Photocatalytic Degradation of Organic Pollutants-Nile Blue, Methylene Blue, and Bentazon Herbicide-Using NiO-ZnO Nanocomposite.

Water pollution poses a significant threat to both human health and ecosystem integrity. Chemical pollutants such as dyes and pesticides affect the water quality and endanger aquatic life. Among the methods for water purification from organic pollutants, photodegradation is certainly a valid technique to decrease such contaminants. In this work, pristine NiO, ZnO, and NiO-ZnO photocatalysts were synthesized by the homogeneous co-precipitation method. X-ray diffraction confirms the formation of a photocatalyst consisting of ZnO (Hexagonal) and NiO (Cubic) structures. The crystalline size was calculated by the Scherrer formula, which is 19 nm for the NiO-ZnO photocatalyst. The band gap measurements of the prepared samples were obtained using the Tauc Plot, equation which is 2.93 eV, 3.35 eV and 2.63 eV for NiO, ZnO, and NiO-ZnO photocatalysts, respectively. The photocatalytic performance of NiO-ZnO nanocomposite was evaluated through the degradation of Methylene Blue and Nile Blue dyes under sunlight, and Bentazon herbicide under a UV light. Photocatalyst degradation efficiency was 95% and 97% for Methylene Blue and Nile Blue in 220 min under sunlight while a degradation of 70% for Bentazon after 100 min under UV light source was found.

Improved Hydrolytic and Mechanical Stability of Sulfonated Aromatic Proton Exchange Membranes Reinforced by Electrospun PPSU Fibers.

The hydrolytic stability of ionomer membranes is a matter of concern for the long-term durability of energy storage and conversion devices. Various reinforcement strategies exist for the improvement of the performances of the overall membrane. We propose in this article the stabilization of membranes based on aromatic ion conducting polymers (SPEEK and SPPSU) by the introduction of an electrospun mat of inexpensive PPSU polymer. Characterization data from hydrolytic stability (mass uptake and dimension change) and from mechanical and conductivity measurements show an improved stability of membranes in phosphate buffer, used for enzymatic fuel cells, and in distilled water. The synergistic effect of the reinforcement, together with the casting solvent and the thermal treatment or blending polymers, is promising for the realization of high stability ionomer membranes.

Impact of Anion Exchange Ionomers on the Electrocatalytic Performance for the Oxygen Reduction Reaction of B-N Co-doped Carbon Quantum Dots on Activated Carbon.

Composite electrocatalytic electrodes made from B-N co-doped carbon quantum dots (CQD) and various anion exchange ionomers (AEI) are studied for the oxygen reduction reaction (ORR) in alkaline solutions. The quantity and positions of dopants in CQD, prepared by hydrothermal synthesis, are analyzed by various spectroscopies, including 11B NMR spectroscopy that evidenced boronic acid at edge sites. The AEI are synthesized with various backbones, including more hydrophilic polysulfone, hydrophobic poly(alkylene biphenyl), and poly(2,6-dimethyl-1,4-phenylene oxide) with intermediate hydrophilicity; the functional groups are trimethylammonium moieties grafted on long (LC) or short (SC) side chains. The CQD/AEI ink is drop-casted on activated carbon paper, and the samples are fixed on a rotating disk electrode and studied in three-electrode configuration in oxygen-saturated 0.1 M KOH. The onset potentials are among the best in the literature (Eonset ≈ 0.94 V vs RHE). The highest electrocatalytic activity is observed for electrodes containing AEI with long side chains; the sample containing PPO LC attains excellent ORR currents approaching that of benchmark Pt/C cloth. The electrocatalytic performances are discussed in view of the many relevant AEI parameters, including hydrophilicity, oxygen permeability, catalyst dispersivity, and ionic conductivity.

A Short Overview of Biological Fuel Cells.

This short review summarizes the improvements on biological fuel cells (BioFCs) with or without ionomer separation membrane. After a general introduction about the main challenges of modern energy management, BioFCs are presented including microbial fuel cells (MFCs) and enzymatic fuel cells (EFCs). The benefits of BioFCs include the capability to derive energy from waste-water and organic matter, the possibility to use bacteria or enzymes to replace expensive catalysts such as platinum, the high selectivity of the electrode reactions that allow working with less complicated systems, without the need for high purification, and the lower environmental impact. In comparison with classical FCs and given their lower electrochemical performances, BioFCs have, up to now, only found niche applications with low power needs, but they could become a green solution in the perspective of sustainable development and the circular economy. Ion exchange membranes for utilization in BioFCs are discussed in the final section of the review: they include perfluorinated proton exchange membranes but also aromatic polymers grafted with proton or anion exchange groups.

Nanostructured, Metal-Free Electrodes for the Oxygen Reduction Reaction Containing Nitrogen-Doped Carbon Quantum Dots and a Hydroxide Ion-Conducting Ionomer.

In this work, we studied the combination of nitrogen-doped carbon quantum dots (N-CQD), a hydroxide-ion conducting ionomer based on polysulfone (PSU) and polyaniline (PANI), to explore the complementary properties of these materials in high-performance nanostructured electrodes for the oxygen reduction reaction (ORR) in alkaline solution. N-CQD were made by hydrothermal synthesis from glucosamine hydrochloride (GAH) or glucosamine hydrochloride and N-Octylamine (GAH-Oct), and PSU were quaternized with trimethylamine (PSU-TMA). The nanocomposite electrodes were prepared on carbon paper by drop-casting. Furthermore, we succeeded in preparing PSU-TMA + PANI + GAH-Oct fibers by electrospinning. The capacitance of the electrodes was investigated by cyclic voltammetry and impedance spectroscopy, which gave similar trends. The ORR was investigated by linear sweep voltammetry at rotating disk electrode speeds between 250 and 2000 rpm in an oxygen-saturated 1 M KOH solution. Koutecky-Levich plots showed that four electrons were exchanged for nanocomposite electrodes containing CQD. The highest reduction currents were measured for the electrodes containing GAH-Oct. The Tafel plots gave the lowest slope and the most positive half-wave potential for PSU-TMA + PANI + GAH-Oct fibers. The best electrocatalytic activity of this electrode could be related to the high amount of graphitic nitrogen in GAH-Oct. Long-term cycling tests showed no significant modification of the onset potential, but a change of the current in the mass transport limited region, indicated the evolution of the microstructure of the nanocomposite ORR electrode modifying the mass transport conditions during the first 400 cycles before reaching stationary conditions. FTIR spectra were used to study possible electrode degradation after the ORR in 1 M KOH: the only change was due to the reaction of PANI emeraldine salt to emeraldine base, whereas the other constituents of the multiphase electrode did not show any degradation.

Anion Exchange Membranes with 1D, 2D and 3D Fillers: A Review.

Hydroxide exchange membrane fuel cells (AEMFC) are clean energy conversion devices that are an attractive alternative to the more common proton exchange membrane fuel cells (PEMFCs), because they present, among others, the advantage of not using noble metals like platinum as catalysts for the oxygen reduction reaction. The interest in this technology has increased exponentially over the recent years. Unfortunately, the low durability of anion exchange membranes (AEM) in basic conditions limits their use on a large scale. We present in this review composite AEM with one-dimensional, two-dimensional and three-dimensional fillers, an approach commonly used to enhance the fuel cell performance and stability. The most important filler types, which are discussed in this review, are carbon and titanate nanotubes, graphene and graphene oxide, layered double hydroxides, silica and zirconia nanoparticles. The functionalization of the fillers is the most important key to successful property improvement. The recent progress of mechanical properties, ionic conductivity and FC performances of composite AEM is critically reviewed.

Silica Containing Composite Anion Exchange Membranes by Sol-Gel Synthesis: A Short Review.

This short review summarizes the literature on composite anion exchange membranes (AEM) containing an organo-silica network formed by sol-gel chemistry. The article covers AEM for diffusion dialysis (DD), for electrochemical energy technologies including fuel cells and redox flow batteries, and for electrodialysis. By applying a vast variety of organically modified silica compounds (ORMOSIL), many composite AEM reported in the last 15 years are based on poly (vinylalcohol) (PVA) or poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) used as polymer matrix. The most stringent requirements are high permselectivity and water flux for DD membranes, while high ionic conductivity is essential for electrochemical applications. Furthermore, the alkaline stability of AEM for fuel cell applications remains a challenging problem that is not yet solved. Possible future topics of investigation on composite AEM containing an organo-silica network are also discussed.

Nanocomposite Anion Exchange Membranes with a Conductive Semi-Interpenetrating Silica Network.

Nanocomposite anion exchange membranes were synthesized based on poly(sulfone trimethylammonium) chloride. A hybrid semi-interpenetrating silica network containing a large amount of quaternary ammonium groups was prepared by two sol-gel routes, in situ with a single precursor, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (TMSP), or ex situ mixing two precursors, TMSP and 3-(2-aminoethylamino)propyldimethoxy-methylsilane (AEAPS). The properties of these hybrid composites and their degradation after immersion in 1 M KOH at 60 °C were studied. The degradation is reduced in the composite materials with a lower decrease in the ion exchange capacity. FTIR spectra showed that a main degradation mechanism with a single precursor TMSP is the dissolution of the hybrid silica network in KOH, whereas it is stable with the mixture of TMSP/AEASP. This conclusion is in agreement with the thermogravimetric analysis. The mechanical properties show a better ductility with a single precursor and higher stiffness and strength, but less ductility, by the ex situ route. The activation energy was between 0.25 and 0.14 eV for Cl and OH ion conduction, respectively, consistent with the migration mechanism.

Stability of Proton Exchange Membranes in Phosphate Buffer for Enzymatic Fuel Cell Application: Hydration, Conductivity and Mechanical Properties.

Proton-conducting ionomers are widespread materials for application in electrochemical energy storage devices. However, their properties depend strongly on operating conditions. In bio-fuel cells with a separator membrane, the swelling behavior as well as the conductivity need to be optimized with regard to the use of buffer solutions for the stability of the enzyme catalyst. This work presents a study of the hydrolytic stability, conductivity and mechanical behavior of different proton exchange membranes based on sulfonated poly(ether ether ketone) (SPEEK) and sulfonated poly(phenyl sulfone) (SPPSU) ionomers in phosphate buffer solution. The results show that the membrane stability can be adapted by changing the casting solvent (DMSO, water or ethanol) and procedures, including a crosslinking heat treatment, or by blending the two ionomers. A comparison with NafionTM shows the different behavior of this ionomer versus SPEEK membranes.

Analysis of temperature-promoted and solvent-assisted cross-linking in sulfonated poly(ether ether ketone) (SPEEK) proton-conducting membranes.

Sulfonated poly(ether ether ketone) (SPEEK) membranes were thermally treated at temperatures between 120 and 160 degrees C. Water uptake measured at different relative humidity values or by full immersion in water between 25 and 145 degrees C was found to depend very strongly on previous thermal treatment and casting solvent. Water-uptake coefficient values as low as 10-15 even upon immersion in water at 100 degrees C were obtained with membranes treated at 160 degrees C. This effect is related to cross-linking by SO2 bridges between macromolecular chains. An important role is also played by the casting solvent: among the investigated solvents, dimethylsulfoxide (DMSO) gave the best results. A chemical kinetics model is outlined that permits the estimation of the relevant kinetic parameters, especially the activation energy of the cross-linking reaction, which was found to be about 60 kJ/mol. These results are of significant importance for the improvement of proton-exchange membrane fuel cells.