Simplified in-situ tailoring of cross-linked self-doped sulfonated polyaniline (S-PANI) membranes for nanofiltration applications

Sulfonated polyaniline (S-PANI) membranes could have wide-ranging applications due to their electrical tunability, antifouling behaviour and chlorine resistance. However, S-PANI membranes below the ultrafiltration (UF) separation range have not been successfully established. This study presents a scalable approach to produce the first in-situ cross-linked S-PANI membranes at nanofiltration (NF) range. S-PANI membranes were produced by non-solvent induced phase separation (NIPS). The presence of sulfonic groups as polymer cross-linking anchors and controlling the coagulation bath's acidic strength resulted in instant stabilisation of the selective layer, which hindered the solvent/non-solvent exchange rate. This enabled the production of a tailored membrane morphology with a dense skin layer, suppressed macro-voids, reduced porosity, enhanced tensile strength, increased hydrophilicity and solvent stability. S-PANI membranes cast in 3 M HCl(aq) with MWCO≈680 g mol−1 (sucrose octa-acetate) showed a rejection of 99 % for PEG 1000 g mol−1 and 91–100 % for dye solution (MW range of 320–1017 g mol−1) compared to 34 % and 74–85 % rejection for a commercial fluoropolymer membrane (nominal MWCO 1000 g mol−1), respectively. The reported approach is simple and can be applied to design new classes of cross-linked solvent stable S-PANI NF membranes

Enhanced adsorption of cationic and anionic dyes from aqueous solutions by polyacid doped polyaniline

A new high surface area polyaniline (PANI) adsorbent was synthesized by matrix polymerization of aniline in the presence of a polyacid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA). Morphological and physicochemical properties of PANI-PAMPSA were characterized by field emission scanning electron microscope (FESEM), Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), nitrogen adsorption/desorption and zeta potential measurement. Adsorption properties were evaluated using methylene blue (MB) and rose bengal (RB) as model dyes.The results showed that PANI-PAMPSA obtained a well-defined porous structure with a specific surface area (126 m2 g−1) over 10 times larger than that of the emeraldine base PANI (PANI-EB) (12 m2 g−1). The maximum adsorption capacities were 466.5 mg g−1 for MB and 440.0 mg g−1 for RB, higher than any other PANI-based materials reported in the literature. The FTIR analysis and zeta potential measurement revealed that the adsorption mechanisms involved π-π interaction and electrostatic interaction. The adsorption kinetics were best described by a pseudo-second-order model, and the adsorption isotherms followed the Langmuir model. The thermodynamic study indicated that the adsorption was a spontaneous endothermic process. Overall, the convenient synthesis and the high adsorption capacity make PANI-PAMPSA a promising adsorbent material for dye removal

Exploiting the electrical conductivity of poly-acid doped polyaniline membranes with enhanced durability for organic solvent nanofiltration

We have developed stable organic solvent nanofiltration (OSN) membranes that are electrically conductive. These membranes overcome key issues with current tuneable membranes: molecular weight cut off (MWCO) limited to the UF-range and lack of filtration stability. Polyaniline (PANI) was in-situ doped by poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA) using chemical oxidative polymerization that leads to formation of interpolymer complex. The PANI-PAMPSA membranes were prepared by phase inversion method and the pore sizes were shrunk by annealing the membranes at temperatures lower than the crosslinking temperature. The membranes were systematically evaluated using visual and chemical analysis and in-filtration experiments. The developed membranes were solvent stable, reusable, had a denser structure and lower MWCO and there was no thermal crosslinking as seen by IR. The solvent permeance obtained were: 0.46, 0.60 and 0.74 Lm −2 h −1 bar −1 for acetone, 2-propanol and methanol respectively, with MWCO below 300 Da and 266 Da for methanol. For the tuneability investigation, when applying an electrical potential (20 V) in a custom-made cross-flow membrane cell, an increase in MWCO and permeance (10.4% and 55.6%, respectively) was observed. These results show that this simple in-situ doping method with heat treatment can produce promising and stable PANI membranes, for OSN processes in different solvents, with the distinctive feature of in-situ performance control by applying external electrical potential. </p

An In-Depth Study of the Use of Eosin Y for the Solar Photocatalytic Oxidative Coupling of Benzylic Amines

The direct utilization of solar light for synthetic photochemistry is a sustainable and efficient technological goal. Herein we report the first in-depth study on the use of the inexpensive organic photocatalyst eosin Y for solar photocatalysis by demonstrating the oxidative coupling of benzylic amines to form imines, a class of valuable intermediates in chemical synthesis. By the use of a unique experimental setup with a custom-built variable-intensity solar light simulator, replication of a natural-sunlight environment was achieved. The relative significance of different variables on the reaction rate constant was quantitatively evaluated through comprehensive experimental design. Reaction kinetics and mechanistic information were obtained using both a batch reactor and a spinning-disc reactor. A maximum pseudo-first-order rate constant of 1.59 × 10^–3 s^–1 was obtained at a maximum turnover frequency of 192 h^–1 through optimization of the reaction conditions. Experiments carried out using a spinning-disc reactor confirmed that the reaction was not mass-transfer-limited but rather photon-transfer-limited