement of Conductivity and Productivity of Polyaniline Emeraldine Salt Using Diverse Treatment Solutions

Thin-Film Nanofiltration membrane of polyaniline Decorated graphene oxide via In-Situ polymerization for ion separation

Ion separation membranes composed of graphene oxide (GO) and polyaniline (PANI) have been successfully synthesized using the in-situ polymerization method. Various PANI species, including emeraldine base (EB PANI), emeraldine salt (ES PANI), and pernigraniline base (PB PANI), were incorporated into the GO matrix and subsequently evaluated. The integration of PANI species into the GO matrix resulted in an increased interlayer distance, enhanced surface positive charge, and greater membrane hydrophobicity. Additionally, incorporating PANI improved the membrane’s mechanical stability and resilience across a range of environmental pH levels. The membrane’s ion separation performance was assessed using feed ions such as Na+, Li+, Mg2+, and Al3+. The PANI GO-ES membrane exhibited the highest separation efficiency for Na+/Al3+ ions, achieving an ideal selectivity value of 76.23 ± 1.25. Conversely, ions with similar sizes and charges demonstrated lower selectivity. The GO-ES PANI membrane also showed superior performance stability compared to other membranes, maintaining a consistent ideal selectivity value for up to 20 h. Overall, the results indicate that the GO-ES PANI membrane offers the best ion separation performance and is recommended for practical applications.

Direct Imaging of Charge/Dopant Distribution in PANI/PSS Thin Films Using Advanced Frequency Modulation Electrostatic Force Microscopy.

This paper presents a detailed study that maps the surface charges and dopant distribution on the electropolymerized thin film of polyaniline-poly(styrenesulfonate) (PANI/PSS). The focus is on two distinct states of PANI/PSS: the fully doped emeraldine salt (ES/PSS) and the dedoped emeraldine base (EB/PSS). This investigation utilizes advanced frequency modulation electrostatic force microscopy (FM-EFM) and atomic force microscopy (AFM). The polymer film comprises polymer grains, and FM-EFM data suggest a non-uniform distribution of dopants on the grain surface, with a higher doped periphery than the core. Quantifying the charge at the periphery and core of ES/PSS and EB/PSS grains provides unique insight into the charge distribution within the polymer film. The charge density is estimated to be 10 times higher in the periphery region (∼120 μC/cm2) than in the core region (∼11 μC/cm2) and 100 times higher than EB/PSS (∼0.8 μC/cm2). We have directly observed the morphological changes of PANI/PSS from the ES/PSS state to the EB/PSS state using the AFM topographic profile. These findings provide a better understanding of the behavior of the charge/dopant distribution on the surface of the polymer films and pave the way for further research and development of PANI/PSS-based electronic devices.

Charge Photogeneration and Transfer in Polyaniline/Titanium Dioxide Heterostructure

The photoinduction process in a p-n heterogeneous structure should be in correlation with the electronic properties of its semiconductor components. Based on that assumption, a double layer made of polyaniline (PANi) and titanium dioxide (TiO2) on glass substrate is used to investigate the charge photogenerated and transferred in the structure. The PANi layer is made by in situ polymerization of aniline in HCl acidic aqueous medium, while the TiO2 layer is made by thermolysis of TiCl3 dilute solution. It has been found that the PANi/TiO2 double layer is a composition of a PANi emeraldine salt layer (p-type semiconductor) covered by a TiO2 rutile layer (n-type conductor), creating a p-n heterogeneous structure. Upon exposure to the excitation light, the light sensitivity of the PANi layer in the PANi/TiO2 structure reveals a response mode distinct from those of the neat PANi layer. The conductance of the PANi layer in the coupling structure shows two modes of response: (1) a negative mode, i.e., a decrease in conductance in response to the excitation light of wavelength 369, 396 and 447 nm, and (2) a positive mode, namely an increase in conductance, as with the excitation light of wavelength 667 nm. On the other hand, the neat PANi layer simply shows a single positive response to excitation light. Those response modes account for a modulation of the PANi/TiO2 depletion region that in turn depends upon the photoexcited electrons and holes in the heterostructure. The diffusion of excess photogenerated electrons and holes over the heterojunction results in an expansion or reduction of depletion width that gives rise to an increase or decrease of the PANi layer conductance, i.e., a positive or negative response, respectively. In addition, the negative mode in response to the excitation light of wavelength 447 nm (~2.8 eV) is assumed to be an impact of the PANi in extending the photoinduction of the TiO2 component into the vision range at the blue region.

(Invited) Energy Transfer in Hybrid Plasmonic-Polymer Nanomaterials

Energy transfer between plasmonic nanoparticles and polymer acceptors is a possible means to overcome fast competing processes such as rethermalization. I will discuss recent work in which we showed that polyaniline (PANI), which readily hybridizes onto gold nanorods (AuNRs), undergoes switchable energy transfer when the PANI chemical structure is modulated between its emeraldine base and salt forms. Energy transfer had not previously been identified as a mechanism in this common hybrid nanomaterial, despite the fact that AUNR/PANI hybrids have been widely studied for refractive index switching. Because energy transfer depends strongly on spectral overlap between the donor (AuNR plasmon) and the acceptor (PANI absorption) spectra, small changes in overlap within a heterogeneously broadened colloidal sample are enough to obscure the effect in ensemble spectroscopy. Single-particle scattering studies exploit the innate heterogeneity of AuNR/PANI samples because we were able to examine the spectral overlap 1 hybrid at a time and show that strong energy transfer can occur when overlap is maximized in either the emeraldine base or salt forms. Thus, the small differences in AuNR/PANI structure turn out to be an advantage when we look one hybrid at a time.

Sensor label with polyaniline-metal composites for meat freshness monitoring

ABSTRACT In this study, ion-track membranes with pore diameters of 2 ± 0.1 μm and a fluence of 107 cm−2, with a thin layer of gold sputtered on one side, were used for the electrochemical synthesis of thin films from a polyaniline (PANI) composite with gold (Au) or silver (Ag) nanoparticles. PET (polyethylene terephthalate ion-track membranes) films with the thin film of TM+PANI/Au and TM+PANI/Ag composites, featuring a developed microstructured surface, were designed. Using ATR-FTIR (Attenuated Total Reflection – Fourier-transform infrared spectroscopy) and Raman spectroscopy, it was determined that PANI was synthesised predominantly in the form of an emeraldine salt, with a minor presence of the emeraldine base form. The TM+PANI/Au and TM+PANI/Ag films exhibited high sensitivity to ammonia, with detection thresholds of approximately 40 mg/L and 20 mg/L, respectively.

Synthesis and Characterization of Polyaniline Emeraldine Salt (PANI-ES) Colloids Using Potato Starch as a Stabilizer to Enhance the Physicochemical Properties and Processability.

Conductive polymers, such as polyaniline (PANI), have interesting applications, ranging from flexible electronics, energy storage devices, sensors, antistatic or anticorrosion coatings, etc. However, the full exploitation of conductive polymers still poses a challenge due to their low processability. The use of compatible stabilizers to obtain dispersible and stable colloids is among the possible solutions to overcome such drawbacks. In this work, potato starch was used as a steric stabilizer for the preparation of colloidal polyaniline (emeraldine salt, ES)/starch composites by exploiting the oxidative polymerization of aniline in aqueous solutions with various starch-to-aniline ratios. The polyaniline/starch bio-composites were subjected to structural, spectroscopic, thermal, morphological, and electrochemical analyses. The samples were then tested for their dispersibility/solubility in a range of organic solvents. The results demonstrated the formation of PANI/starch biocomposites with a smaller average size than starch particles, showing improved aqueous dispersion and enhanced solubility in organic solvents. With respect to previously reported PANI-EB (emeraldine base)/starch composites, the novel colloids displayed a lower overall crystallinity, but the conductive nature of PANI-ES enhanced its electrochemical properties, resulting in richer redox chemistry, particularly evident in its oxidation behavior, as observed through cyclic voltammetry. Finally, as proof of the improved processability, the colloids were successfully integrated into a thin polyether sulfone (PES) membrane.

FeCo/PANI composites as electromagnetic shields in the X-band: An understanding of the loss mechanisms

The growing dependence on electronic devices functioning within the microwave frequency range, coupled with the need for miniaturization, has resulted in increased instances of electromagnetic interference (EMI) in such devices. Besides altering device performance, the associated health hazards due to electromagnetic radiations have necessitated the urgency for developing efficient electromagnetic shielding materials. Here, highly magnetic FeCo nanoparticles, approximately 200 nm in diameter, have been used as magnetic filler materials in emeraldine base (PANI – EB) and emeraldine salt (PANI – ES) forms of polyaniline to understand the EMI shielding response in X-band frequency range (8.2–12.4 GHz). Composites using 10 % and 25 % FeCo by weight have been prepared using a physical mixing approach and uniform dispersion within the polymer matrix is ascertained using FE-SEM imaging and EDX elemental maps. Structural and magnetic properties of FeCo remain unaltered after the grind mixing process, as confirmed by XRD and VSM measurements. With the total shielding effectiveness remaining sufficiently low at 2–3 dB in FeCo/PANI – EB, significant enhancement to up to 40 dB is achieved in composites prepared in PANI – ES. Detailed investigations of electromagnetic parameters of the composites reveal the importance of the magnetic filler to achieve an absorption-dominated shielding of electromagnetic waves.

The influence of anions in the ionic liquid-water mixtures on the conformational structures of emeraldine base and emeraldine salt form of polyaniline

The development of antifouling membranes for water filtration applications is challenging. Conducting polymers can show enhanced antifouling characteristics by blending with various polymers, nanomaterials, and Ionic liquids (ILs). In this paper, we perform an all-atom molecular dynamics simulation on a conducting polymer polyaniline (PANI) immersed in IL-water mixtures. Two forms of PANI were considered, namely Emeraldine base (EB) and Emeraldine salt (ES) as well as two different water-mixed ILs are considered namely (a) 1-ethyl-3-methyl imidazolium [EMIM]+ hexafluorophosphate [PF6]- and (b) 1-ethyl-3-methyl imidazolium [EMIM]+ tetra-fluoroborate [BF4]-. We present various intra- and inter-molecular structural properties, solvation thermodynamics, and dynamic properties. We observe that with an increase in IL concentration, the radius of gyration (Rg) value shows a decrease for ES in pure state in both ILs; on the other hand, we see a minimal increase in the Rg values of EB in both ILs. The dihedral angle distribution analysis shows a combination of gauche and trans state for ES, whereas trans state is more pronounced for the case of EB in both water-IL mixtures. The radial distribution function (RDF) analysis between the ortho, meta carbons of the benzene rings, and the amine groups on ES with [BF4]- and [PF6]- show significant structural peaks. On the other hand, EB and ES show lower interaction with the water molecules. The number of hydrogen bonds (h-bonds) between polymer and water is higher for EB than ES in both IL-water mixtures. The hydrogen bond lifetime (τ) values show one-fold higher values for EB than ES. The self-diffusion coefficient (D) values of water show a decrease with an increase in IL concentration. The thermodynamic properties solvation enthalpy (ΔH) and excess molar volume (VmE) for both ES and EB show a more favorable solvation in [EMIM]+[BF4]- when compared to [EMIM]+[PF6]- with an increase in IL concentration. These observations are crucial for selecting ILs and designing sustainable polymers for antifouling membranes.

Sintesis polianilin (PANi) dengan metode polimerisasi interfasial sebagai bahan dasar pembuatan sensor gas amonia (NH3)

One of the main components in IoT-based devices is sensors. Polyaniline is a conductive polymer that has great potential to be developed as an active layer for chemical sensors because it has high sensitivity, is easy to synthesize and its electrical conductivity can be adjusted. This study aims to synthesize and characterize polyaniline using the interfacial polymerization method. In this study, polyaniline was synthesized by varying the aniline concentration of 2, 3, and 5 M, then its functional groups were characterized using FTIR and its conductivity and sensitivity were measured with an LCR meter. The result shows that polyaniline is in the form of emeraldine salt which is characterized by the formation of absorption bands at concentrations of 2, 3, and 5 M, respectively, 1,141.86 cm-1, 1,139 cm-1 and 1,139.93 cm-1. The highest conductivity was obtained at a concentration of 2 M, namely 4.9x10-5 and a sensitivity of 82.8% for an ammonia concentration of 100 ppm. So it can be concluded that the polyaniline obtained is a form of semiconducting emeraldine salt.

Anionic Dye Removal with a Thin Cationic Polyaniline Coating on Cellulosic Biomaterial.

This paper reports the development of novel adsorbent materials using polyaniline (PANI) grafted onto Posidonia (POS) fibers, aimed at efficiently removing phenol red (PSP), an anionic dye, from aqueous solutions. The synthesis involved the copolymerization of aniline grafted on the surface of the POS and aniline monomer in solution, resulting in a chemically bound thin PANI layer on the POS bioadsorbent. Structural characteristics and binding affinities of these adsorbents with PANI under its emeraldine salt (POS@PANI-ES) or emeraldine base (POS@PANI-EB) forms are reported. The rapid adsorption kinetics observed are attributed to enhanced accessibility to PANI adsorption sites on the POS surface. The binding percentages of PSP to POS@PANI-ES and POS@PANI-EB materials were found to be 97 and 50%, respectively, after 15 min of contact time. The Langmuir model for localized adsorption sites and the Volmer model for nonlocalized adsorption as a mobile layer were fitted to the experimental adsorption isotherms of PSP to POS@PANI-EB and POS@PANI-ES, yielding the thermodynamic parameters of adsorption. The adsorption capacities of PSP on POS@PANI-EB and POS@PANI-ES were 37.8 and 71.5 μmol g-1, respectively. The adsorption of PSP remained above 80% at moderate salt concentrations of around 0.1 mol L-1; however, higher concentrations of NaCl and CaCl2 in PSP solutions significantly reduced the adsorption on POS@PANI-ES.

Controlling the morphology and properties of electrodeposited polyaniline layer on TiO2 nanotubes

Polyaniline (PANI) layers were electrodeposited, as the conductive emeraldine salt phase (PANI (ES)), on the surface of titanium dioxide nanotubes (TiO2 NTs) to evaluate the protective and photo(electro)chemical performance. TiO2 NTs plates were obtained by anodization, in a two-electrode in the undivided cell. The adjustment of the electropolymerization parameters (e.g. aniline concentration, cycles number in cyclic voltammetry, TiO2 cathodic polarization) allowed the control of the PANI (ES) morphology and film thickness, changing the charge recombination dynamics on the PANI (ES)/TiO2 and PANI (ES)/liquid interfaces. It was observed that lower aniline concentrations resulted in the best control of the electropolymerization process, which ensured the deposition of thin films. The TiO2 NTs/PANI (ES) interface was characterized by absorption and vibrational spectroscopies, and scanning electron microscopy. Electronic and photo(electro)chemical properties of the TiO2 NTs/PANI (ES) films were characterized by photoelectrochemical measurements and electrochemical impedance spectroscopy.

Electrochemical Sensing of Cadmium and Lead Ions in Water by MOF-5/PANI Composites.

For the first time, composites of metal-organic framework MOF-5 and conjugated polymer polyaniline (PANI), (MOF-5/PANI), prepared using PANI in its conducting (emeraldine salt, ES) or nonconducting form (emeraldine base, EB) at various MOF-5 and PANI mass ratios, were evaluated as electrode materials for the electrochemical detection of cadmium (Cd2+) and lead (Pb2+) ions in aqueous solutions. Testing of individual components of composites, PANI-ES, PANI-EB, and MOF-5, was also performed for comparison. Materials are characterized by Raman spectroscopy, scanning electron microscopy (SEM) and dynamic light scattering (DLS), and their electrochemical behavior was discussed in terms of their zeta potential, structural, morphology, and textural properties. All examined composites showed high electrocatalytic activity for the oxidation of Cd and Pb to Cd2+ and Pb2+, respectively. The MOF/EB-1 composite (71.0 wt.% MOF-5) gave the highest oxidation currents during both individual and simultaneous detection of two heavy metal ions. Current densities recorded with MOF/EB-1 were also higher than those of its individual components, reflecting the synergistic effect where MOF-5 offers high surface area for two heavy metals adsorption and PANI offers a network for electron transfer during metals' subsequent oxidation. Limits of detection using MOF/EB-1 electrode for Cd2+ and Pb2+ sensing were found to be as low as 0.077 ppm and 0.033 ppm, respectively. Moreover, the well-defined and intense peaks of Cd oxidation to Cd2+ and somewhat lower peaks of Pb oxidation to Pb2+ were observed at voltammograms obtained for the Danube River as a real sample with no pretreatment, which implies that herein tested MOF-5/PANI electrodes could be used as electrochemical sensors for the detection of heavy metal ions in the real water samples.

Epoxy coating reinforced with graphene-PANI nanocomposites for enhancement of corrosion-resistance performance of mild steel in saline water

Protective coatings enriched with different types of chemical additives, functional fillers, and nanostructured materials are gaining immense interest to minimize corrosion. The present work demonstrates the synthesis of chemically functionalized reduced graphene oxide (rmGO) and emeraldine salt form of polyaniline (PANI-ES)-based rmGO-PANI-ES nanocomposites as protective functional fillers for epoxy coating to inhibit mild steel corrosion. The oxidative polymerization of aniline into PANI-ES is initiated on nitrogen-rich active sites of rmGO, and it propagates along the basal plane of rmGO, eventually enwrapped the graphene sheets by interfacially grown PANI-ES. The synthesis of rmGO-PANI-ES nanocomposites and their chemical, morphological, crystalline, and structural characteristics are examined by the FTIR, 13C NMR, XPS, XRD, Raman, SEM, and HRTEM analyses. The multiple interactions between the highly polar nitrogen-rich rmGO-PANI-ES nanocomposites and the epoxy matrix strengthened the coating and increased the hardness and elastic modulus. The corrosion inhibition performance of epoxy coating enriched with the rmGO-PANI-ES nanocomposites is probed by electrochemical impedance spectroscopic (EIS) and salt spray tests using an accelerated corrosive environment (3.5 wt% NaCl). The rmGO-PANI-ES-15 nanocomposite having 0.15 wt% rGO in epoxy coating showed superior corrosion inhibition performance. The total electrochemical impedance of epoxy coating (8.7 ×103 Ω.cm2) increased to 4.7 ×1015 Ω.cm2 after incorporating 1 wt% rmGO-PANI-ES-15 nanocomposite. The enhancement of electrochemical impedance by ∼12 orders of magnitude demonstrates the effectiveness of the rmGO-PANI-ES nanocomposites for corrosion mitigation in a harsh corrosive environment. The high surface area and remarkable structural barrier of the 2D chemically functionalized graphene furnished excellent protective coverage. The PANI-ES of rmGO-PANI-ES nanocomposites formed a passive layer of fully reduced leucoemeraldine base of PANI (PANI-LEB) on the coating-mild steel interface by accepting the electrons, generated during the anodic oxidation of iron. These events collectively increase the impedance by multifolds and inhibit steel corrosion. The present findings revealed that graphene-enriched conductive polymeric nanocomposites-based coatings can be promising solution to mitigate corrosion of metal-based installations in a marine environment.

Conductive nano-Al/polyaniline composites prepared via mechanical milling

The conductive nano-Al/polyaniline composites were prepared by the milling method in the solid state. Here, aluminum nanostructures were prepared in two different mechanical methods, wire drawing and wire milling in the presence of lubricant oil. The effects of the preparation methods on the structures and morphologies of aluminum nanostructures were investigated by XRD and FESEM. The results show that the shape and size of aluminum nanoparticles in the preparation by the wire drawing method are significantly different than the wire milling method. The aluminum nanostructures were prepared by milling method have flake-like nanosheets while the wire drawing method leads to the formation of spherical ultrafine nanoparticles, which particles size are in the range of 30–60 nm. Then, polyaniline was produced using a solid-state polymerization process by the chemical reaction between aniline hydrochloride and potassium peroxydisulfate. Finally, nano-Al/polyaniline composites were prepared by mechanical milling at room temperature. The quantitative analysis was carried out with the materials analysis using diffraction (MAUD) method and weight fraction for aluminum and PANI were calculated 6.66% and 93.34%, respectively. Electrical conductivity measurements show the conductivity (1.2 × 10−2 S cm−1 at 25 °C) for polyaniline emeraldine salt and (1.02 × 10−3 S cm−1 at 25 °C) in nanocomposite respectively. The results show that by adding aluminum nanoparticles to the polymer the conductivity of nanocomposite (Al/PANI-ES) is lower than that for pure (PANI-ES). Thermogravimetry and differential thermal analysis curves show pure (PANI-ES) and nanocomposite (Al/PANI-ES) have a similar thermal degradation process. The total weight loss in TG curve of pure PANI-ES, in the temperature range 45–800 °C is 46.28% but, total weight loss observed in nanocomposite is 38.67%. Therefore, nanocomposite has higher thermal stability than that of the pure PANI-ES.

Preparation of a polyaniline/ZnO-NPs composite for the visible-light-driven hydrogen generation

Compositions of ZnO nanoparticles and polyaniline, in the form of emeraldine salt, were manufactured as thin layers by using the spin-coating method. Then, the effect of polyaniline content on their photoelectrochemical characteristics was studied. Results indicate that all the samples are sensitive to light. Besides, with 0.30% of PANI, the composite sample demonstrates the highest photocurrent density; also, its photocurrent increment starts to increase at a voltage of ⁓ 1.23 V (vs. RHE), which is approximately in accordance with the theoretical potential of water electrolysis. Furthermore, since the rate of electron–hole recombination in this composite sample is the lowest, it possesses the highest photoelectrochemical efficiency. Main findings were analyzed with respect to UV–visible absorption and photoluminescence spectra as well as SEM micrographs of the samples and Raman spectral measurements. Besides, electrochemical impedance spectroscopy analysis was applied to both pure ZnO and the sample with the best response. Effects of drying temperature and layer thickness were also investigated.

Co-doped polyaniline composites for biological application: Morphological, functional, optical and antibacterial activities

In the present work, we have successfully synthesized co-doped polyaniline (PANI) composites with various organic acids DBSA, phthalic acid, oxalic acid and Calotropis proceralatex using a simple chemical oxidative polymerization method. The structural, optical, surface morphology and antibacterial analyses were carried out for the synthesized PANI (DBSA-Phthalic acid), PANI (DBSA-Oxalic acid) and PANI (DBSA-C.Procera latex) composites. The structural characterization using XRD and FT-IR measurements confirmed the formation of emeraldine salt form of PANI from the observed characteristic peaks of PANI in all the composites. The observed UV–visible absorption and PL emission peaks also assured the synthesis of PANI in emeraldine form. SEM micrographs of PANI (DBSA-phthalic acid) composites exhibited continuous rock-like agglomerated structure. The antibacterial activity tested against medically important bacteria Bacillus subtilisrevealed a maximum inhibition zone for the DBSA-phthalic acid doped PANI composites when compared with other composites. The average value of zone of inhibition for the PANI composites is found to be 21–24 nm. The minimum inhibitory concentration (MIC) is found to be 1 mg/L for all the PANI composites whereas the minimum bactericidal concentration (MBC) is found to be 60 mg/L for PANI (DBSA-Phthalic acid) and 80 mg/L for PANI (DBSA-Oxalic acid), PANI (DBSA-C.Procera latex) composites. A larger and clear zone of inhibition exhibited by the synthesized co-doped PANI composites confirms their potential as an effective antibacterial agent.

Noncovalent functionalisation of polyaniline with the ionic liquid: An unneeded asset to prepare the emeraldine salt form of polyaniline using protic ionic liquids as polymerisation medium

Noncovalent functionalisation of polyaniline with the ionic liquid: An unneeded asset to prepare the emeraldine salt form of polyaniline using protic ionic liquids as polymerisation medium

Environmental Potential of Carbonized MOF-5/PANI Composites for Pesticide, Dye, and Metal Cations-Can They Actually Retain Them All?

The environmental application of the carbonized composites of the Zn-containing metal-organic framework MOF-5 and polyaniline (PANI) in its emeraldine salt and base forms (C-(MOF-5/PANI)) was investigated for the first time. Textural properties and particle size distributions revealed that composites are dominantly mesoporous and nanoscale in nature, while Raman spectroscopy revealed the ZnO phase beneath the carbon matrix. Adsorption of pesticide, dye, and metal cation on C-(MOF-5/PANI) composites in aqueous solutions was evaluated and compared with the behavior of the precursor components, carbonized MOF-5 (cMOF), and carbonized PANIs. A lower MOF-5 content in the precursor, a higher specific surface area, and the pore volume of the composites led to improved adsorption performance for acetamiprid (124 mg/g) and Methylene Blue (135 mg/g). The presence of O/N functional groups in composites is essential for the adsorption of nitrogen-rich pollutants through hydrogen bonding with an estimated monolayer capacity twice as high as that of cMOF. The proton exchange accompanying Cd2+ retention was associated with the Zn/Cd ion exchange, and the highest capacity (9.8 mg/g) was observed for the composite synthesized from the precursor with a high MOF-5 content. The multifunctionality of composites was evidenced in mixtures of pollutants where noticeably better performance for Cd2+ removal was found for the composite compared to cMOF. Competitive binding between three pollutants favored the adsorption of pesticide and dye, thereby hindering to some extent the ion exchange necessary for the removal of metal cations. The results emphasize the importance of the PANI form and MOF-5/PANI weight ratio in precursors for the development of surface, porosity, and active sites in C-(MOF-5/PANI) composites, thus guiding their environmental efficiency. The study also demonstrated that C-(MOF-5/PANI) composites retained studied pollutants much better than carbonized precursor PANIs and showed comparable or better adsorption ability than cMOF.