Morphological studies on the agglomeration of FeCo supported nitrogen-doped reduced graphene oxide catalyst prepared at varying annealing temperature

One of the barriers to the large-scale commercialization of proton exchange membrane fuel cells (PEMFCs) is the high-priced of noble metals such as platinum (Pt). Therefore, in this paper, bimetallic electrocatalyst FeCo supported nitrogen-doped reduced graphene oxide (FeCo-NG) for oxygen reduction reaction (ORR) is proposed and has been successfully prepared through annealing of a mixture containing Fe, Co salts, dicyandiamide (DCDA) and graphene oxide (GO). The starting material GO appeared to be in multilayer sheets through scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis. Due to the high annealing temperature and the absence of the surfactant, agglomeration of FeCo nanoparticles was observed from the morphology analysis. The macrostructure size of the metals particles was observed to be increased over temperature. As the temperature increases, the agglomeration gets more intense because of the increased of van der Waals cohesive forces between the nanoparticles. In addition, the weak electrostatic interaction between the metal cations with the nitrogen and the GO sheets could also be the cause of the agglomeration. The weak electrostatic interaction caused the nanoparticles (Fe and Co) not attracted onto the GO sheets thus inhibit the reduction of FeCo and GO to occur in situ simultaneously. It is believed that the agglomeration of the electrocatalyst FeCo-NG could results to poor electrocatalytic activity of PEMFC

Supercapacitor performance gains from structural modification of carbon electrodes using gamma radiations

The performance of supercapacitors (SC) strongly depends on how their activated carbon (AC) electrodes were synthesized from precursor materials and pretreatments applied to them. This study investigates the effect of direct and filtered gamma radiations applied as pretreatments to the AC. The exposure doses used were from 0.1 kGy to 6 kGy. The high gamma-energy and high dose of the pretreatment broke the randomly orientated graphitic crystal lattices inside AC particles and disturbed the existing functional group populations. The filtered radiation pretreatment at 1 kGy, which contains a higher composition of secondary electrons than direct radiation pretreatment, yields AC with the best overall SC performance. The SC cell made from 1 kGy filtered radiation pretreatment AC showed higher specific capacitance 73.1 % (218.58 F g-1), specific energy 73.54 % (10.96 W h kg-1) and specific power of 8.36 % (155.67 W kg-1) compared to the sample without any radiation pretreatment. This study explicitly shows the benefit of secondary electrons in the radiation field, which produce decisively defect sites on the AC lattices for gains in SC performance

Aryl diazonium modification for improved graphite fibre brush in microbial fuel cell

Aryl diazonium salts are coupling agents that assist in molecules attachment to interfaces for sensing purposes. Despite not being fully explored and not yet widely applicable for cell-based sensors, the high stability of aryl diazonium salt formed sensing system is highly favorable in biological applications. Carbon-based electrodes are the most commonly used in aryl diazonium modification due to its post grafting stable C-C bond formation. Here, salt bridge based microbial fuel cells (MFCs) were used to study on the effect of aryl diazonium modification on the anode graphite fibre brush. Aryl diazonium salts were in situ generated by the diazonation of p-phenylenediamine with NaNO2 in HCl solution. The electrochemical performance of the aryl diazonium modified graphite brush MFC was measured and compared with the unmodified graphite brush MFC. The power output of the modified graphite brush bioanode was higher (8.33 W/m3) than the unmodified graphite brush (7.60 W/m3) after 20 days of operation with ferricyanide as the catholyte. After 70 days of operation using phosphate buffer solution as the catholyte, the Pmax of modified brush was three times higher (0.06 W/m3) than of the unmodified brush (0.02 W/m3), which indicates an enhanced binding towards the substrate that facilitates a better electron transfer between the microbial and electrode surface

Influence of Fe–N–C morphologies on the oxygen reduction reaction in acidic and alkaline media

The development of nonnoble metal oxygen reduction reaction (ORR) catalysts for fuel cells has been motivated by the high cost and limited supply of noble metals, as well as the desire to improve the performance and durability of this type of energy conversion device. In this study, nonnoble Fe–N–C catalyst was synthesized using a zeolitic imidazole framework (ZIF-8), poly (aniline), and 10,10′-dibromo-9,9′-bianthry as precursors to produce Fe–N–C with hollow sphere (HS), amorphous bulky structure (B), and sheet-like thin sheet (N) structure. The Fe–N–C catalyst was analysed in terms of their shape, crystal structure, pore characteristics, and elemental composition. Among all the Fe–N–C catalysts, Fe–N–C_HS had the highest total surface area, followed by Fe–N–C_B and Fe–N–C_N. To evaluate their ORR catalytic activity, a half-cell electrochemical experiment with.1 M KOH and.1 M HClO 4 as the alkaline and acidic electrolytes was conducted. This study revealed that Fe–N–C_HS exhibited the highest onset potential but the Fe–N–C_B has the highest limiting current density in alkaline medium; meanwhile, in acidic media, Fe–N–C_HS shows the best ORR performance with the highest onset potential and limiting current. This highly porous Fe–N–C_HS catalyst also demonstrated active site activation and excellent stability compared with the other samples as well as commercial Pt/C in acidic electrolyte, which suggests its potential for application in proton exchange membrane fuel cells (PEMFCs)

Kinetics of Oxygen Reduction Reaction of Polymer-Coated MWCNT-Supported Pt-Based Electrocatalysts for High-Temperature PEM Fuel Cell

Sluggish oxygen reduction reaction (ORR) of electrodes is one of the main challenges in fuel cell systems. This study explored the kinetics of the ORR reaction mechanism, which enables us to understand clearly the electrochemical activity of the electrode. In this research, electrocatalysts were synthesized from platinum (Pt) catalyst with multi-walled carbon nanotubes (MWCNTs) coated by three polymers (polybenzimidazole (PBI), sulfonated tetrafluoroethylene (Nafion), and polytetrafluoroethylene (PTFE)) as the supporting materials by the polyol method while hexachloroplatinic acid (H2PtCl6) was used as a catalyst precursor. The oxygen reduction current of the synthesized electrocatalysts increased that endorsed by linear sweep voltammetry (LSV) curves while increasing the rotation rates of the disk electrode. Additionally, MWCNT-PBI-Pt was attributed to the maximum oxygen reduction current densities at −1.45 mA/cm2 while the minimum oxygen reduction current densities of MWCNT-Pt were obtained at −0.96 mAcm2. However, the ring current densities increased steadily from potential 0.6 V to 0.0 V due to their encounter with the hydrogen peroxide species generated by the oxygen reduction reactions. The kinetic limiting current densities (JK) increased gradually with the applied potential from 1.0 V to 0.0 V. It recommends that the ORR consists of a single step that refers to the first-order reaction. In addition, modified MWCNT-supported Pt electrocatalysts exhibited high electrochemically active surface areas (ECSA) at 24.31 m2/g of MWCNT-PBI-Pt, 22.48 m2/g of MWCNT-Nafion-Pt, and 20.85 m2/g of MWCNT-PTFE-Pt, compared to pristine MWCNT-Pt (17.66 m2/g). Therefore, it can be concluded that the additional ionomer phase conducting the ionic species to oxygen reduction in the catalyst layer could be favorable for the ORR reaction

Ionic Liquid in Phosphoric Acid-Doped Polybenzimidazole (PA-PBI) as Electrolyte Membranes for PEM Fuel Cells: A Review

Increasing world energy demand and the rapid depletion of fossil fuels has initiated explorations for sustainable and green energy sources. High-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) are viewed as promising materials in fuel cell technology due to several advantages, namely improved kinetic of both electrodes, higher tolerance for carbon monoxide (CO) and low crossover and wastage. Recent technology developments showed phosphoric acid-doped polybenzimidazole (PA-PBI) membranes most suitable for the production of polymer electrolyte membrane fuel cells (PEMFCs). However, drawbacks caused by leaching and condensation on the phosphate groups hindered the application of the PA-PBI membranes. By phosphate anion adsorption on Pt catalyst layers, a higher volume of liquid phosphoric acid on the electrolyte–electrode interface and within the electrodes inhibits or even stops gas movement and impedes electron reactions as the phosphoric acid level grows. Therefore, doping techniques have been extensively explored, and recently ionic liquids (ILs) were introduced as new doping materials to prepare the PA-PBI membranes. Hence, this paper provides a review on the use of ionic liquid material in PA-PBI membranes for HT-PEMFC applications. The effect of the ionic liquid preparation technique on PA-PBI membranes will be highlighted and discussed on the basis of its characterization and performance in HT-PEMFC applications

Use of Fe3O4 Nanoparticles for Enhancement of Biosensor Response to the Herbicide 2,4-Dichlorophenoxyacetic Acid

Magnetic nanoparticles of Fe3O4 were synthesized and characterized using transmission electron microscopy and X-ray diffraction. The Fe3O4 nanoparticles were found to have an average diameter of 5.48 ±1.37 nm. An electrochemical biosensor based on immobilized alkaline phosphatase (ALP) and Fe3O4 nanoparticles was studied. The amperometric biosensor was based on the reaction of ALP with the substrate ascorbic acid 2-phosphate (AA2P). The incorporation of the Fe3O4 nanoparticles together with ALP into a sol gel/chitosan biosensor membrane has led to the enhancement of the biosensor response, with an improved linear response range to the substrate AA2P (5-120 μM) and increased sensitivity. Using the inhibition property of the ALP, the biosensor was applied to the determination of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). The use of Fe3O4 nanoparticles gives a two-fold improvement in the sensitivity towards 2,4-D, with a linear response range of 0.5-30 μgL-1. Exposure of the biosensor to other toxicants such as heavy metals demonstrated only slight interference from metals such as Hg2+, Cu2+, Ag2+ and Pb2+. The biosensor was shown to be useful for the determination of the herbicide 2, 4-D because good recovery of 95-100 percent was obtained, even though the analysis was performed in water samples with a complex matrix. Furthermore, the results from the analysis of 2,4-D in water samples using the biosensor correlated well with a HPLC method

Hybrid Composite Membrane of Phosphorylated Chitosan/Poly (Vinyl Alcohol)/Silica as a Proton Exchange Membrane

Chitosan is one of the natural biopolymers that has been studied as an alternative material to replace Nafion membranes as proton change membranes. Nevertheless, unmodified chitosan membranes have limitations including low proton conductivity and mechanical stability. The aim of this work is to study the effect of modifying chitosan through polymer blending with different compositions and the addition of inorganic filler on the microstructure and physical properties of N-methylene phosphonic chitosan/poly (vinyl alcohol) (NMPC/PVA) composite membranes. In this work, the NMPC biopolymer and PVA polymer are used as host polymers to produce NMPC/PVA composite membranes with different compositions (30–70% NMPC content). Increasing NMPC content in the membranes increases their proton conductivity, and as NMPC/PVA-50 composite membrane demonstrates the highest conductivity (8.76 × 10−5 S cm−1 at room temperature), it is chosen to be the base membrane for modification by adding hygroscopic silicon dioxide (SiO2) filler into its membrane matrix. The loading of SiO2 filler is varied (0.5–10 wt.%) to study the influence of filler concentration on temperature-dependent proton conductivity of membranes. NMPC/PVA-SiO2 (4 wt.%) exhibits the highest proton conductivity of 5.08 × 10−4 S cm−1 at 100 °C. In conclusion, the study shows that chitosan can be modified to produce proton exchange membranes that demonstrate enhanced properties and performance with the addition of PVA and SiO2

Effect of Modified Natural Filler O-Methylene Phosphonic κ-Carrageenan on Chitosan-Based Polymer Electrolytes

The potential for using O-methylene phosphonic κ-carrageenan (OMPk) as a filler in the chitosan-based polymer electrolyte N-methylene phosphonic chitosan (NMPC) was investigated. OMPk, a derivative of κ-carrageenan, was synthesized via phosphorylation and characterized using infrared spectroscopy (IR) and nuclear magnetic resonance (NMR). Both the IR and NMR results confirmed the phosphorylation of the parent carrageenan. The solid polymer electrolyte (SPE)-based NMPC was prepared by solution casting with different weight percentages of OMPk ranging from 2 to 8 wt %. The tensile strength of the polymer membrane increased from 18.02 to 38.95 MPa as the amount of OMPk increased to 6 wt %. However, the increase in the ionic conductivity did not match the increase in the tensile strength. The highest ionic conductivity was achieved with 4 wt % OMPk, which resulted in 1.43 × 10−5 Scm−1. The κ-carrageenan-based OMPk filler strengthened the SPE while maintaining an acceptable level of ionic conductivity

Synthesis and characterization of modified κ-carrageenan for enhanced proton conductivity as polymer electrolyte membrane.

Polymer electrolyte membranes based on the natural polymer κ-carrageenan were modified and characterized for application in electrochemical devices. In general, pure κ-carrageenan membranes show a low ionic conductivity. New membranes were developed by chemically modifying κ-carrageenan via phosphorylation to produce O-methylene phosphonic κ-carrageenan (OMPC), which showed enhanced membrane conductivity. The membranes were prepared by a solution casting method. The chemical structure of OMPC samples were characterized using Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance (1H NMR) spectroscopy and 31P nuclear magnetic resonance (31P NMR) spectroscopy. The conductivity properties of the membranes were investigated by electrochemical impedance spectroscopy (EIS). The characterization demonstrated that the membranes had been successfully produced. The ionic conductivity of κ-carrageenan and OMPC were 2.79 × 10-6 S cm-1 and 1.54 × 10-5 S cm-1, respectively. The hydrated membranes showed a two orders of magnitude higher ionic conductivity than the dried membranes