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.

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.

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.

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).

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.

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.

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.

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.

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.

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.

Electrochemical reduction of carbon dioxide (CO₂) to useful products is an emerging power-to-X concept, which aims to produce chemicals and fuels with renewable electricity instead of fossil fuels. Depending on the catalyst, a range of chemicals can be produced from CO₂ electrolysis at industrial-scale current densities, high Faraday efficiencies, and relatively low cell voltages. One of the main challenges for up-scaling the process is related to (bi)carbonate formation (carbonation), which is a consequence of performing the reaction in alkaline media to suppress the competing hydrogen evolution reaction. The parasitic reactions of CO₂ with the alkaline electrolytes result in (bi)carbonate precipitation and flooding in gas diffusion electrodes, CO₂ crossover to the anode, low carbon utilization efficiencies, electrolyte carbonation, pH-drift in time, and additional cost for CO₂ and electrolyte recycling. We present a critical review of the causes, consequences, and possible solutions for the carbonation effect in CO₂ electrolyzers. The mechanism of (bi)carbonate crossover in different cell configurations, its effect on the overall process design, and the economics of CO₂ and electrolyte recovery are presented. The aim is to provide a better understanding of the (bi)carbonate problem and guide research directions to overcome the challenges related to low-temperature CO₂ electrolysis in alkaline media.

The preferential orientation of the perovskite (PVK) is typically accomplished by manipulation of the mixed cation/halide composition of the solution used for wet processing. However, for PVKs grown by thermal evaporation, this has been rarely addressed. It is unclear how variation in crystal orientation affects the optoelectronic properties of thermally evaporated films, including the charge carrier mobility, lifetime, and trap densities. In this study, we use different intermediate annealing temperatures Tinter between two sequential evaporation cycles to control the Cs0.15FA0.85PbI2.85Br0.15 orientation of the final PVK layer. XRD and 2D-XRD measurements reveal that when using no intermediate annealing primarily the (110) orientation is obtained, while when using Tinter = 100 °C a nearly isotropic orientation is found. Most interestingly for Tinter > 130 °C a highly oriented PVK (100) is formed. We found that although bulk electronic properties like photoconductivity are independent of the preferential orientation, surface related properties differ substantially. The highly oriented PVK (100) exhibits improved photoluminescence in terms of yield and lifetime. In addition, high spatial resolution mappings of the contact potential difference (CPD) as measured by KPFM for the highly oriented PVK show a more homogeneous surface potential distribution than those of the nonoriented PVK. These observations suggest that a highly oriented growth of thermally evaporated PVK is preferred to improve the charge extraction at the device level.