Electrochem, Volume 3, Issue 1 (March 2022) – 11 articles

Ferrocene-based porous organic polymers (FPOPs) were prepared from phenol-formaldehyde polymer (Bakelite) and phenol as starting materials; and two possible mechanisms for polymerization were discussed. Solid-state ¹³C CP-MAS NMR, FTIR, powder XRD, elemental analysis and ICP (Fe, Na, B) were performed to characterize the prepared materials. The two synthetic approaches produced polymers with different pore sizes: the FPOP synthesized through Bakelite presented a higher surface area (52 m² g⁻¹) when compared to the one obtained by the bottom-up polymerization from phenol (only 5 m² g⁻¹). Thermogravimetric analysis confirmed the thermal stability of the material, which decomposed at 350 °C. Furthermore, cyclic voltammetry (CV) of the new FPOP on modified electrodes, in ACN and 0.1 M TBAP as an electrolyte, showed fully reversible electron transfer, which is similar to that observed for the ferrocene probe dissolved in the same electrolyte. As a proof-of-concept for an electrochromic device, this novel material was also tested, with a color change detected between yellow/brownish coloration (reduced form) and green/blue coloration (oxidized form). The new hybrid FPOP seems very promising for material science, energy storage and electrochromic applications, as well as for plastic degradation. Full article

In the present era, different allotropes of carbon have been discovered, and graphene is the one among them that has contributed to many breakthroughs in research. It has been considered a promising candidate in the research and academic fields, as well as in industries, over the last decade. It has many properties to be explored, such as an enhanced specific surface area and beneficial thermal and electrical conductivities. Graphene is arranged as a 2D structure by organizing sp² hybridized C with alternative single and double bonds, providing an extended conjugation combining hexagonal ring structures to form a honeycomb structure. The precious structure and outstanding characteristics are the major reason that modern industry relies heavily on graphene, and it is predominantly applied in electronic devices. Nowadays, lithium-ion batteries (LIBs) foremostly utilize graphene as an anode or a cathode, and are combined with polymers to use them as polymer electrolytes. After three decades of commercialization of the lithium-ion battery, it still leads in consumer electronic society due to its higher energy density, wider operating voltages, low self-discharge, noble high-temperature performance, and fewer maintenance requirements. In this review, we aim to give a brief review of the domination of graphene and its applications in LIBs. Full article

The development of energy storage devices with better performance relies on the use of innovative materials and electrolytes, aiming to reduce the carbon footprint through the screening of low toxicity electrolytes and solvent-free electrode design protocols. The application of nanostructured carbon materials with high specific surface area, to prepare composite electrodes, is being considered as a promising starting point towards improving the power and energy efficiency of energy storage devices. Non-aqueous electrolytes synthesized using greener approaches with lower environmental impact make deep eutectic solvents (DES) promising alternatives for electrochemical energy storage and conversion applications. Accordingly, this work proposes a systematic study on the effect of the composition of DES containing a diol and an amide as HBD (hydrogen bond donor: 1,2-propylene glycol and urea), on the electrochemical performance of graphene and graphite composite electrodes/DES electrolyte interface. Glassy carbon (GC) was selected as the bare electrode material substrate to prepare the composite formulations since it provides an electrochemically reproducible surface. Gravimetric capacitance was measured for commercial graphene and commercial graphite/GC composite electrodes in contact with choline chloride, complexed with 1,2-propylene glycol, and urea as the HBD in 1:2 molar ratio. The electrochemical stability was followed by assessing the charge/discharge curves at 1, 2, and 4 A g⁻¹. For comparison purposes, a parallel study was performed using commercial graphite. A four-fold increase in gravimetric capacitance was obtained when replacing commercial graphite (1.70 F g⁻¹) by commercial graphene (6.19 F g⁻¹) in contact with 1,2-propylene glycol-based DES. When using urea based DES no significant change in gravimetric capacitance was observed when commercial graphite is replaced by commercial graphene. Full article

Scavenging of electrogenerated superoxide radical anion (O₂^•−) by pyrogallol (PyH₃) was investigated on the basis of cyclic voltammetry and in situ electrolytic electron spin resonance spectrum in N,N-dimethylformamide with the aid of density functional theory (DFT) calculations. Quasi-reversible dioxygen/O₂^•− redox couple was modified by the presence of PyH₃, suggesting that O₂^•− was scavenged by PyH₃ through proton-coupled electron transfer (PCET) involving two proton transfer and one electron transfer. DFT calculation suggested that the pre-reactive formation of a hydrogen-bond (HB) complex and the subsequent concerted two-proton-coupled electron transfer characterized by catechol moiety in PyH₃ is plausible mechanism that embodies the superior kinetics of the O₂^•− scavenging by PyH₃ as shown in the electrochemical results. Furthermore, it was clarified that the three hydroxyl groups of PyH₃ promote the formation of HB complex, in comparative analyses using related compounds, resulting in the promotion of the O₂^•− scavenging. Full article

Several studies have shown the development of electrochemical biosensors based on enzymes immobilized in metal–organic frameworks (MOFs). Although enzymes have unique properties, such as efficiency, selectivity, and environmental sustainability, when immobilized, these properties are improved, presenting significant potential for several biotechnological applications. Using MOFs as matrices for enzyme immobilization has been considered a promising strategy due to their many advantages compared to other supporting materials, such as larger surface areas, higher porosity rates, and better stability. Biosensors are analytical tools that use a bioactive element and a transducer for the detection/quantification of biochemical substances in the most varied applications and areas, in particular, food, agriculture, pharmaceutical, and medical. This review will present novel insights on the construction of biosensors with materials based on MOFs. Herein, we have been highlighted the use of MOF for biosensing for biomedical, food safety, and environmental monitoring areas. Additionally, different methods by which immobilizations are performed in MOFs and their main advantages and disadvantages are presented. Full article

A theoretical model of amperometric enzyme electrodes has been developed in which chemical amplification occurs in a single enzyme membrane via cyclic substrate conversion. The system is based on non-stationary diffusion equations with a nonlinear factor related to the Michaelis–Menten kinetics of the enzymatic reaction. By solving the nonlinear equations using the AGM technique, simple analytical expressions of concentration substrate, product, and amperometric current response are derived. Further, biosensor sensitivity, resistance, and gain are obtained from the current. MATLAB programming was used to carry out the digital simulation. The analytical results are validated with the numerical results. The effect of substrate concentration, maximum enzymatic rate, and membrane thickness on biosensor response was evaluated. Full article

Alkylphosphonic acids are well known for their ability to form self-assembled monolayers on hydroxide surfaces. A crucial step to understanding fundamentally how these surfaces are created is the elucidation of the interaction process that leads to such interface creation. In this study, we employed electrochemical impedance spectroscopy (EIS), Monte Carlo and molecular dynamics to understand this process. The interaction with the Cu(111) surface of three different alkylphosphonic acids (hexyl-, octyl- and decylphosphonic acids) is evaluated in an aqueous acidic and in an ethanol solution by Monte Carlo and molecular dynamics simulations, while EIS measurements are used to put in evidence the impact of the layer made in ethanol on copper protection. Nyquist diagrams of copper samples modified with an alkylphosphonic monolayer showed a higher polarization resistance that mitigates the copper corrosion in an aqueous acid medium. The phase–frequency Bode plots had higher and broader phase maxima for a modified copper surface with phosphonic moieties, which confirmed the ability of this organic layer to prevent copper corrosion. Full article

Estimating the accurate State of Charge (SOC) of a battery is important to avoid the over/undercharging and protect the battery pack from low cycle life. Current methods of SOC estimation use complex equations in the Extended Kalman Filter (EKF) and the equivalent circuit model. In this paper, we used a Feed Forward Neural Network (FNN) to estimate the SOC value accurately where battery parameters such as current, voltage, and charge are mapped directly to the SOC value at the output. A FNN could self-learn the weights with each training data point and update the model parameters such as weights and bias using a combination of two gradient descents (Adam). This model comprises the Dropout technique, which can have many neural network architectures by dropping the neuron/mode at each epoch/training cycle using the same weights and biases. Our FNN model was trained with data comprising different current rates and tested for different cycling data, for example, 5th, 10th, 20th, and 50th cycles and at a different cutoff voltage (4.5 V). The battery used for estimating the SOC value was a Na-ion based battery, which is highly non-linear, and it was fabricated in a house using Na_0.67Fe_0.5Mn_0.5O₂ (NFM) as a cathode and Na metal as a reference electrode. The FNN successfully estimated the SOC value for the highly non-linear nature of the Na-ion battery at different current rates (0.05 C, 0.1 C, 0.5 C, 1 C, 2 C), for different cycling data, and at higher cut-off voltage of –4.5 V Na^+, reaching the R² value of ~0.97–~0.99, ~0.99, and ~0.98, respectively. Full article

The corrosion behavior of mild steel in a 1 M aqueous sulfuric acid medium in the presence and absence of the drug Pantoprazole was investigated using potentiodynamic polarization and quantum chemical calculations as well as Monte Carlo and molecular dynamic simulations. The potentiodynamic experiments indicated that this molecule, as a result of its adsorption on a mild steel surface, functioned as a mixed inhibitor. The goal of the study was to use theoretical calculations to acquire a better understanding of how inhibition works. The adsorption behavior of the examined compounds on the Fe (1 1 0) surface was calculated using a Monte Carlo simulation. Furthermore, the molecules were studied using density functional theory (DFT), especially the PBE functional, to determine the relationship between the molecular structure and the corrosion inhibition behavior of the chemical under research. The adsorption energies of Pantoprazole (in its three different protonation states) iron were calculated more precisely using molecular mechanics with periodic boundary conditions (PBC). The predicted theoretical parameters were found to be in agreement with the experimental data, which was a considerable help in understanding the corrosion inhibition mechanism displayed by this chemical. Full article

Fuel cells are a promising alternative to non-renewable energy production industries such as petroleum and natural gas. The cathodic oxygen reduction reaction (ORR), which makes fuel cell technology possible, is sluggish under normal conditions. Thus, catalysts must be used to allow fuel cells to operate efficiently. Traditionally, platinum (Pt) catalysts are often utilized as they exhibit a highly efficient ORR with low overpotential values. However, Pt is an expensive and precious metal, posing economic problems for commercialization. Herein, advances in carbon-based catalysts are reviewed for their application in ORRs due to their abundance and low-cost syntheses. Various synthetic methods from different renewable sources are presented, and their catalytic properties are compared. Likewise, the effects of heteroatom and non-precious metal doping, surface area, and porosity on their performance are investigated. Carbon-based support materials are discussed in relation to their physical properties and the subsequent effect on Pt ORR performance. Lastly, advances in fuel cell electrolytes for various fuel cell types are presented. This review aims to provide valuable insight into current challenges in fuel cell performance and how they can be overcome using carbon-based materials and next generation electrolytes. Full article