The removal of nitrate (NO3−) from water and its subsequent valorization for various applications are crucial due to environmental, health, and economic considerations. A promising method for its removal is the process of electrocatalytic reduction of nitrate. Copper/nickel (Cu/Ni) composite electrodes have demonstrated potential for this process in aqueous solution, however, the effect of thin Cu film coated on Ni using physical vapor deposition (PVD) has not been investigated for NO3− removal. Here, the PVD technique was employed to deposit a thin film of Cu onto a Ni plate to form Cu-Ni composite electrodes of varying Cu thicknesses (25–100 nm), enabling the investigation of the influence of the Cu film thickness on NO3− reduction. Electrodes prepared using PVD were utilized for electrocatalytic nitrate reduction (NO3RR) for the first time. The Cu-Ni electrodes were analyzed using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to examine the deposited Cu film which is critical for NO3− reduction and ammonium (NH4+) selectivity. The Cu film was found to be uniformly distributed on the Ni plate without any additional contamination. Cyclic voltammetry was performed to obtain the information on electron transfer between the Cu-Ni electrode and the nitrogen (N2) species on the surface. NO3− was primarily reduced to NH4+, with no significant difference in the NO3− conversion rate observed as a function of the Cu thickness. As the Cu thickness increased, the current density decreased. This study also investigated the effect of stirring on NO3− reduction, considering potential applications where rotation or stirring is not feasible such as in some batteries. The findings of this investigation indicate that thin film coated electrodes fabricated using the PVD method exhibit capability for NO3− elimination through electrocatalytic reduction processes.

The pursuit of scalable and efficient electrode materials is essential for advancing lithium-ion battery (LIB) technologies. Among the anode candidates, spinel-structured ZnMn2O4 (ZMO) is attractive due to its high theoretical capacity (∼1008 mAhg−1), environmental friendliness, and cost-effectiveness. However, large volume expansion during lithium insertion/extraction and poor electrical conductivity limit its long-term performance. Conventional ZMO nanostructure synthesis involves complex, multi-step processes requiring high-temperature calcination, making them time-consuming and unsuitable for large-scale production. To overcome these challenges, we developed a rapid, one-pot microwave-assisted hydrothermal synthesis technique to fabricate a ZnMn2O4/α-MnO2 (ZMO/α-MO) nanocomposite. This method reduces processing time and enables in-situ formation of a mixed morphology. The composite consists of nano-polyhedral ZnMn2O4 integrated with 1D α-MnO2 nanowires, which buffer volume changes and enhance structural stability during cycling. The synergistic architecture improves electron transport, reduces lithium-ion diffusion paths, and provides superior mechanical resilience. Electrochemical results showed that the ZMO/α-MO nanocomposite as an anode material in the Li half-cell delivered a high discharge capacity of 891.6 mAhg−1 at 100 mAg−1 after 100 cycles. The electrode exhibited stable cycling across varying current densities and self-adaptive capacity recovery at different rates. These performance enhancements are attributed to improved reaction kinetics enabled by its porous structure, high surface area, and controlled volume expansion of ZMO nanoparticles composited with α-MnO2 nanowires. This green, scalable, and time-saving synthesis strategy offers promising potential for next-generation high-performance LIBs.

2D materials, characterized by their extensive surface area and customizable chemical and electronic properties, offer compelling advantages as advanced materials. These unique attributes pave the way for the development of next-generation electronics and optoelectronics, photo- and electro-catalysis, energy storage and conversion devices, and sensors. The most prominent and commonly available 2D transition metal dichalcogenide, molybdenum disulfide (MoS₂), has already shown its potential for advanced applications. However, its relatively unfavorable electronic structure and limited intrinsic conductivity lower its suitability for applications that require high conductivity, such as electrocatalysts. One way to enhance its conductivity is by electrochemically intercalating alkali metal ions, e.g., Na⁺ and K⁺, into its layered structure, potentially adjusting its electronic structure. Here, we present a comprehensive investigation into the atomic-scale intercalation mechanism using molecular dynamics simulations, complemented by experimental analysis of structural and electronic properties at the macro scale through various characterization techniques. It is demonstrated that the hydration shell of ions serves as an energy barrier to intercalation as it undergoes a structural change during the intercalation. When alkali metal ions are intercalated into MoS₂, they introduce more defects and enhance conductivity. Notably, these effects are more pronounced for potassium than for sodium.

This research presents a novel investigation into the intricate relationship between temperature and the performance of polymeric triboelectric nanogenerators experimentally and theoretically. A comprehensive investigation has been conducted to delve into the underlying mechanisms governing the temperature dependence of a triboelectric nanogenerator. The study centers on a meticulously fabricated triboelectric nanogenerator using a polyimide (PI) nanofiber membrane and encompasses a broad temperature spectrum, analyzing behavior at both room temperature and elevated temperatures. The developed PI nanofiber membrane functions as a versatile platform for converting mechanical energy into electrical with potential to harvest energy even from ultra-low frequency movements like the human pulse or the act of scratching. Additionally, the material boasts a sophisticated triboelectric response strategy. This means it exhibits its peak performance within a specific temperature range, optimizing energy conversion efficiency under these conditions. Open circuit voltage (VOC) reaches 11.76 V at 160 °C, an 84.4 % improvement compared to room temperature. A Kelvin probe force microscopy (KPFM) and fast Fourier transform (FFT) analyses have been performed for the first time to decouple the energy conversion mechanism, confirming its primary dependence on triboelectricity. A comprehensive theoretical study explores the working mechanisms of contact electrification (CE) and the triboelectric effect (TE) during temperature elevation in these nanogenerators (TENGs). This work highlights the potential of PI nanofibers as high-performance, flexible nanogenerators, particularly for applications requiring operation in smart, high-temperature environments. The emphasis on decoupling the mechanism through novel techniques and a theoretical framework on the temperature dependence strengthens the originality and contribution of the study.

The increasing concentration of CO2 is a serious concern for the environment. Electrochemical conversion of CO2 into valuable products, including fuels, offers a viable solution and helps close the carbon-neutral cycle. Metal-organic framework (MOF) composites, due to their high porosity, large surface area, and significant chemical tunability, are considered to be a promising class of catalyst materials for the CO2 reduction reaction (CO2RR). This chapter focuses on the fundamentals of CO2RR and mechanism of the reaction followed by discussing the recent advancements in MOF composite electrocatalysts for CO2RR including MOF-supported electrocatalysts, conductive-supported MOF composites, graphene and carbonous MOF composites, MOF-MXenes, MOF-polymers, and polyoxometalate.

Titanium surfaces featuring high-aspect ratio (HAR) nanopillars can have antimicrobial and osteogenic properties. Nevertheless, the impact of these surfaces on immune cells and their potential for immunomodulation remain unclear. In this study, the effects of HAR titanium nanopillars produced by dry-etching (DETi) on the response of unstimulated (M0) and pro-inflammatory (M1) murine macrophages (J774A.1) have been explored. The findings revealed changes in the morphology and crystallinity of the DETi nanopillars along their height. After 48 h of culture, both M0 and M1 stimulated macrophages displayed a more elongated morphology, a smoother cell surface, and shorter cellular protrusions on the more hydrophilic and rough DETi surfaces. Furthermore, DETi surfaces induced polarization of M0 cells towards M2 phenotypes, whereas M1 stimulated cells showed M2-like elongated morphologies while maintaining a stronger pro-inflammatory response to DETi surfaces relative to the glass control. The findings indicate that the DETi surfaces can induce morphological changes in macrophages and specific immunomodulatory effects depending on their initial phenotype, highlighting the potential of such biomaterials to incorporate an immunomodulatory biofunctionality next to the osteogenic and bactericidal ones.

The dream corrosion inhibitor would work for every substrate–environment combination, and the protection would be sustained indefinitely with an irreversible barrier layer when exposed to aggressive and changing environmental conditions. However our prior electrochemical experiments on AA2024-T3 have shown that despite the initial inhibition, all of the tested molecules had reversible bonds that limit their inhibition performance and applicability in dynamic environments, with the exception of 3-amino-1,2,4-triazole-5-thiol, which still showed 42% inhibition efficiency after being exposed to 0.1M NaCl only for three days. To our knowledge, this is the first mechanistic study that explains the origin of such quasi-sustained inhibition by an organic molecule under dynamic and aggressive conditions relevant to aerospace alloys. Potentiodynamic polarization, atomic force microscopy and scanning Kelvin probe force microscopy (AFM/SKPFM), X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) complemented by density functional theory (DFT) calculations were used to identify the molecular mechanism responsible for the quasi-stable adsorption provided by 3-amino-1,2,4-triazole-5-thiol. Our findings suggest that a sulphatization of the Al-(hydr)oxide is the key contributor to the quasi-sustained corrosion inhibition. Sustained molecule adsorption over intermetallics in trace amounts was also observed, but their presence was insufficient to inhibit corrosion.

The development of advanced catalysts with innovative nanoarchitectures is critical for addressing energy and environmental challenges such as the electrochemical CO₂ reduction reaction (CO₂ RR). Herein, the synthesis of an innovative copper–sulfur planar structure, Cu–S–BDC, within a metal–organic framework (MOF) catalyst is presented, which demonstrates 100% selectivity toward formate as the sole carbon product. Structural analysis and surface characterizations reveal that Cu–S–BDC exhibits quasi-2D inorganic building units, with Cu bonded to two S-CH (Formula presented.) groups and one BDC linker, while carboxylate groups adopt a bridging coordination mode. This unique arrangement not only imparts remarkable structural stability but also enhances the electronic properties of the MOF, as evidenced by a narrow bandgap of 1.203 eV that facilitates efficient charge transfer and increased electrochemical current density in CO (Formula presented.) RR. Notably, it offers a Faradaic efficiency of 92% for formate at an overpotential as low as −0.4 V versus the reversible hydrogen electrode (RHE) in an aqueous electrolyte of 1 m KOH, as well as a current density of −25.8 mA cm² at −0.9 V versus RHE, averaged over 24 h of electrolysis. This study highlights a fresh perspective in the field of MOF electrocatalysts by demonstrating that engineering the metal coordination environment can significantly enhance the electronic properties and consequently improve the electrocatalytic performance of these materials.

Biodegradable membranes are crucial for environmental applications, offering sustainable and low-impact solutions. These membranes play a vital role in biodegradable batteries by separating the anode and cathode while facilitating proton movement. The aim of this study is to develop a biodegradable membrane using biodegradable polymers such as chitosan (CS) and polyvinyl alcohol (PVA), reinforced with filter paper. In this research, a cost effective, biodegradable membranes using CS, PVA, and a 1:1 CS/PVA composite through solution-casting method were synthesized. The membranes were reinforced with cellulose filter paper and coated with water-resistant graphene conductive ink. Performance metrics, including swelling ratios, water uptake, ion exchange capacity, oxygen diffusion, proton conductivity, and degradation in compost tea, were evaluated. Uncoated CS membrane exhibited the highest water uptake (94.10%), while uncoated PVA membrane demonstrated the highest swelling ratio (150%) and ion exchange capacity (3.94 meq/g). Coated CS/PVA membrane showed the lowest oxygen diffusion coefficient (0.058 × 10−5 cm2/s) and the highest proton conductivity (1.74 mS/cm). All membranes exhibited slow degradation over 100 days. The findings of this research have significant implications beyond the laboratory, presenting a biodegradable, cost-effective, and environmentally sustainable alternative to conventional membranes. These membranes can be utilized in the construction of biobatteries, which, in turn, can be employed to power low-cost devices.

Titanium dioxide (TiO₂) has been widely used as a photocatalyst in CO₂ reduction reaction (CO₂RR) due to its low cost, high stability, and strong absorption in the close-to-visible ultra-violet (UV) range. However, TiO₂ films suffer from poor selectivity in CO₂ reduction due to their unfavorable electronic properties. In this work, we address this challenge by fabricating ultra-thin (14 nm) defective TiO₂ films (TiO₂-DTF) to enhance the selectivity of CO₂RR towards formate. TiO₂ sol was prepared using a facile and reproducible sol-gel method and directly deposited onto the surface of the electrode, forming a uniform, ultra-thin TiO₂ layers with a high number of defects. The activity of the TiO₂-DTF catalyst was studied in both photochemical and photoelectrochemical CO₂RR, indicating that the applied potential increases both the yield and selectivity of CO₂RR to formate. The TiO₂-DTF photocathode exhibited remarkable formate production during CO₂ reduction, achieving exceptional Faradaic efficiencies of up to 45 %. To elucidate the mechanism of photoelectrochemical CO₂RR on TiO₂-DTF, an in-situ attenuated total reflection Fourier-transform infrared spectroscopy (in-situ ATR-FTIR) was used and experimental results were supported by density functional theory (DFT) calculations. This study demonstrates that ultra-thin highly defective TiO₂ film, prepared using the cost-effective and environmentally friendly sol-gel method, can be used as photoelectrocatalyst for CO₂ reduction.

Optimizing the deposition parameters in the fabrication of passivating contacts for crystalline silicon solar cells is critical for improving efficiency. This study explored the influence of varying RF power of Plasma-Enhanced Chemical Vapor Deposition (PECVD) on the quality of hydrogenated intrinsic amorphous silicon ( a-Si:H) films. The aim is to manufacture in-situ phosphorous-doped poly-Si/SiO_x/c-Si passivating contacts with a-Si:H as buffer layer between the tunnelling oxide and the n-type poly-Si. The microstructure factor of our intrinsic layers increases from 0.176 to 0.804, that is from higher to lower film density, as the RF power increases from 5 W to 55 W. Analysis using X-ray Photoelectron Spectroscopy and Optical Microscopy indicates that the Si content in SiO_x is correlated with the formation of pinholes. Our detailed analysis showed that varying the RF power when depositing a-Si:H contacting layer is crucial in altering both the Si⁴⁺ content in SiO_x and the pinhole density, due to the interplay between the plasma etching and the buffering effects during of the a-Si:H layer growth. Notably, the sample processed with 25 W exhibited the maximum pinhole density, the lowest Si⁴⁺ content in SiO_x and the deepest phosphorus in-diffusion, potentially yielding superior results in passivation quality and contact resistivity under optimized PECVD conditions.

Electrochemical CO₂ reduction (CO₂R) to chemicals and fuels has made tremendous progress since the introduction of gas diffusion electrodes (GDEs) to overcome mass-transfer limitations and enable industrial-scale current densities. The advancement in the field, however, has come with new challenges that are related to the stability and degradation of the GDE due to flooding issues, which currently hinder the scale-up. Here, we investigated the effect of six different binding materials (Nafion, polytetrafluoroethylene, Fumion, Pention, poly(vinyl alcohol), and polypyrrole) on the stability and performance of Ag-based GDEs for CO₂R to CO in alkaline media. All binders show a decrease in the Faraday efficiency (FE) of CO and increase in hydrogen evolution reaction over time. The most hydrophilic GDE based on polypyrrole can uphold a higher FE of CO for longer times, which is contrary to a common belief that low wettability is required for long-term stability. By using a range of tools (SEM-EDX, SEM-FIB, X-ray diffraction, and contact angle measurements) for the postelectrolysis characterization of the GDEs, we show that the performance loss is related to flooding, bi(carbonate) precipitation, and catalyst agglomeration. These results contribute to a better understanding of the stability issues in GDE-based CO₂ electrolyzers.

The search for non-toxic alternatives to hexavalent chromium based corrosion inhibitors requires a comprehensive understanding of the factors critical to effective corrosion protection. Key considerations include the evolution of corrosion inhibition with inhibitor concentrations and exposure times, the inhibition efficacy in the presence and following absence of inhibitors, and the stability of inhibition upon polarisation. In our electrochemical comparison of promising organic molecules with sodium dichromate, we found that even top-performing candidates can lead to premature conclusions if such critical factors are overlooked. While organic molecules can match the inhibition performance of chromates under specific conditions, this can be misleading when considering concentration, time, and polarisation dependent behaviour. Initial high performance can also be deceptive in dynamic environments, as we observed that the inhibition provided by most organic molecules drastically decreases when the inhibitor is absent in the electrolyte. These observations call for broader comprehensive inhibitor robustness studies that take into account factors including time, concentration, stability, and polarisation effects in inhibitor efficacy analysis.

In the search for effective high-tech materials for energy conversion and storage devices, spinel-structured nickel ferrite (NiFe₂O₄) has been identified as a promising anode material for lithium-ion batteries (LIBs). However, the influence of different morphologies and surface properties of NiFe₂O₄ nanoparticles on battery performance is hardly addressed. To understand the effect of different morphologies and surface properties on the lithium-ion storage performance, NiFe₂O₄ nanoparticles were synthesized through four different synthesis conditions: NFO-S, NFO-U, NFO-G, and NFO-C. The formation of polycrystalline inverse spinel NiFe₂O₄ was confirmed through XRD, FTIR, and Raman spectroscopy. The morphologies of the obtained samples were studied using FESEM, and it was found that the four different synthesis conditions employed here enabled us to obtain NiFe₂O₄ with four different morphologies. The surface chemistry, surface area and porosity of the NiFe₂O₄ samples were respectively characterized using XPS and BET. The electrochemical performance of the four NiFe₂O₄ samples as anode material was studied by fabricating lithium-ion half-cells. NiFe₂O₄ sample obtained from surfactant-free synthesis condition (NFO-S) displayed a high initial discharge and charge capacity of 2258 mAh/g and 1815 mAh/g, respectively at the current density of 100 mA/g. Even after 100 cycles, NFO-S showed a better discharge capacity of 116 mAh/g at the current density of 100 mA/g, compared to the other samples studied here. The observed higher capacity of the NFO-S sample is attributed to the higher surface area (40.8 m²/g) and pore volume (0.190 cm³/g). The NiFe₂O₄ sample prepared with cationic CTAB surfactant (NFO-C) showed better cyclic stability with a stable coulombic efficiency of 98.5% at the 100th cycle, mainly attributed to its nanocube morphology with lower surface area (16.1 m²/g) and pore volume (0.087 cm³/g).

There is no denying that the world is heading towards an era powered by green energy resources. The need for highly efficient devices for sustainable energy storage and utilization is vital in transitioning towards the full-time realization of renewable energy for our society. In the last four decades, there have been groundbreaking developments in the large-scale commercialization of Li-ion batteries, electric vehicles, and solar power, all made possible by an in-depth understanding of the science of materials. Theoretically, there exists no problem in the production of green hydrogen, as oxides of Ir, Rh, and Pt, and the elements themselves, are excellent catalysts for the electrochemical hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) with fast kinetics. Thus, more work remains to be done in the area of green energy material technology. The problem lies with the critical availability and cost of these materials, which is the underlying motivation for finding alternative energy materials and technologies. This energy transition era presents us with an opportunity to expand our horizons and knowledge in chemical engineering, materials science, and allied fields through two-dimensional (2D) nanomaterials. These materials exhibit intriguing characteristics in contrast to their bulk counterparts, coupled with interchangeable electronic properties depending on the synthesis methodologies employed. The chapter begins by introducing the family of graphene nanosheets and expands into a discussion of advanced 2D families, such as transition metal dichalcogenides (TMDs), MXenes, transition metal oxides (TMOs), and hexagonal boron nitride (h-BN).

Creating durable, eco-friendly coatings for long-term corrosion protection requires innovative strategies to streamline design and development processes, conserve resources, and decrease maintenance costs. In this pursuit, machine learning emerges as a promising catalyst, despite the challenges presented by the scarcity of high-quality datasets in the field of corrosion inhibition research. To address this obstacle, we have created an extensive electrochemical library of around 80 inhibitor candidates. The electrochemical behaviour of inhibitor-exposed AA2024-T3 substrates was captured using linear polarisation resistance, electrochemical impedance spectroscopy, and potentiodynamic polarisation techniques at different exposure times to obtain the most comprehensive electrochemical picture of the corrosion inhibition over a 24-h period. The experimental results yield target parameters and additional input features that can be combined with computational descriptors to develop quantitative structure–property relationship (QSPR) models augmented by mechanistic input features.

Three imidazole-based compounds (imidazole, 2-mercaptobenzimidazole, and 2-mercapto-1-methylbenzimidazole) were studied as corrosion inhibitors of Cu, Zn, and a family of Cu-xZn brass alloys (x = 10−40 wt%) in 3 wt% NaCl solution. The composition of inhibitor layers on the surface was studied using X-ray photoelectron and infrared spectroscopies. The molecular adsorption modes on Cu and Zn were modelled using density-functional theory (DFT) calculations. Mercapto-based inhibitors act as efficient inhibitors on all materials studied due to the formation of inhibitor layer through bonding with nitrogen and sulphur atoms. In contrast, imidazole is a moderate inhibitor for Zn, while it is much less efficient for Cu.

Hydrogen gained momentum as a viable alternative to crude-derived fuels. Scalable production of green hydrogen harnessing solar energy emerged as one of the promising sustainable options that can be facilitated by photocatalyst-assisted water splitting. One-step and two-step photoexcitation systems for overall water splitting (OWS) processes gained much importance because of the ease with which they can be scaled up. This chapter gives a profound insight into the fundamental aspects of these systems, along with a broader picture regarding their possible pathway for commercial implementation. Thermodynamic and kinetic requisites of these novel systems have been described in detail and a critical appraisal of the selectivity of co-catalysts in the photocatalytic OWS process is presented. Subsequently, this chapter provides a comprehensive focus on various novel scalability studies like thin film systems, baggie reactors and the solar hydrogen farm project. The ultimate motive of this chapter is to summarize the current state-of-the-art strategies for producing green hydrogen through heterogeneous photocatalysis and the various limitations it possesses that preclude the system from reaching the market so far. By this it will motivate people to develop innovative pathways that would rectify the problems associated with it.

When no hydrogen can reach the Pt catalyst in the anode for the hydrogen oxidation reaction (HOR) of an operating proton exchange membrane fuel cell (PEMFC), the anode potential increases and causes the cell potential to be reversed compared to normal operation conditions. During this reversal, the oxygen evolution reaction (OER) and carbon oxidation reaction (COR) will occur at the anode, where the COR has devastating consequences for the electrode. Introducing an OER catalyst limits the COR to occur, which makes a reversal tolerant anode (RTA). In this research, RTAs are differentiated by applying different ball milling times during catalyst layer processing, forming big and small OER (IrO_x/TiO_x) and HOR (Pt/C) catalyst particles. The two different particle sizes were electrochemically tested using a rotating disc electrode (RDE). Both catalyst sizes show a decrease in OER activity (mA cm⁻²) accompanied by loss of the ionomer in a self-developed accelerated stress test (AST). The small particle RTAs show higher OER activity as a result of increased surface area. However, during a chronopotentiometry measurement, which mimics a fuel cell reversal, the small particle coatings show a worse reversal tolerance. This phenomenon can be attributed to the increased difficulty in removing oxygen bubbles.