Electrochem, Volume 3, Issue 3 (September 2022) – 16 articles

Mass transport of different species plays a crucial role in electrochemical conversion of CO${}_2$ due to the solubility limit of CO${}_2$ in aqueous electrolytes. In this study, we investigate the transport of CO${}_2$ and other ionic species through the electrolyte and the membrane, and its impact on the scale-up process of HCOO${}^{-}$/HCOOH formation. The mass transport of ions to the electrode and the membrane is modelled at constant current density. The mass transport limitations of CO${}_2$ on the formation of HCOO${}^{-}$/HCOOH is investigated at different pressures ranges from 5–40 bar. The maximum achievable partial current density of formate/formic acid is increased with increasing CO${}_2$ pressure. We use an ion exchange membrane model to understand the ion transport behaviour for both the monopolar and bipolar membranes. The cation exchange (CEM) and anion exchange membrane (AEM) model show that ion transport is limited by the electrolyte salt concentrations. For 0.1 M KHCO${}_3$, the AEM reaches the limiting current density more quickly than the CEM. For the BPM model, ion transport across the diffusion layer on either side of the BPM is also included to understand the concentration polarization across the BPM. The model revealed that the polarization losses across the bipolar membrane depend on the pH of the electrolyte used for the CO${}_2$ reduction reaction (CO₂RR). The polarization loss on the anolyte side decreases with an increasing pH, while, on the cathode side, it increases with increasing catholyte pH. With this combined model for the electrode reactions and the membrane transport, we are able to account for the various factors influencing the polarization losses in the CO${}_2$ electrolyzer. To complete the analysis, we simulated the full cell polarization curve and fitted with the experimental data. Full article

Electrochemical immunosensors are often described as innovative strategies to tackle urgent epidemiological needs, such as the detection of SARS-CoV-2 main biomarker, the spike glycoprotein. Nevertheless, there is a great variety of receptors, especially recombinant antibodies, that can be used to develop these biosensing platforms, and very few reports compare their suitability in analytical device design and their sensing performances. Therefore, this short report targeted a brief and straightforward investigation of the performance of different impedimetric biorecognition surfaces (BioS) for SARS-CoV-2, which were crafted from three commonly reported recombinant antibodies and molecularly-imprinted polymer (MIP) nanoparticles (nanoMIP). The selected NanoMIP were chosen due to their reported selectivity to the receptor binding domain (RBD) of SARS-CoV-2 spike glycoprotein. Results showed that the surface modification protocol based on MUDA and crosslinking with EDC/NHS was successful for the anchoring of each tested receptor, as the semicircle diameter of the Nyquist plots of EIS increased upon each modification, which suggests the increase of R_ct due to the binding of dielectric materials on the conductive surface. Furthermore, the type of monoclonal antibody used to craft the BioS and the artificial receptors led to very distinct responses, being the RBD5305 and the NanoMIP-based BioS the ones that showcased the highest increment of signal in the conditions herein reported, which suggests their adequacy in the development of impedimetric immunosensors for SARS-CoV-2 spike glycoprotein. Full article

The design and preparation of novel, high-efficiency, and low-cost heterogeneous catalysts are important topics in academic and industry research. In the past, inorganic materials, metal oxide, and carbon materials were used as supports for the development of heterogeneous catalysts due to their excellent properties, such as high specific surface areas and tunable porous structures. However, the properties of traditional pristine carbon materials cannot keep up with the sustained growth and requirements of industry and scientific research, since the introduction of nitrogen atoms into carbon materials may significantly enhance a variety of their physicochemical characteristics, which gradually become appropriate support for synthesizing supported transition metal catalysts. In the past several decades, the transition metal anchored on nitrogen-doped carbon catalysts has attracted a tremendous amount of interest as potentially useful catalysts for diverse chemical reactions. Compared with original carbon support, the doping of nitrogen atoms can significantly regulate the physicochemical properties of carbon materials and allow active metal species uniformly dispersed on the support. The various N species in support also play a critical role in accelerating the catalytic performance in some reactions. Besides, the interaction between support and transition metal active sites can offer an anchor site to stabilize metal species during the preparation process and then improve reaction performance, atomic utilization, and stability. In this review, we highlight the recent advances and the remaining challenges in the preparation and application of transition metal anchored on nitrogen-doped carbon catalysts. Full article

A three-dimensional (3D) hybrid nanostructure of Fe₃O₄ nanoparticles uniformly anchored on vertically-aligned carbon nanotubes (VACNTs) was fabricated by a facile two-step method. Assisted by supercritical carbon dioxide (SCCO₂), the Fe precursor was firstly absorbed on CNT surface and then transformed into Fe₃O₄ nanoparticles by vacuum thermal annealing. Owing to the synergetic effects of well-distributed Fe₃O₄ nanoparticles (~7 nm) and highly conductive VACNTs, the hybrid electrode exhibits a high specific capacitance of 364.2 F g⁻¹ at 0.5 A g⁻¹ within the potential range from −0.9 to +0.1 V in Na₂SO₃ electrolyte and an excellent cycling stability of 84.8% capacitance retention after 2000 cycles at a current density of 4 A/g. This 3D hybrid architecture consisting of aligned CNTs and pseudocapacitive metal oxide may be a promising electrode for high-performance supercapacitors. Full article

Conducting polymers (CPs) are highly conjugated organic macromolecules, where the electrical charge is transported in intra- and inter-chain pathways. Polyacetylene, polythiophene and its derivatives, polypyrrole and its derivatives, and polyaniline are among the best-known examples. These compounds have been used as electrode modifiers to gain sensitivity and selectivity in a large variety of analytical applications. This review, after a brief introduction to the electrochemistry of CPs, summarizes the application of CPs’ electrode interfaces towards heavy metals’ detection using potentiometry, pulse anodic stripping voltammetry, and alternative non-classical electrochemical methods. Full article

The mathematical model proposed by Chapman and Antano (Electrochimica Acta, 56 (2010), 128–132) for the catalytic electrochemical–chemical (EC’) processes in an irreversible second-order homogeneous reaction in a microelectrode is discussed. The mass-transfer boundary layer neighbouring an electrode can contribute to the electrode’s measured AC impedance. This model can be used to analyse membrane-transport studies and other instances of ionic transport in semiconductors and other materials. Two efficient and easily accessible analytical techniques, AGM and DTM, were used to solve the steady-state non-linear diffusion equation’s infinite layers. Herein, we present the generalized approximate analytical solution for the solute, product, and reactant concentrations and current for the small experimental values of kinetic and diffusion parameters. Using the Matlab/Scilab program, we also derive the numerical solution to this problem. The comparison of the analytical and numerical/computational results reveals a satisfactory level of agreement. Full article

In this work, we report the synthesis of an active material for supercapacitors (SCs), namely α-Fe₂O₃/carbon composite (C-Fe₂O₃) made of elongated nanoparticles linearly connected into a worm-like morphology, by means of electrospinning followed by a calcination/carbonization process. The resulting active material powder can be directly processed in the form of slurry to produce SC electrodes with mass loadings higher than 1 mg cm⁻² on practical flat current collectors, avoiding the need for bulky porous substrate, as often reported in the literature. In aqueous electrolyte (6 M KOH), the so-produced C-Fe₂O₃ electrodes display capacity as high as ~140 mAh g⁻¹ at a scan rate of 2 mV s⁻¹, while showing an optimal rate capability (capacity of 32.4 mAh g⁻¹ at a scan rate of 400 mV s⁻¹). Thanks to their poor catalytic activity towards water splitting reactions, the electrode can operate in a wide potential range (−1.6 V–0.3 V vs. Hg/HgO), enabling the realization of performant quasi-symmetric SCs based on electrodes with the same chemical composition (but different active material mass loadings), achieving energy density approaching 10 Wh kg⁻¹ in aqueous electrolytes. Full article

PCBs (polychlorinated biphenyls) are a very large group of organic compounds that have between two and ten chlorine atoms attached to the biphenyl. These compounds have an acute impact as environmental pollutants, causing cancer and other adverse health effects in humans. It is therefore imperative to develop techniques for the cost-effective detection of PCBs at very low concentrations in ecosystems. In this paper, a novel label-free, indirect, competitive electrochemical immunosensor was first developed with a PCB-BSA conjugate. It is shown herein to compete with free PCBs for binding to the anti-PCB polyclonal primary antibody (IgY). Then, we used a secondary antibody to enhance the sensitivity of the sensor for the detection of PCB in a sample. It has been successfully immobilized on an 11-mercaptoundecanoic acid (11-MUA)-modified gold electrode via a carbodiimide-coupling reaction using cross-linking 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide (NHS) on the electrode surface. The immunosensor was investigated by cyclic voltammetry and differential pulse voltammetry in a standard solution of [Fe(CN)₆]^3−/4−. A linear range of 0.011–220 ng/mL⁻¹ and a limit of detection (LOD) of 0.11 ng/mL⁻¹ for PCBs detection were achieved by the developed immunosensor, showing advantages over conventional assays. The novel label-free electrochemical immunosensor discussed in this paper is a solution for simple, rapid, cost-effective sample screening in a portable, disposable format. The proposed immunosensor has good sensitivity, and it can prove to be an adequate real-time monitoring solution for PCBs in soil samples or other samples. Full article

The profiling, or fingerprinting, of distinct varieties of the Plantae kingdom is based on the bioactive ingredients, which are systematically segregated to perform their detailed analysis. The secondary products portray a pivotal role in defining the ecophysiology of distinct plant species. There is a crucial role of the profiling domain in understanding the various features, characteristics, and conditions related to plants. Advancements in variable technologies have contributed to the development of highly specific sensors for the non-invasive detection of molecules. Furthermore, many hyphenated techniques have led to the development of highly specific integrated systems that allow multiplexed detection, such as high-performance liquid chromatography, gas chromatography, etc., which are quite cumbersome and un-economical. In contrast, electrochemical sensors are a promising alternative which are capable of performing the precise recognition of compounds due to efficient signal transduction. However, due to a few bottlenecks in understanding the principles and non-redox features of minimal metabolites, the area has not been explored. This review article provides an insight to the electrochemical basis of plants in comparison with other traditional approaches and with necessary positive and negative outlooks. Studies consisting of the idea of merging the fields are limited; hence, relevant non-phytochemical reports are included for a better comparison of reports to broaden the scope of this work. Full article

Two different types of alkaloids are successfully extracted from two plants Artemisia vulgaris (AV) and Solanum tuberosum (ST) in the laboratory and used as corrosion inhibitors for mild steel samples. The corrosion inhibition potential of these alkaloids is determined by weight loss and potentiodynamic polarization measurement methods. Based on the weight loss measurement study of a sample immersed for 6 h in 1000 ppm inhibitor solution of AV and ST alkaloids, the corrosion inhibition efficiency is found to be 92.58% and 90.79%, respectively. The potentiodynamic polarization measurement shows 88.06% and 83.22% corrosion inhibition efficiency for AV and ST alkaloids, respectively, for the sample immersed for 1 h in 1000 ppm inhibitor solution. These promising efficiency and suitable immersion time effect can lead to the development of good green inhibitors. Full article

The impact of doping concentration and thickness of n-InGaN and p-InGaN regions on the power conversion efficiency of single junction-based InGaN solar cells was studied by the Silvaco ATLAS simulation software. The doping concentration 5 × 10¹⁹ cm⁻³ and 1 × 10¹⁵ cm⁻³ were optimized for n-InGaN and p-InGaN regions, respectively. The thickness of 300 nm was optimized for both n-InGaN and p-InGaN regions. The highest efficiency of 22.17% with J_sc = 37.68 mA/cm², V_oc = 0.729 V, and FF = 80.61% was achieved at optimized values of doping concentration and thickness of n-InGaN and p-InGaN regions of InGaN solar cells. The simulation study shows the relevance of the Silvaco ATLAS simulation tool, as well as the optimization of doping concentration and thickness of n- and p-InGaN regions for solar cells, which would make the development of high-performance InGaN solar cells low-cost and efficient. Full article

The amount of anodically dissolved charge of silver by linear sweep stripping voltammetry has been observed to be smaller than that of the potentiostatically deposited charge. The imbalance in the charge is opposite to the participation in the double-layer capacitance. This can be explained in terms of the negative capacitive current, which is caused by dipoles of generated redox charge (Ag⁺) with counterions (NO₃⁻). Lower concentrations of counterions may suppress the capacitance to retain the equality of the charge. This prediction is examined in this work by the oxidation of silver film at various concentrations of NO₃⁻ by anodic stripping voltammetry. The capacitance decreased with a decrease in the salt concentrations less than 0.05 mol dm⁻³. Low concentrations of salts prevent loss of the anodic charge in electroanalysis. This dependence was related with the lifespan of generated silver nitrate dipoles and is described theoretically. Full article

Here, we report the performance of a biodegradable polymer-based Plastic chip Electrode (PCE) as a current collector in supercapacitor applications. Its production was evaluated using two redox materials (conducting polymers polyaniline and poly(3,4-ethylene dioxythiophene)) and a layered material, rGO. The conducting polymers were directly deposited over the Eco-friendly PCE (EPCE) using the galvanostatic method. The rGO was prepared in the conventional way and loaded over the EPCE using a binder. Both conducting polymers and rGO showed proper specific capacitance compared to previous studies with regular current collectors. Electrodes were found highly stable during experiments in high acidic medium. The supercapacitive performance was evaluated with cyclic voltammetry, charge–discharge measurements, and impedance spectroscopy. The supercapacitive materials were also characterized for their electrical and microscopic properties. Polyaniline and PEDOT were deposited over EPCEs showing >150 Fg⁻¹ and >120 Fg⁻¹ specific capacitance, respectively, at 0.5 Ag⁻¹. rGO continued to show higher particular capacitance of >250 Fg⁻¹ with excellent charge–discharge cyclic stability. The study concludes that EPCs can be used as promising electrodes for electrical energy storage applications. Full article

A mathematical model of an ideal biotrickling filter (BF) system that inoculates a recently identified strain of Chelatococcus daeguensis TAD1 and brings about efficient nitrogen oxide treatment is discussed. The proposed model is based on nonlinear mass transport equations at the gas–biofilm interface. Using Akbari–Ganji’s technique, approximate analytical expressions for the nitric oxide concentration in the gaseous and biofilm phases were developed for all feasible system parameters. In addition, to investigate the dynamic behaviour of the system, a numerical analysis of the problem is provided using MATLAB tools. To demonstrate this new approach, graphical data are provided and quantitatively discussed. This theoretical result has good agreement with the numerical simulation (MATLAB) results for the experimental values of parameters. Full article

Reactivity of (2E)-3-(3,4-dihydroxyphenyl)prop-2-enoic acid (caffeic acid), classified as a hydroxycinnamic acid (HCA) derivative, toward electrogenerated superoxide radical anion (O₂^•−) was investigated through cyclic voltammetry, in situ electrolytic electron spin resonance spectrometry, and in situ electrolytic ultraviolet–visible spectrometry in N,N-dimethylformamide (DMF), aided by density functional theory (DFT) calculations. The quasi-reversible redox of dioxygen/O₂^•− is modified in the presence of caffeic acid, suggesting that O₂^•− is scavenged by caffeic acid through proton-coupled electron transfer. The reactivities of caffeic acid toward O₂^•− are mediated by the ortho-diphenol (catechol) moiety rather than by the acryloyl group, as experimentally confirmed in comparative analyses with other HCAs. The electrochemical and DFT results in DMF suggested that a concerted two-proton-coupled electron transfer mechanism proceeds via the catechol moiety. This mechanism embodies the superior kinetics of O₂^•− scavenging by caffeic acid. Full article

In the field of automated technology research and development, trajectory tracking plays a crucial role in the energy consumption of the vehicle’s power battery. Reducing the deviation between the actual trajectory and the reference trajectory is the focus of trajectory tracking research. This paper proposes the use of the model predictive control (MPC) method to reduce the deviation of lateral and longitudinal position between the actual driving trajectory and the reference trajectory. First, the driving conditions of the vehicle are reflected by establishing the vehicle dynamics model. Then, the MPC trajectory tracking controller is built by designing the objective function with constraints; Finally, the feasibility of this approach was verified by a joint Carsim-Simulink simulation. The simulation results show that the MPC controller designed in this paper can track the trajectory better, and reduce the lateral and longitudinal position deviation. To a certain extent, the battery energy consumption is reduced and the accuracy of the tracking trajectory and the safety of vehicle driving are improved. Full article