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An Otsu-threshold- and Canny-edge-detection-based fast Hough transform (FHT) approach to lane detection was proposed to improve the accuracy of lane detection for autonomous vehicle driving. During the last two decades, autonomous vehicles have become very popular, and it is constructive to avoid traffic accidents due to human mistakes. The new generation needs automatic vehicle intelligence. One of the essential functions of a cutting-edge automobile system is lane detection. This study recommended the idea of lane detection through improved (extended) Canny edge detection using a fast Hough transform. The Gaussian blur filter was used to smooth out the image and reduce noise, which could help to improve the edge detection accuracy. An edge detection operator known as the Sobel operator calculated the gradient of the image intensity to identify edges in an image using a convolutional kernel. These techniques were applied in the initial lane detection module to enhance the characteristics of the road lanes, making it easier to detect them in the image. The Hough transform was then used to identify the routes based on the mathematical relationship between the lanes and the vehicle. It did this by converting the image into a polar coordinate system and looking for lines within a specific range of contrasting points. This allowed the algorithm to distinguish between the lanes and other features in the image. After this, the Hough transform was used for lane detection, making it possible to distinguish between left and right lane marking detection extraction; the region of interest (ROI) must be extracted for traditional approaches to work effectively and easily. The proposed methodology was tested on several image sequences. The least-squares fitting in this region was then used to track the lane. The proposed system demonstrated high lane detection in experiments, demonstrating that the identification method performed well regarding reasoning speed and identification accuracy, which considered both accuracy and real-time processing and could satisfy the requirements of lane recognition for lightweight automatic driving systems.

Graphene is a unique nanocarbon nanostructure, which has been frequently used to form nanocomposites. Green-synthesized graphene has been focused due to environmentally friendly requirements in recent technological sectors. A very important application of green-synthesized graphene-based nanocomposite has been observed in energy storage devices. This state-of-the-art review highlights design, features, and advanced functions of polymer/green-synthesized graphene nanocomposites and their utility in supercapacitor components. Green graphene-derived nanocomposites brought about numerous revolutions in high-performance supercapacitors. The structural diversity of conjugated polymer and green graphene-based nanocomposites has facilitated the charge transportation/storage capacity, specific capacitance, capacitance retention, cyclability, and durability of supercapacitor electrodes. Moreover, the green method, graphene functionality, dispersion, and matrix–nanofiller interactions have affected supercapacitance properties and performance. Future research on innovative polymer and green graphene-derived nanocomposites may overcome design/performance-related challenging factors for technical usages.

With the development of intelligent transportation systems, research into intelligent traffic signal control has received considerable attention. To date, many traffic signal control models have been studied, where most of the models concentrate on how to minimize travel time, vehicle delay, and the number of stops or how to maximize capacity. This study introduces the Garra Rufa–inspired (GRI) algorithm, which is used to optimize traffic signal control modelling considering the number of vehicles in a queue. GRI has the characteristics of using the decision variables of the code as the operation object, directly using the objective function value for the search information, using multiple search points at the same time, and using probability search technology. Theoretical analysis of intelligent optimization and research into application methods were carried out to resolve the problem of traffic signal optimization control. The output of the GRI algorithm was compared, calibrated, and validated with SIDRA. Furthermore, to obtain more comprehensive results, the genetic algorithm (GA) and particle swarm optimization (PSO) were also compared. The results of the analysis show that the GRI decreases by 10.1% (intersection A) and 16.5% (intersection B) in the number of vehicles in the queue.

By collecting and analyzing relevant literature results, we demonstrate that the nanostructuring of polypyrrole (PPy) electrodes is a crucial strategy to achieve high performance and stability in energy devices such as fuel cells, lithium batteries and supercapacitors. In this critic and comprehensive review, we focus the attention on the electrochemical methods for deposition of PPy, nanostructures and potential applications, by analyzing the effect of different physico-chemical parameters, electro-oxidative conditions including template-based or template-free depositions and cathodic polymerization. Diverse interfaces and morphologies of polymer nanodeposits are also discussed.

Titanium and its alloys have superior electrochemical properties compared to other alloy systems due to the formation of a protective TiO2 film on metal surfaces. The ability to generate the protective oxide layer will depend upon the type of alloy to be used. The aim of this work was to characterize the electrochemical corrosion behavior of titanium Ti-CP2 and alloys Ti-6Al-2Sn-4Zr-2Mo, Ti-6Al-4V, and Ti Beta-C. Samples were anodized in 1 M H2SO4 and H3PO4 solutions with a current density of 0.025 A/cm2. Electrochemical tests on anodized alloys were carried out using a three-electrode cell and exposed in two electrolytes, i.e., 3.5 wt % NaCl and 3.5 wt % H2SO4 solutions at room temperature. Scanning electron microscopy (SEM) was used to observe the morphology of anodized surfaces. The electrochemical techniques used were cyclic potentiodynamic polarization (CPP) and electrochemical noise (EN), based on the ASTM-G61 and G199 standards. Regarding EN, two methods of data analysis were used: the frequency domain (power spectral density, PSD) and time-frequency domain (discrete wavelet transform). For non-anodized alloys, the results by CCP and EN indicate icorr values of ×10−6 A/cm2. However, under anodizing conditions, the icorr values vary from ×10−7 to ×10−9 A/cm2. The PSD Ψ0 values are higher for non-anodized alloys, while in anodized conditions, the values range from −138/−122 dBi (A2·Hz−1)1/2 to −131/−180 dBi (A2·Hz−1)1/2. Furthermore, the results indicated that the alloys anodized in the H3PO4 bath showed an electrochemical behavior that can be associated with a more homogeneous passive layer when exposed to the 3.5 wt % NaCl electrolyte. Alloys containing more beta-phase stabilizers formed a less homogeneous anodized layer. These alloys are widely used in aeronautical applications; thus, it is essential that these alloys have excellent corrosion performance in chloride and acid rain environments.

Arsenic (III) is a toxic contaminant in water bodies, especially in drinking water reservoirs, and it is a great challenge to remove it from wastewater. For the successful extraction of arsenic (III), a nanocomposite material (ZnO–CuO/g–C3N4) has been synthesized by using the solution method. The large surface area and plenty of hydroxyl groups on the nanocomposite surface offer an ideal platform for the adsorption of arsenic (III) from water. Specifically, the reduction process involves a transformation from arsenic (III) to arsenic (V), which is favorable for the attachment to the –OH group. The modified surface and purity of the nanocomposite were characterized by SEM, EDX, XRD, FT–IR, HRTEM, and BET models. Furthermore, the impact of various aspects (temperatures, pH of the medium, the concentration of adsorbing materials) on adsorption capacity has been studied. The prepared sample displays the maximum adsorption capacity of arsenic (III) to be 98% at pH ~ 3 of the medium. Notably, the adsorption mechanism of arsenic species on the surface of ZnO–CuO/g–C3N4 nanocomposite at different pH values was explained by surface complexation and structural variations. Moreover, the recycling experiment and reusability of the adsorbent indicate that a synthesized nanocomposite has much better adsorption efficiency than other adsorbents. It is concluded that the ZnO–CuO/g–C3N4 nanocomposite can be a potential candidate for the enhanced removal of arsenic from water reservoirs.

In recent years, graphene has attracted the interest of many researchers working on LIB anode materials owing to its unique 2D structure, thermal stability, and fast electron transfer. In this work, RGO/Cu/Cu2O nanocomposites were synthesized through a hydrothermal procedure. The as-prepared nanocomposites exhibited a high lithium storage capacity with improved cycling stability and great rate performance, i.e., the discharge capacity was 371.8 mAh/g after 100 cycles at a current density of 500 mA/g. These excellent properties were associated with the sheet structure symmetry of graphene enriched with the multifunctional Cu-Cu2O component, which prevented aggregation and accommodated the volume changes of the anode material during the charge–discharge tests. The RGO/Cu/Cu2O composite conferred to the LIB anode the ability to resist electrode cracking. The approach proposed in this paper can be also generalized for the synthesis of other carbon-based anode materials for LIBs.

Methanol permeation is the main issue of Nafion membranes when they are used as a polymer electrolyte membrane (PEM) in direct methanol fuel cells (DMFCs). In the current study, novel nanocomposite polymer membranes are prepared by the integration of surface-modified sepiolite (MS) in polyvinylidene fluoride grafted polystyrene (PVDF-g-PS) copolymer as PEM in DMFCs. Sepiolite surface is chemically modified using vinyltriethoxysilane and analyzed by fouriertransform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Nanocomposite PVDF-g-PS/MS membranes are prepared by phase inversion technique and subsequently treated with chlorosulfonic acid to induce sulfonic acid (SO3H) active sites at the membrane surface. The prepared nanocomposite membranes (S-PPMS) are analyzed for their physicochemical characteristics in terms of water uptake percentage, cation exchange capacity (CEC), proton conductivity (σ), and methanol permeability. MS dispersion in the copolymer matrix is proved through morphological SEM examination. The S-PPMS membranes exhibit increased proton conductivity due to the presence of well-dispersed MS and surface functional –SO3H groups. A peak power density of 210 mWcm−2 is recorded for S-PPMS10 at 110 °C which is higher than the output obtained from Nafion-117. These promising results indicate the potential utilization of prepared nanocomposite PEMs for DMFC application.

The rare earth (Yb3+) substituted W-type hexagonal ferrites with composition CaPb2-xYbxFe16O27 (x = 0.0, 0.5, 1.0, 1.5, 2.0) were synthesized by a facile and cost-effective sol-gel auto combustion method with post heat treatment. The synthesized hexagonal ferrites were characterized by a variety of analytical techniques, and an impedance analyzer was used to investigate the effects of Ytterbium on structural, magnetic, spectral and dielectric properties. The relationship between their impedance, structure and dielectric properties was investigated. The X-ray diffraction patterns verify the presence of single-phase W-type hexagonal ferrites. Physical properties such as Dbulk (bulk density), Dxrd (X-ray density), and P (porosity) of the CaPb2-xYbxFe16O27 W-type hexagonal ferrites were calculated. The bulk density of all the samples was decreased, and X-ray intensity was increased with the Ytterbium replacement in the W-type hexaferrite. By adding Yb3+ ions, the lattice parameters, cell volume and X-ray density were reduced due to the substitution of ytterbium with smaller ionic radii compared to the lead ion with large ionic radii. The AC-conductivity was increased from (1.523 × 10−5 to 6.699 × 10−5) Ωcm−1. The dielectric constant and tangent loss was found to decrease substantially. The magnetic properties were found to enhance by the substitution of Yb3+. The low coercivity value of Yb3+ substituted W-type hexagonal ferrites are suitable for magnetic recording media operated at a high-frequency regime. The enhancement of electrical, dielectric and magnetic characteristics suggests these materials as promising for multi-layer chip inductors (MLCIs) circuit applications.

The presence of major heavy metals including Pb2+, Cu2+, Co2+, Ni2+, Hg2+, Cr6+, Cd2+, and Zn2+ in water is of great concern because they cannot degrade or be destroyed. They are toxic even at very low concentrations. Therefore, it is necessary to remove such toxicants from water. In the current study, polydopamine carbon nanotubes (PD-CNTs) and polysulfone (PS) composite membranes were prepared. The structural and morphological features of the prepared PDCN composite membranes were studied using FTIR, XRD, SEM, and EDS. The potential application of PDCNs for heavy metal removal was studied for the removal of Pb2+, Cr6+, and Cd2+ from wastewater. The maximum removal efficiency of 96.1% was obtained for Cr6+ at 2.6 pH using a composite membrane containing 1.0% PD-CNTs. The removal efficiencies decreased by 64.1 and 73.4, respectively, by enhancing the pressure from 0.50 up to 0.85 MPa. Under the same circumstances, the percentages of Pb+2 removal at 0.49 bar by the PDCNS membranes containing 0.5% and 1.0% PD-CNT were 70 and 90.3, respectively, and decreased to 54.3 and 57.0, respectively, upon increasing the pressure to 0.85 MPa. The results showed that PDCNS membranes have immense potential for the removal of heavy metals from water.

Initially, pristine polymers were used to develop corrosion-resistant coatings. Later, the trend shifted to the use of polymeric nanocomposites in anti-corrosion materials. In this regard, graphene has been identified as an important corrosion-resistant nanomaterial. Consequently, polymer/graphene nanocomposites have been applied for erosion protection applications. Among polymers, conducting polymers (polyaniline, polypyrrole, polythiophene, etc.) and nonconducting polymers (epoxy, poly(methyl methacrylate), etc.) have been used as matrices for anticorrosion graphene nanocomposites. The corrosion-resistant polymer/graphene nanocomposites have found several important applications in biomedical fields such as biocompatible materials, biodegradable materials, bioimplants, tissue engineering, and drug delivery. The biomedical performance of the nanomaterials depends on the graphene dispersion and interaction with the polymers and living systems. Future research on the anti-corrosion polymer/graphene nanocomposite is desirable to perceive further advanced applications in the biomedical arenas.

Two-dimensional (2D) tri-TMDCs carrier dynamics provide a platform for studying excitons through Ultrafast Pump-Probe Transient Absorption Spectroscopy. Here we studied the ZrTe3 nanosheets (NTs) exciton dynamics by transient absorption (TA) spectrometer. We observed different carrier dynamics in the ZrTe3 NTs sample at different pump powers and with many wavelengths in the transient absorption spectrometer. The shorter life decay constant is associated with electron-phonon relaxation. Similarly, the longer-life decay constant represents the long live process that is associated with charge separation. The interactions between carrier-phonons at nanoscale materials can be changed by phonons quantum confinements. The hot carrier lifetime determined the strength of carrier phonon interactions. The value of fast decay in the conduction band is due to carrier relaxation or the carrier gets trapped due to surface states or localized defects. The value of slow decay is due to the recombination of surface state and localized defects processes. The lifetime declines for long wavelengths as size decreases. Whereas, during short wavelength-independent decay, carrier characteristics have been observed. TA spectroscopy is employed to investigate insight information of the carrier’s dynamical processes such as carrier lifetime, cooling dynamics, carrier diffusion, and carrier excitations. The absorption enhanced along excitons density with the increase of pump power, which caused a greater number of carriers in the excited state than in the ground state. The TA signals consist of trap carriers and (electron-hole) constituents, which can be increased by TA changes that rely on photoexcitation and carrier properties.

Application of polymer-flooding systems in secondary and tertiary oil recovery represents a real challenge for oil industry. In this work, our main objective is to explore possibilities of making use of xanthan-g-polyacrylamide for polymer flooding in a particular Devonian oilfield of medium salinity. The graft polymer was synthesized by using microwave-assisted graft copolymerization reaction of acrylamide on xanthan. The synthesized copolymer with optimized grafting parameters has been characterized by Infrared Spectroscopy and Thermal Analysis (DSC). Rheological analysis by steady shear and oscillatory flow experiments have been subsequently performed for xanthan and grafted xanthan under reservoir conditions. In steady shear, as expected the grafted polymer solutions flow as shear-thinning materials and apparent viscosity showed good fits with Cross’s model. The viscosity losses due to salinity or temperature are more controlled for the grafted xanthan compared to pristine xanthan. When the grafted polymer concentration is increased to 2000 ppm the losses were halved. In oscillatory shear, the copolymer solutions followed a global behavior of semi-dilute entangled systems, furthermore, all dynamic properties were influenced by the brine salinity. Compared to xanthan, the elastic properties of xanthan-g-polyacrylamide solutions have been significantly improved in saline media and the losses in elasticity of grafted polymer solutions are lower.

The density of states and quantum capacitance of pure and doped Nb2N and Nb4N3 single-layer and multi-layer bulk structures are investigated using density functional theory calculations. The calculated value of quantum capacitance is quite high for pristine Nb2N and decent for Nb4N3 structures. However for cobalt-doped unpolarized structures, significant increase in quantum capacitance at Fermi level is observed in the case of Nb4N3 as compared to minor increase in case of Nb2N. These results show that pristine and doped Nb2N and Nb4N3 can be preferred over graphene as the electrode material for supercapacitors. The spin and temperature dependences of quantum capacitance for these structures are also investigated.

Soft matter is a class of materials with flexibility properties and the ability to easily deform and self-assemble into complex structures. Some examples of materials with these features are fluids, polymers, colloids, gels, and also some biological compounds [...]

Environmental pollution caused by heavy metal ions has become a major health problem across the world. In this study, a selective colorimetric sensor based on starch functionalized silver nanoparticles (St-Ag NPs) for rapid detection of Hg2+ in real samples was developed. The environmentally friendly green approach was utilized to synthesize starch functionalized silver nanoparticles (St-AgNPs). A multi-technique approach involving UV-Vis absorption spectroscopy, Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and scanning electron microscope (SEM) was used for the characterization of St-Ag NPs. These starch functionalized AgNPs were tested for the detection of heavy metals at 25 °C. The screening process revealed clear changes in the AgNPs color and absorption intensity only in the presence of Hg2+ due to the redox reaction between Ag0 and Hg2+. The color and absorption intensity of nanoparticles remain unchanged in the presence of all the other tested metals ion. The proposed method has strong selectivity and sensitivity to Hg2+ ions, with a detection limit of 1 ppm revealed by UV-visible spectrophotometry. The proposed procedure was found to be successful for the detection of Hg2+ in real samples of tap water.

Supercapacitors provide remarkable eco-friendly advancement in energy conversion and storage with a huge potential to control the future economy of the entire world. Currently, industries focus on the design and engineering aspects of supercapacitors with high performance (high energy), flexibility (by the use of composite polymer based electrolytes), high voltage (ionic liquid) and low cost. The paper reviews the modelling techniques like Empirical modelling, Dissipation transmission line models, Continuum models, Atomistic models, Quantum models, Simplified analytical models etc. proposed for the theoretical study of Supercapacitors and discusses their limitations in studying all the aspects of Supercapacitors. It also reviews the various software packages available for Supercapacitor (SC) modelling and discusses their advantages and disadvantages. The paper also reviews the Experimental advancements in the field of electric double layer capacitors (EDLCs), pseudo capacitors and hybrid/asymmetric supercapacitors and discusses the commercial progress of supercapacitors as well.

The high specific strength, good corrosion resistance, and great biocompatibility make titanium and its alloys the ideal materials for biomedical metallic implants. Ti-6Al-4V alloy is the most employed in practical biomedical applications because of the excellent combination of strength, fracture toughness, and corrosion resistance. However, recent studies have demonstrated some limits in biocompatibility due to the presence of toxic Al and V. Consequently, scientific literature has reported novel biomedical β-Ti alloys containing biocompatible β-stabilizers (such as Mo, Ta, and Zr) studying the possibility to obtain similar performances to the Ti-6Al-4V alloys. The aim of this review is to highlight the corrosion resistance of the passive layers on biomedical Ti-6Al-4V and β-type Ti alloys in the human body environment by reviewing relevant literature research contributions. The discussion is focused on all those factors that influence the performance of the passive layer at the surface of the alloy subjected to electrochemical corrosion, among which the alloy composition, the method selected to grow the oxide coating, and the physicochemical conditions of the body fluid are the most significant.

Polymeric nanocomposite foams have attracted increasing research attention for technical reasons. Poly(methyl methacrylate) is a remarkable and viable thermoplastic polymer. This review highlights some indispensable aspects of poly(methyl methacrylate) nanocomposite foams with nanocarbon nanofillers (carbon nanotube, graphene, etc.) and inorganic nanoparticles (nanoclay, polyhedral oligomeric silsesquioxane, silica, etc.). The design and physical properties of poly(methyl methacrylate) nanocomposite foams have been deliberated. It has been observed that processing strategies, nanofiller dispersion, and interfacial interactions in poly(methyl methacrylate)–nanofiller have been found essential to produce high-performance nanocellular foams. The emergent application areas of the poly(methyl methacrylate) nanocomposite foams are electromagnetic interference shielding, sensors, and supercapacitors.

Considerable efforts are underway to rationally design and synthesize novel electrode materials for high-performance supercapacitors (SCs). However, the creation of suitable materials with high capacitance remains a big challenge for energy storage devices. Herein, unique three-dimensional (3D) ZnO hexagonal cubes on carbon cloth (ZnO@CC) were synthesized by invoking a facile and economical hydrothermal method. The mesoporous ZnO@CC electrode, by virtue of its high surface area, offers rich electroactive sites for the fast diffusion of electrolyte ions, resulting in the enhancement of the SC’s performance. The ZnO@CC electrode demonstrated a high specific capacitance of 352.5 and 250 F g−1 at 2 and 20 A g−1, respectively. The ZnO@CC electrode revealed a decent stability of 84% over 5000 cycles at 20 A g−1 and an outstanding rate-capability of 71% at a 10-fold high current density with respect to 2 A g−1. Thus, the ZnO@CC electrode demonstrated improved electrochemical performance, signifying that ZnO as is promising candidate for SCs applications.

In this study we are presenting the synthesis of MnO2 nanorods using hydrothermal method assisted by facile tri-ethanolamine-ethoxylate. Structural (x-ray diffraction, Rietveld refinement), functional (Fourier Transform Infrared spectroscopy and x-ray Photoelectron Spectroscopy) and morphological (Field emission scanning electron microscope, Transmission electron microscopy) characterization conform the β-MnO2 nanostructure with a rod-like morphology and uniform thickness. The morphological variations of the nanorod thickness can be easily controlled by simply monitoring the reaction temperature. Comparative investigations of β-MnO2 samples synthesized at two different reaction temperatures (viz. 100 °C and 120 °C) used as a supercapacitive electrode material have been performed with the aid of different electrochemical techniques. With different electrolytes (Li2SO4 and Na2SO4), supercapacitor device is tested using Cyclic voltammetry, impedance spectroscopy and galvanostatic charge discharge. Interestingly, the low temperature synthesized β-MnO2 nanorods sample exhibit superior electrochemical performance in 1 mol l−1 Li2SO4 electrolyte in terms of high specific capacitance (462 Fg−1 at10 mVs−1), energy density (9.72 WhKg−1), and outstanding cyclic stability (90.26% over 2000 cycles).

A tapered-end flow Zn–air fuel cell (ZAFC), mechanically refuelable with Zn microspheres, was employed to study the effect of aging of KOH electrolyte on the Zn anode. A complete description of the architecture of the adopted cell is reported. The electrochemical characterization of the ZAFC was performed by long-term current discharge tests in galvanostatic mode. An insightful investigation on the particulate Zn anode consisting of spheres of diameter 0.4 mm was performed by means of X-ray diffraction (XRD), scanning electron microscope (SEM), and Raman spectroscopy in order to characterize the crystallographic structure, surface morphology, and chemical nature of residual metal and solid corrosion products. Electrochemical impedance spectroscopy (EIS) allowed to obtain information on the charge-transfer mechanism of zinc anode reaction and on the thickness, compactness, and blocking features of the passive film as a function of the aging of the electrolyte. The results of our analysis revealed the formation of a passive layer of zinc consisting of a white and porous film of ZnO precipitate (type I) and a light-gray to black compact film (type II). The failure of the particulate anode was chiefly caused by the increase in zincate concentration in the electrolyte, but it was enhanced by the nonuniform spatial current distribution due to the instability of the passive film at high pH.

In the current research work, palladium (Pd) nanoparticles were electrochemically deposited on a nitrogen doped montmorillonite (CNx-MMT) support using the underpotential deposition (UPD) method. The prepared Pd based composite electrode was studied as an electrocatalyst for methanol fuel oxidation. The catalysts and the supporting materials montmorillonite, acid activated montmorillonite, and nitrogen doped montmorillonite (MMT, HMMT and CNx-HMMT) were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS) and electrochemical characterization by cyclic voltammetry (CV). The results indicated that Pd supported on CNx-HMMT possesses enhanced electrocatalytic activity and stability compared to commercial Pd/C, which was attributed to its higher electrochemical surface area (ECSA) (23.00 m2 g−1). The results demonstrated the potential application of novel Pd/CNx-HMMT composite nanomaterial as electrocatalysts for methanol electrooxidation in direct methanol fuel cells (DMFCs).

In this review, the efforts done by different research groups to enhance the performance of the electric double-layer capacitors (EDLCs), regarding the effect of the modification of activated carbon structures on the electrochemical properties, are summarized. Activated carbon materials with various porous textures, surface chemistry, and microstructure have been synthesized using several different techniques by different researchers. Micro-, meso-, and macroporous textures can be obtained through the activation/carbonization process using various activating agents. The surface chemistry of activated carbon materials can be modified via: (i) the carbonization of heteroatom-enriched compounds, (ii) post-treatment of carbon materials with reactive heteroatom sources, and (iii) activated carbon combined both with metal oxide materials dan conducting polymers to obtain composites. Intending to improve the EDLCs performance, the introduction of heteroatoms into an activated carbon matrix and composited activated carbon with either metal oxide materials or conducting polymers introduced a pseudo-capacitance effect, which is an additional contribution to the dominant double-layer capacitance. Such tricks offer high capacitance due to the presence of both electrical double layer charge storage mechanism and faradic charge transfer. The surface modification by attaching suitable heteroatoms such as phosphorus species increases the cell operating voltage, thereby improving the cell performance. To establish a detailed understanding of how one can modify the activated carbon structure regarding its porous textures, the surface chemistry, the wettability, and microstructure enable to enhance the performance of the EDLCs is discussed here in detail. This review discusses the basic key parameters which are considered to evaluate the performance of EDLCs such as cell capacitance, operating voltage, equivalent series resistance, power density, and energy density, and how these are affected by the modification of the activated carbon framework.

Background: Ordered arrays of 1D iron(oxyhydr)oxide nanostructures have potential applications in magnetic recording mediums, lithium batteries, supercapacitors, and thermal production of α-, β-, γ-type Fe2O3. Large surface areas with three-dimensional architectures, such as nanotubes, are encouraged because the easy access of ion, gas, liquid and radiation assures high ion exchange capacity, sensing and catalytic activities. Objective: In this work, the morphological evolution of Fe-oxyhydroxide electrodeposition inside AAM pores has been followed for the first time by selecting two relevant electrochemical conditions of synthesis producing high quality morphologies of nanotubes. Methods: Iron(oxyhydr)oxide nanotubes have been synthesized by cathodic electrodeposition at a constant current in classic three-electrode cell. Two different electrolytic baths have been studied: (i) an aqueous bath consisting of 5 mM FeCl3+5 mM KF+0.1 M KCl+1 M H2O2 (H-Fe) and (ii) an ethanolic bath consisting of 0.3 M FeCl3 + 0.1 M KCl (Et-Fe). Results: XRD, Raman and SEM results on the iron(oxyhydr)oxide nanotubes suggest different mechanisms of chemical precipitation mechanisms in Et-Fe alcoholic solution (dehydration and rearrangement within the ferrihydrite aggregates) and H-Fe aqueous solution (dissolution/ reprecipitation). The morphological evolution of the growing nanostructure to nanotubes inside AAM in the two baths agrees very well with the overpotential vs. time curves, the kinetic growth of the nanotubes arrays and a growth mechanism governed by the relative mass transfer processes involving both OH- and Fe ions. Conclusion: The morphological evolution of Fe-oxyhydroxide cathodic electroprecipitation inside AAM pores in two relevant electrochemical baths containing Fe(III) (aqueous/H-Fe and alcoholic/Et- Fe) has been followed for the first time by a comprehensive SEM analysis accompanied by electrochemical, structural and kinetic growth of the nano-electrodeposits. : The detailed SEM results collected in this work allowed to recommend template electrogeneration of base in ethanol solution containing Fe(III) chloride as a relevant procedure to obtain high-quality, compact and well-ordered Fe oxy-hydroxide nanotubes.

Electrical energy storage based on Zn–air concepts is experiencing increasing interest for applications ranging from consumer electronics to automotive and grid storage, owing to their high energy density, intrinsic safety, environmental friendliness, and low cost. Their implementation is nevertheless daunted by several materials science riddles, affecting the actually available power density and durability. In this scenario, in operando dynamic physicochemical information at length scales between mesoscopic and nanometric is highly desirable for knowledge-based advancements. This overview summarizes recent contributions of in situ and quasi- in situ X-ray methods – absorption and fluorescence microspectroscopies and microtomography – to studies of cathodes, anodes, and model cells.

Flat, free-standing chitosan/phosphotungstic acid (PTA) polyelectrolyte membranes were prepared by in-situ ionotropic gelation process at room temperature on porous alumina support firstly impregnated by H3PW12O40. Scanning electron microscopy revealed the formation of compact and homogeneous membranes, whose thickness resulted to be dependent on chitosan concentration and reticulation time. X-ray diffraction and Fourier transform infrared spectroscopy (FTIR) evidenced the formation of almost amorphous membrane without appreciable concentration of not protonated NH2 groups and PTA3- ions with preserved Keggin structure. Membranes were tested as proton conductor in low temperature H2-O2 fuel cell allowing to get peak power densities up to 300mWcm-2. Electrochemical impedance measurements allowed to estimate polyelectrolytes' conductivity up to 28mScm-1 at room temperature.

Electrodeposition and ageing under oxygen reduction reaction (ORR) of Mn-X/PPy (X=Co, Mg, Ni; PPy=polypyrrole) and Mn-Ag/G (G=graphene) composite electrocatalysts have been studied by quasi-in-situ soft X-ray absorption and fluorescence microspectroscopy. The fabricated materials exhibit micro-grained morphologies in which Mn is present mainly as Mn2+, accompanied by combinations of Co0/Co2+ and Ni0/Ni2+. Ageing leads to the formation of progressively larger mesoscopic aggregates. Initial ageing yields more active Mn3+ and Mn4+, in agreement with an improved ORR behaviour. Prolonged ageing causes the loss of Mn3+ and Mn4+ from the surface, in correlation with a degradation of the ORR response. In the investigated ageing period, Mn-Mg/PPy exhibits the best durability, with about half of the catalyst grains still showing the presence of Mn3+/Mn4+, while the others consist mainly of Mn2+. In Mn-Ni/PPy, the Ni2+ content tends to increase with ageing whereas Co3+ forms in the Mn-Co/PPy composites.

Electrodeposition of manganese/polypyrrole (Mn/PPy) nanocomposites has been recently shown to be a technologically relevant synthesis method for the fabrication of Oxygen Reduction Reaction (ORR) electrocatalysts. In this study we have grown such composites with a potentiostatic anodic/cathodic pulse-plating procedure and characterised them by a multi-technique approach, combining a suite of in situ and ex situ spectroscopic methods with electrochemical measurements. We have thus achieved a sound degree of molecular-level understanding of the hybrid co-electrodeposition process consisting of electropolymerisation of polypyrrole with incorporation of Mn. By in situ Raman spectroscopy we followed the formation of MnOx and the polymer by monitoring the build-up and development of the relevant vibrational bands. The compositional and chemical-state distribution of the as-deposited material has been investigated ex situ by soft X-ray fluorescence (XRF) mapping and micro-absorption spectroscopy (micro-XAS). XRF shows that the spatial distribution of Mn is consistent in a rather wide range of current densities (c.d.s), while micro-XAS reveals a mixture of Mn valencies, with higher oxidation states prevailing at higher c.d.s. Pyrolysis of electrodeposits, desirable for obtaining more durable and active catalysts, has been followed in situ by photoelectron microspectroscopy, allowing to assess the evolution of: (i) the electrodeposit morphology, resulting in a uniform distribution of nanoparticles; (ii) the chemical state of manganese, changing from a mixture of valences to a final state consisting of Mn(III) and Mn(IV) oxides and (iii) the bonding nature of nitrogen, from initially N-pyrrolic to a combination of pyridinic and Mn–N/graphitic.

In this paper we report on the fabrication and testing of a novel concept of sealed electrochemical microcell for in situ soft X-ray microspectroscopy in transmission, dedicated for nonvacuum compatible electrolytes. The microcell, fabricated using ultraviolet lithography, at variance with previous versions of electrochemical wet cells, that featured an optical window glued on top of the electrode system and a very limited electrolyte volume, the device presented here is a single solid block based around a microfabricated channel with fixed optical windows and apt for microfluidic work. Moreover, this cell allows to employ an advanced electrodic geometry developed in our group - so far used only in open electrochemical cells for work with vacuum-compatible electrolytes - also with low-vapor pressure liquids, possibly saturated with the required gases. The cell optimal electrode design allows three-electrode electrochemical control typical of traditional electrochemical experiments. The first electrochemical experiments with this new cell explore the electrochemical growth of a Co-polypyrrole, a composite electrocatalyst material with promising performance to replace the expensive Pt catalyst in fuel-cell oxygen electrodes. Morphological and chemical-state distributions of Co codeposited with polypyrrole has been followed as a function of time and position, yielding unprecedented information on the processes relevant to the synthesis of this catalyst.

Stoichiometric CdSe nanotubes (NTs) with a length of ∼700 nm have been successfully grown by one-step electrochemical technique into anodic alumina membranes. Cyclovoltammetric method has been performed using porous anodic alumina as template electrode and an electrochemical bath containing Cd 2+ ions and SeO 2 . The as-prepared NTs have been identified as face-centred-cubic CdSe by XRD, while micro-Raman analysis reveals the typical peaks of nanostructured CdSe. The stoichiometric deposition of CdSe NTs formation is suggested by EDX analysis, with an average atomic percentage of Cd:Se of ∼0.93. Photoelectrochemical measurements reveal that CdSe NTs are photoactive materials with direct band gap of 1.75 eV and n-type semiconducting behaviour.

Understanding the lateral variations in the elemental and chemical state of constituents induced by electrochemical reactions at nanoscales is crucial for the advancement of electrochemical materials science. This requires in situ studies to provide observables that contribute to both modeling beyond the phenomenological level and exactly transducing the functionally relevant quantities. A range of X-ray coherent diffraction imaging (CDI) approaches have recently been proposed for imaging beyond the diffraction limit with potentially dramatic improvements in time resolution with chemical sensitivity. In this paper, we report a selection of ptychography results obtained in situ during the electrodeposition of a metal–polymer nanocomposite. Our selection includes dynamic imaging during electrochemically driven growth complemented with absorption and phase spectroscopy with high lateral resolution. We demonstrate the onset of morphological instability feature formation and correlate the chemical state of Mn with the local growth rate controlled by the current density distribution resulting from morphological evolution.

The photoelectrochemical polymerization of poly(3,4-ethylenedioxythiophene), PEDOT, was successfully realized on anodic film grown to 50 V on magnetron sputtered niobium. Photocurrent Spectroscopy was employed to study the optical properties of Nb/Nb 2 O 5 /PEDOT/electrolyte interface in a large range of potential, and to get an estimate of the band gap and flat band potential of both the oxide and the polymer. Scanning Electron Microscopy was used to study the morphology of PEDOT. Both the optical and morphological features of the photoelectrochemically grown polymer were compared with those showed by PEDOT electropolymerized on gold conducting substrate.

The preparation of Ce(OH)3/CeO2 nanostructures (NSs) through electrogeneration of base into anodic alumina membranes was studied. The effects of solvent (alcohol and/or water), Ce3? partner anion nature (chloride or nitrate) and concentration, applied potential or current density in driving the morphology toward nanowires (NWs) and/or nanotubes (NTs) was described. The structural analysis performed by X-Ray Diffraction and Raman Spectroscopy allowed to evidence that the presence of Ce(IV) into the nanostructures strongly depends on the oxygen content in the growing environment.

This paper reports on the quantitative assessment of the oxygen reduction reaction (ORR) electrocatalytic activity of electrodeposited Mn/polypyrrole (PPy) nanocomposites for alkaline aqueous solutions, based on the Rotating Disk Electrode (RDE) method and accompanied by structural characterizations relevant to the establishment of structure-function relationships. The characterization of Mn/PPy films is addressed to the following: (i) morphology, as assessed by Field-Emission Scanning Electron Microscopy (FE-SEM) and Atomic Force Microscope (AFM); (ii) local electrical conductivity, as measured by Scanning Probe Microscopy (SPM); and (iii) molecular structure, accessed by Raman Spectroscopy; these data provide the background against which the electrocatalytic activity can be rationalised. For comparison, the properties of Mn/PPy are gauged against those of graphite, PPy, and polycrystalline-Pt (poly-Pt). Due to the literature lack of accepted protocols for precise catalytic activity measurement at poly-Pt electrode in alkaline solution using the RDE methodology, we have also worked on the obtainment of an intralaboratory benchmark by evidencing some of the time-consuming parameters which drastically affect the reliability and repeatability of the measurement.

The stability of pyrolyzed Mn–Co/polypyrrole (PPy) nanocomposites towards the Oxygen Reduction Reaction (ORR) in alkaline solution, was studied with a close-knit group of complementary microscopic and space-resolved spectroscopic approaches: Atomic Force Microscopy (AFM), Scanning and High-Resolution Transmission Electron Microscopy (SEM, HRTEM) and identical-location Scanning PhotoElectron Microscopy (SPEM). Tracking quasi-in situ the morphochemical evolution of the Mn–Co/PPy catalyst upon electrochemical aging under ORR conditions by this multi-technique approach, has allowed to clarify the key physico-chemical processes underlying the dramatic impact of Co additions to stability improvement. Keywords: Mixed manganese oxides, Polypyrrole, Oxygen reduction, Electrocatalysis, Nanocomposites, X-ray photoelectron microspectroscopy

In this paper, we demonstrate that nanoscale membrane electrode assemblies, functioning in a H 2/O 2 fuel cell, can be fabricated by impregnation of anodic alumina porous membranes with Nafion® and phosphotungstic acid. Porous anodic alumina is potentially a promising material for thin-film micro power sources because of its ability to be manipulated in micro-machining operations. Alumina membranes (Whatman, 50 μm thick, and pore diameters of 200 nm) impregnated with the proton conductor were characterized by means of scanning electron microscopy, X-ray diffraction, and thermal analysis. The electrochemical characterization of the membrane electrode assemblies was carried out by recording the polarization curves of a hydrogen-oxygen 5 cm 2 fuel cell working at low temperatures (25∈÷∈80 °C) in humid atmosphere. Our assemblies realized with alumina membranes filled with phosphotungstic acid and Nafion® reach respectively the peak powers of 20 and 4 mW/cm 2 at room temperature using hydrogen and oxygen as fuel and oxidizer.

Low energy X-ray fluorescence (XRF) and soft X-ray absorption (XAS) microspectroscopies at high space-resolution are employed for the investigation of the coelectrodeposition of composites consisting of a polypyrrole(PPy)-matrix and Mn-based ternary dispersoids, that have been proposed as promising electrocatalysts for oxygen-reduction electrodes. Specifically, we studied Mn–Co–Cu/PP, Mn–Co–Mg/PPy and Mn–Ni–Mg/PPy co-electrodeposits. The Mn–Co–Cu system features the best ORR electrocatalytic activity in terms of electron transfer number, onset potential, half-wave potential and current density. XRF maps and micro-XAS spectra yield compositional and chemical state distributions, contributing unique molecular-level information on the pulse-plating processes. Mn, Ni, Co and Mg exhibit a bimodal distribution consisting of mesoscopic aggregates of micrometric globuli, separated by polymer-rich ridges. Within this common qualitative scenario, the individual systems exhibit quantitatively different chemical distribution patterns, resulting from specific electrokinetic and electrosorption properties of the single components. The electrodeposits consist of Mn3+,4+-oxide particles, accompanied by combinations of Co0/Co2+, Ni0/Ni2+ and Cu0,+/Cu2+ resulting from the alternance of cathodic and anodic pulses. The formation of highly electroactive Mn3+,4+ in the as-fabricated material is a specific feature of the ternary systems, deriving from synergistic stabilisation brought about by two types of bivalent dopants as well as by galvanic contact to elemental metal, this result represents a considerable improvement in material quality with respect to previously studied Mn/PPy and Mn-based/PPy binaries.

The electrochemical fabrication of alumina membranes by anodizing of aluminium in phosphoric acid and oxalic acid solutions, in the temperature interval from −1 to 16 °C, was investigated in order to study the influence of different parameters (initial treatment of aluminium surface, nature and composition of electrolyte, temperature) on the final characteristics of the membranes. Porous layers were grown using a linear potential scan at 0.2 V s −1 up to 160 V in H 3 PO 4 solution and 70 V in oxalic acid solution. The efficiency of porous layer formation was calculated by using Faraday's law and weight measurements. Pore size distribution and porosity of membranes prepared in 0.4 M H 3 PO 4 were found to be dependent on temperature, while in 0.04 M smaller pore size and lower porosity were obtained, independent of temperature. Highly ordered structures were formed by aluminium anodizing in 0.15 M oxalic acid solution at 70 V. A uniform pore diameter of about 90 nm was found, independent of temperature. A porosity value of about 26% was achieved and it was found to be independent of temperature for membranes prepared in oxalic acid. Porous layers grown either in H 3 PO 4 or oxalic acid solution crystallized at temperatures around 870–890 °C. For membranes formed in oxalic acid the pyrolysis of oxalate anions also occurs.

This paper reports an in situ study of the anodic behavior of a model solid oxide electrolysis cell (SOEC) by means of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) combined with near edge X-ray absorption fine structure (NEXAFS) measurements. The focus is on the anodic surface chemistry of MnOx, a model anodic material already considered in cognate SOFC-related studies, during electrochemical operation in CO2, CO2/H2O and H2O ambients. The XPS and NEXAFS results we obtained, complemented by electrochemical measurements and SEM characterisation, reveal the chemical evolution of Mn under electrochemical control. MnO is the stable chemical form at open-circuit potential (OCP), while Mn3O4 forms under anodic polarisation in all the investigated gas ambients. Carbon deposits are present on the Mn electrode at OCP, but they are readily oxidised under anodic conditions. Prolonged operation of the MnOx anode leads to pitting of the Mn films, damaging of the triple-phase boundary region and also to formation of discontinuities in the Mn patch. This is accompanied by chemical transformations of the electrolyte and formation of ZrC without impact on the surface chemistry of the Mn-based anode.

This study deals with the morphological and chemical-state changes caused by the degradation of nanocomposite electrocatalysts – fabricated by pulsed potentiostatic co-electrodeposition and subsequently pyrolysed – under oxygen reduction reaction (ORR) conditions in aqueous alkaline solution. Variations in shape, dimensions and chemical state of the Mn-centres were followed by quasi-in situ synchrotron-based scanning photoelectron microscopy with submicron lateral resolution, combined with ex situ Raman measurements, in correspondence of different cyclovoltammetric ageing stages. The decline of the electrocatalytic performance is accompanied by size variations of the MnOx particles that are initially ~ 30 nm in diameter, then shrink to ~ 10 nm and subsequently grow to ~ 45 nm after prolonged ORR. Concerning chemical state, the pristine Mn0,II nanoparticles are converted to MnIII,IV oxy-hydroxides as a result of a dissolution/redeposition process favoured by the oxygen environment.