A Mechanistic Overview of the Current Status and Future Challenges of Aluminum Anode and Electrolyte in Aluminum-Air Batteries.

Aluminum-air batteries (AABs) are regarded as attractive candidates for usage as an electric vehicle power source due to their high theoretical energy density (8100 Wh kg-1 ), which is considerably higher than that of lithium-ion batteries. However, AABs have several issues with commercial applications. In this review, we outline the difficulties and most recent developments in AABs technology, including electrolytes and aluminum anodes, as well as their mechanistic understanding. First, the impact of the Al anode and alloying on battery performance is discussed. Then we focus on the impact of electrolytes on battery performances. The possibility of enhancing electrochemical performances by adding inhibitors to electrolytes is also investigated. Additionally, the use of aqueous and non-aqueous electrolytes in AABs is also discussed. Finally, the challenges and potential future research areas for the advancement of AABs are suggested.

A Mechanistic Overview of the Current Status and Future Challenges in Air Cathode for Aluminum Air Batteries.

Aluminum air batteries (AABs) are a desirable option for portable electronic devices and electric vehicles (EVs) due to their high theoretical energy density (8100 Wh K-1 ), low cost, and high safety compared to state-of-the-art lithium-ion batteries (LIBs). However, numerous unresolved technological and scientific issues are preventing AABs from expanding further. One of the key issues is the catalytic reaction kinetics of the air cathode as the fuel (oxygen) for AAB is reduced there. Additionally, the performance and price of an AAB are directly influenced by an air electrode integrated with an oxygen electrocatalyst, which is thought to be the most crucial element. In this study, we covered the oxygen chemistry of the air cathode as well as a brief discussion of the mechanistic insights of active catalysts and how they catalyze and enhance oxygen chemistry reactions. There is also extensive discussion of research into electrocatalytic materials that outperform Pt/C such as nonprecious metal catalysts, metal oxide, perovskites, metal-organic framework, carbonaceous materials, and their composites. Finally, we provide an overview of the present state, and possible future direction for air cathodes in AABs.

Preface to the Special Issue on Recent Advances in Electrochemical Energy Storage.

Energy conversion, consumption, and storage technologies are essential for a sustainable energy ecosystem. Energy storage technologies like batteries, supercapacitors, and fuel cells bridge the gap between energy conversion and consumption, ensuring a reliable energy supply. From ancient methods to modern advancements, research has focused on improving energy storage devices. Challenges remain, including performance, environmental impact and cost, but ongoing research aims to overcome these limitations. A special issue titled "Recent Advances in Electrochemical Energy Storage" presents cutting-edge progress and inspiring further development in energy storage technologies.

Transition-metal-based Catalysts for Electrochemical Synthesis of Ammonia by Nitrogen Reduction Reaction: Advancing the Green Ammonia Economy.

Ammonia (NH3 ), a cornerstone in the chemical industry, has historically been pivotal for producing various valuable products, notably fertilizers. Its significance is further underscored in the modern energy landscape, where NH3 is seen as a promising medium for hydrogen storage and transportation. However, the conventional Haber-Bosch process, which accounts for approximately 170 million ton of NH3 produced globally each year, is energy-intensive and environmentally damaging. The electrochemical nitrogen reduction reaction (NRR) emerges as a sustainable alternative that operates in ambient conditions and uses renewable energy sources. Despite its potential, the NRR faces challenges, including the inherent stability of nitrogen and its competition with the hydrogen evolution reaction. Transition metals, especially ruthenium (Ru) and molybdenum (Mo), have demonstrated promise as catalysts, enhancing the efficiency of the NRR. Ru excels in catalytic activity, while Mo offers robustness. Strategies like heteroatom doping are being pursued to mitigate NRR challenges, especially the competing hydrogen evolution reaction. This review delves into the advancements of Ru and Mo-based catalysts for electrochemical ammonia synthesis, elucidating the NRR mechanisms, and championing the transition towards a greener ammonia economy. It also seeks to elucidate the core principles underpinning the NRR mechanism. This shift aims not only to address challenges inherent to traditional production methods but also to align with the overarching goals of global sustainability.

Facile Chemical Synthesis of Co-Ru-Based Heterometallic Supramolecular Polymer for Electrochemical Oxidation of Bisphenol A: Kinetics Study at the Electrode/Electrolyte Interface.

Regardless of the adverse effects of Bisphenol A (BPA), its use in industry and in day-to-day life is increasing at a higher rate every year. In the present study, a simple and reliable chemical approach was used to develop an efficient BPA sensor based on a Co-Ru-based heterometallic supramolecular polymer (polyCoRu). Surface morphology and elemental analysis were examined using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Furthermore, functional group analysis was accomplished by Fourier transform infrared spectroscopy (FT-IR). UV-vis spectroscopy was used to confirm the complexation in the ratio of 0.5:0.5:1 (metal 1/metal 2/ligand). Electrochemical characterization of the synthesized polyCoRu was conducted using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analyses. The study identified two distinct linear dynamic ranges for the detection of BPA, 0.197-2.94 and 3.5-17.72 µM. The regression equation was utilized to determine the sensitivity and limit of detection (LOD), resulting in values of 0.6 µA cm-2 µM-1 and 0.02 µM (S/N = 3), respectively. The kinetics of BPA oxidation at the polyCoRu/GCE were investigated to evaluate the heterogeneous rate constant (k), charge transfer coefficient (α), and the number of electrons transferred during the oxidation and rate-determining step. A probable electrochemical reaction mechanism has been presented for further comprehending the phenomena occurring at the electrode surface. The practical applicability of the fabricated electrode was analyzed using tap water, resulting in a high percentage of recovery ranging from 96 to 105%. Furthermore, the reproducibility and stability data demonstrated the excellent performance of polyCoRu/GCE.

Intrinsic Properties of GO/RGO Bilayer Electrodes Dictate Their Inter-/Intralayer Intractability to Modulate Their Capacitance Performance.

The demand for high-capacity energy storage along with high power output and faster charging has made supercapacitors a key area of energy research. The charge storage capacity of capacitors is largely dependent on the electrode materials utilized. To that end, graphene oxide (GO) and reduced GO (RGO) have been extensively employed for preparing supercapacitors. However, to date, no study has reported utilizing a GO/RGO bilayer electrode material for supercapacitor application. Herein, we report the synthesis of GO/RGO bilayer electrodes on fluorine-doped tin oxide (FTO) conducting substrates with four different combinations, namely, RGO-RGO, RGO-GO, GO-RGO, and GO-GO. Electrochemical capacitance analysis based on a symmetrical electrode configuration revealed that FTO-GO-RGO electrodes had the best areal capacitance performance. However, the highest specific areal capacitance (27.85 mF/cm2) for both symmetric/asymmetric configurations was achieved with FTO-GO-RGO as the anode and FTO-GO-GO as the cathode. The heterogeneous capacitance performance of the GO/RGO bilayer systems was analyzed based on structural characterization and computational simulation methods. Based on our analysis, we identified that inter-/intralayer molecular interaction of the GO/RGO bilayer sheets through the confinement pressure effect might have prompted their unique physicochemical properties. This work highlights the importance of probing multilayer GO/RGO electrode fabrication methods for preparation of high-capacity supercapacitors through fine-tuning their structural and molecular properties.

Nanostructured Nickel-based Non-enzymatic Electrochemical Glucose Sensors.

Glucose detection is considered a significant area and has remained the topic of considerable attention. Remarkable technological advancements have been observed in diabetes monitoring in the past decades. This continual progress helps to track recent trends in development as well as identify challenging issues in glucose sensor construction. Thus, a comprehensive synopsis of the most recent advancements and developments in the study of nickel (Ni) nanostructure-based sensors for efficient trace-level glucose detection, following non-enzymatic and electrochemical methods, is provided in this review. Moreover, this review is intensively focused on the methodologies for the structure, morphology, preparation, and enforcement of a variety of Ni nanostructures, including Ni nanosheets with metals, Ni nanospheres with metals/mixed metals, Ni-metal nanocomposites, metal nanoparticles-decorated Ni nanowires, Ni nanoparticles, Ni-decorated metal nanotube arrays, Ni nanoneedles and nanorods with metals, nanoporous, nanoplates, nanocoated Ni with metal composites, and Ni-composed hybrid nanostructures. Various demonstrations and categorizations are provided on Ni-based nanostructures for a clear understanding for diverse readers.

Recent Advances in Carbon and Metal Based Supramolecular Technology for Supercapacitor Applications.

As the world moves towards renewable and sustainable energy sources, the need for systems that can quickly and safely store this energy is also rising. Supercapacitors (SCs) are among the most promising alternatives to conventional lithium-ion batteries. SCs are more stable, have higher-power densities, and can be charged much faster. However, SCs have their issues, and three of the main drawbacks of current SCs are 1) lower energy densities, 2) high cost of production, and 3) safety concerns in wearable devices. In this review, we discuss recent progress made in supramolecule-based SCs (SSCs). In supramolecular systems, molecules are held stable using non-covalent-type bonds. This allows for a flexible system in which the molecular interaction sites can easily break and reform at low energy, allowing for exposure of highly active sites and self-healing. When heterometal atoms are introduced into these supramolecular systems, this allows for further activation of the metal sites through the metal-metal interaction along with the metal-ligand interactions. This review discusses different types of SSCs (carbon-based and metal-incorporated) that have been utilized in recent years depending on their synthesis process. The working principle of SSCs and the utilization of different supramolecular elements that enhance the performance of SCs have also been discussed.

Recent Advancements in Electrochemical Deposition of Metal-Based Electrode Materials for Electrochemical Supercapacitors.

The demand for energy storage devices with high energy and power densities has increased tremendously in this rapidly growing world. Conventional capacitors, fuel cells, and lithium-ion batteries have been used as energy storage devices for the long term. However, supercapacitors are one of the most promising energy storage devices because of their high specific capacitance, high power density, and longer cycle life. Recent research has focused on synthesizing transition-metal oxides/hydroxides, carbon materials, and conducting polymers as supercapacitor electrode materials. The performance of supercapacitors can be improved by altering electrolytes, electrode materials, current collectors, experimental temperatures, and film thickness. Thousands of papers on supercapacitors have already been published, reflecting the significance and elucidating how much demanding such energy storage devices for this fast-growing generation. This review aims to illustrate the electrode materials loaded on various conductive substrates by electrochemical deposition employed for supercapacitors to provide broad knowledge on synthetic pathways, which will pave the way for future research. We also discussed the basic parameters involved in supercapacitor studies and the advantages of the electrochemical deposition techniques through literature analysis. Finally, future trends and directions on exploring metals/metal composites toward designing and constructing viable, high-class, and even newly featured flexible energy storage materials, electrodes, and systems are presented.

Graphene and Carbon Nanotube-based Electrochemical Sensing Platforms for Dopamine.

Dopamine (DA) is an important neurotransmitter, which is created and released from the central nervous system. It plays a crucial role in human activities, like cognition, emotions, and response to anything. Maladjustment of DA in human blood serum results in different neural diseases, like Parkinson's and Schizophrenia. Consequently, researchers have started working on DA detection in blood serum, which is undoubtedly a hot research area. Electrochemical sensing techniques are more promising to detect DA in real samples. However, utilizing conventional electrodes for selective determination of DA encounters numerous problems due to the coexistence of other materials, such as uric acid and ascorbic acid, which have an oxidation potential close to DA. To overcome such problems, researchers have put their focus on the modification of bare electrodes. The aim of this review is to present recent advances in modifications of most used bare electrodes with carbonaceous materials, especially graphene, its derivatives, and carbon nanotubes, for electrochemical detection of DA. A brief discussion about the mechanistic phenomena at the electrode interface has also been included in this review.

Metal Nanoparticles for Electrochemical Sensing: Progress and Challenges in the Clinical Transition of Point-of-Care Testing.

With the rise in public health awareness, research on point-of-care testing (POCT) has significantly advanced. Electrochemical biosensors (ECBs) are one of the most promising candidates for the future of POCT due to their quick and accurate response, ease of operation, and cost effectiveness. This review focuses on the use of metal nanoparticles (MNPs) for fabricating ECBs that has a potential to be used for POCT. The field has expanded remarkably from its initial enzymatic and immunosensor-based setups. This review provides a concise categorization of the ECBs to allow for a better understanding of the development process. The influence of structural aspects of MNPs in biocompatibility and effective sensor design has been explored. The advances in MNP-based ECBs for the detection of some of the most prominent cancer biomarkers (carcinoembryonic antigen (CEA), cancer antigen 125 (CA125), Herceptin-2 (HER2), etc.) and small biomolecules (glucose, dopamine, hydrogen peroxide, etc.) have been discussed in detail. Additionally, the novel coronavirus (2019-nCoV) ECBs have been briefly discussed. Beyond that, the limitations and challenges that ECBs face in clinical applications are examined and possible pathways for overcoming these limitations are discussed.

Green Synthesis of Gold and Silver Nanoparticles by Using Amorphophallus paeoniifolius Tuber Extract and Evaluation of Their Antibacterial Activity.

In this report, we discussed rapid, facile one-pot green synthesis of gold and silver nanoparticles (AuNPs and AgNPs) by using tuber extract of Amorphophallus paeoniifolius, and evaluated their antibacterial activity. AuNPs and AgNPs were synthesized by mixing their respective precursors (AgNO3 and HAuCl4) with tuber extract of Amorphophallus paeoniifolius as the bio-reducing agent. Characterization of AuNPs and AgNPs were confirmed by applying UV-vis spectroscopy, field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), and energy dispersive X-ray spectroscopy (EDS). From UV-vis characterization, surface plasmon resonance spectra were found at 530 nm for AuNPs and 446 nm for AgNPs. XRD data confirmed that both synthesized nanoparticles were face-centered cubic in crystalline nature, and the average crystallite sizes for the assign peaks were 13.3 nm for AuNPs and 22.48 nm for AgNPs. FTIR data evaluated the characteristic peaks of different phytochemical components of tuber extract, which acted as the reducing agent, and possibly as stabilizing agents. The antibacterial activity of synthesized AuNPs and AgNPs were examined in Muller Hinton agar, against two Gram-positive and four Gram-negative bacteria through the disc diffusion method. AuNPs did not show any inhibitory effect, while AgNPs showed good inhibitory effect against both Gram-positive and Gram-negative bacteria.

Enhancing the Performance of Dye Sensitized Solar Cells Using Silver Nanoparticles Modified Photoanode.

In this study, silver nanoparticles were synthesized, characterized, and applied to a dye-sensitized solar cell (DSSC) to enhance the efficiency of solar cells. The synthesized silver nanoparticles were characterized with UV-Vis spectroscopy, dynamic light scattering, transmission electron microscopy, and field emission scanning electron microscopy. The silver nanoparticles infused titanium dioxide film was also characterized by Fourier transform infrared and Raman spectroscopy. The performance of DSSC fabricated with silver nanoparticle-modified photoanode was compared with that of a control group. The current and voltage characteristics of the devices as well as the electrochemical impedance measurements were also carried out to assess the performance of the fabricated solar cells. The solar-to-electric efficiency of silver nanoparticles based DSSC was 1.76%, which is quite remarkable compared to the 0.98% realized for DSSC fabricated without silver nanoparticles.

Computational Approach to Understanding the Electrocatalytic Reaction Mechanism for the Process of Electrochemical Oxidation of Nitrite at a Ni-Co-Based Heterometallo-Supramolecular Polymer.

Here, we report a semiempirical quantum chemistry computational approach to understanding the electrocatalytic reaction mechanism (ERM) of a metallic supramolecular polymer (SMP) with nitrite through UV/vis spectral simulations of SMP with different metal oxidation states before and after interactions with nitrite. In one of our recent works, by analyzing the electrochemical experimental data, we showed that computational cyclic voltammetry simulation (CCVS) can be used to predict the possible ERM of heterometallo-SMP (HMSMP) during electrochemical oxidation of nitrite (Islam T.ACS Appl. Polym. Mater.2020, 2( (2), ), 273-284). However, CCVS cannot predict how the ERM happens at the molecular level. Thus, in this work, we simulated the interactions between the repeating unit (RU) of the HMSMP polyNiCo and nitrite to understand how the oxidation process took place at the molecular level. The RU for studying the ERM was confirmed through comparing the simulated UV/vis and IR spectra with the experimental spectra. Then, the simulations between the RU of the polyNiCo and various species of nitrite were done for gaining insights into the ERM. The simulations revealed that the first electron transfer (ET) occurred through coordination of NO2 - with either of the metal centers during the two-electron-transfer oxidation of nitrite, while the second ET followed a ligand-ligand charge transfer (LLCT) and metal-ligand charge transfer (MLCT) pathway between the NO2 species and the RU. This ET pathway has been proposed by analyzing the transition states (TSs), simulated UV/vis spectra, energy of the optimized systems, and highest occupied molecular orbital-lowest occupied molecular orbital (HOMO-LUMO) interactions from the simulations between the RU and nitrite species.

Green Chemistry Synthesis of Silver Nanoparticles and Their Potential Anticancer Effects.

Nanobiotechnology has grown rapidly and become an integral part of modern disease diagnosis and treatment. Biosynthesized silver nanoparticles (AgNPs) are a class of eco-friendly, cost-effective and biocompatible agents that have attracted attention for their possible biomedical and bioengineering applications. Like many other inorganic and organic nanoparticles, such as AuNPs, iron oxide and quantum dots, AgNPs have also been widely studied as components of advanced anticancer agents in order to better manage cancer in the clinic. AgNPs are typically produced by the action of reducing reagents on silver ions. In addition to numerous laboratory-based methods for reduction of silver ions, living organisms and natural products can be effective and superior source for synthesis of AgNPs precursors. Currently, plants, bacteria and fungi can afford biogenic AgNPs precursors with diverse geometries and surface properties. In this review, we summarized the recent progress and achievements in biogenic AgNPs synthesis and their potential uses as anticancer agents.

Porous tal palm carbon nanosheets: preparation, characterization and application for the simultaneous determination of dopamine and uric acid.

A novel porous tal palm carbon nanosheet (PTPCN) material was synthesized from the leaves of Borassus flabellifer (tal palm) and used for developing an electrochemical sensor through modifying a glassy carbon electrode (GCE) simply by drop-casting on it a solution of the material for the sensitive simultaneous detection of dopamine (DA) and uric acid (UA), even in the presence of interfering species. The drop-casting solution was prepared by simply dispersing the PTPCNs in ethanol without using any other binding materials (e.g. Nafion). The surface morphologies of the PTPCNs were studied through field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high resolution TEM (HRTEM). Energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction spectroscopy (XPS) studies revealed the chemical composition of the PTPCNs' surface. Their structural properties were studied using X-ray diffraction (XRD) and Raman spectroscopy. Brunauer-Emmett-Teller (BET) analysis confirmed the surface area and pore volume to be 1094.53 m2 g-1 and 0.74 cm3 g-1, respectively, while Barrett-Joyner-Halenda (BJH) pore-size distribution showed the average pore size to be 22 nm. The sufficiently large surface area and pore-size distribution suggested better electrocatalytic properties compared to the average modifying materials. The modified electrode (PTPCNs/GCE) was characterized through impedimetric and CV techniques in standard potassium ferricyanide solution for evaluating their charge-transfer resistance and electrochemical properties. The limits of detection (S/N = 3) were 0.17 µM and 0.078 µM and the sensitivities were 1.2057 µA µM-1 cm-2 and 2.693 µA µM-1 cm-2 for UA and DA, respectively. The possible interactions that took place between the PTPCNs and the analytes that aided in the enhancement of the electroanalytical performance of the PTPCNs/GCE are discussed based on the experimental findings and established theoretical concepts. The PTPCNs/GCE was successfully employed for analyzing real samples, like dopamine injection and urine.

TiO2 paste formulation for crack-free mesoporous nanocrystalline film of dye-sensitized solar cells.

Using a doctor-blade method, a highly viscous titanium dioxide (TiO2) paste was deposited on a glass substrate coated with fluorine doped tin oxide (FTO). The paste was mainly composed of commercially available TiO2 nanoparticles (P25) and hydroxypropyl cellulose (HPC) as organic filler. Varying the content of HPC in the TiO2 paste changed the physical properties of the mesoporous TiO2 layer, particularly its porosity and surface area. From the quantification of dyes on Ti2, layer and the electrochemical impedance spectroscopy (EIS) study of the dye-sensitized solar cells (DSSCs), the surface area of the TiO2 film was found to have decreased. This came with the increase of HPC content while the porosity of the film increased, consistent with the concurrent decrease of short-circuit current density (Jsc) and efficiency (eta). The increased porosity greatly affected the electron transport through the TiO2 film by decreasing the coordination number of the TiO2 particles resulting to a decrease of the electron diffusion coefficient.

Carbon nanotubes on fluorine-doped tin oxide for fabrication of dye-sensitized solar cells at low temperature condition.

The multi-walled carbon nanotubes (MWCNTs), electrophoretically deposited on fluorine-doped tin oxide (FTO), were employed as charge-collecting channels in the TiO2 photoelectrode of dye-sensitized solar cells (DSSCs) fabricated at 200 degrees C. The CNT-networks at the conducting substrate increased the charge collection efficiency of the porous TiO2 film, while the short circuit current increased up to ca. 43% under optimized condition. However, the significant decrease in the open-circuit voltage (Voc) up to ca. 132 mV resulted in the failure of the overall cell efficiency improvement. Findings reveal that the transfer process for the back electron is mainly responsible for the significant Voc drop when the MWCNTs were deposited at the electron-collecting substrate of the photoelectrode. The study demonstrates that electrophoretic deposition of MWCNTs on charge collecting substrate would be applicable to introduce an effective charge-collecting channel for the fabrication of flexible DSSCs under low temperature sintering condition.

Fermi energy level tuning for high performance dye sensitized solar cells using sp2 selective nitrogen-doped carbon nanotube channels.

Here, we find that doping sp(2) selective nitrogen, N sp(2), into carbon nanotube (CNT) channels induces a positive shift in the Fermi level of TiO(2) photoelectrodes. It is found that this results in the large diffusion coefficient of solar driven electrons for increasing the photocurrent as well as in the low recombination rate for improving open circuit voltage with 0.74 V, which could not be overcome by using pristine CNT channels with 0.66 V.

Spatial arrangement of carbon nanotubes in TiO2 photoelectrodes to enhance the efficiency of dye-sensitized solar cells.

Three electrode structures with different spatial arrangements of carbon nanotubes (CNTs) in the mesoporous TiO(2) layer were employed in dye-sensitized solar cells to study the effect of surface states at the interface formed by the incorporation of CNTs. It was found that the decay of open circuit voltage (V(oc)) was significantly minimized by avoiding the direct contact of nanotubes to the conducting substrate by introducing a thin buffer layer of TiO(2) while maintaining the superior electron collection efficiency from the incorporation of nanotubes.