Fabrication of binder-less metal electrodes for electrochemical water splitting - A review.

The escalating demand for green hydrogen (H2) as a sustainable energy carrier has attracted intensive research into efficient water electrolysis methods. Promising candidates have emerged as binder-less metal electrodes, which enhance electrochemical performance and durability by reducing electron hindrance and avoiding binder degradation. Despite their potential, a comprehensive understanding of various binder-less fabrication techniques remains limited in the existing literature. As the main objective, this review paper aims to bridge this gap by providing an in-depth analysis of state-of-the-art fabrication methods for binder-less metal electrodes utilized in electrochemical water splitting. Recognizing the critical need for sustainable hydrogen production, the advantages of binder-less electrodes over conventional binder-based counterparts are elucidated, with emphasis placed on their role in promoting cost-effectiveness, improved stability, and enhanced catalytic activity. Techniques such as Hydrothermal/Solvothermal, Electrodeposition, Chemical/Vapor Deposition, and Laser-based fabrication are systematically examined, with their respective advantages, drawbacks, and comparison being highlighted. Drawing upon relevant examples from literature, insights on other aspects and recent trends are also provided, such as the performance of binder-less metal electrodes at industrial-scale current densities (0.1-1 A/cm2) or their potential as photoactive catalysts. Additionally, future directions in the field of binder-less electrode fabrication and the exploration of innovative techniques are also discussed, ensuring that the trajectory of research aligns with the evolving demands of sustainable energy production. The "what's next" section highlights areas of further investigation and potential avenues for technological advancement.

Advanced Fabrication of 3D Micro/Nanostructures of Gallium Oxide with a Tuned Band Gap and Optical Properties.

Gallium oxide (Ga2O3) is a promising material for high-power semiconductor applications due to its wide band gap and high breakdown voltage. However, the current methods for fabricating Ga2O3 nanostructures have several disadvantages, including their complex manufacturing processes and high costs. In this study, we report a novel approach for synthesizing ß-Ga2O3 nanostructures on gallium phosphide (GaP) using ultra-short laser pulses for in situ nanostructure generation (ULPING). We varied the process parameters to optimize the nanostructure formation, finding that the ULPING method produces high-quality ß-Ga2O3 nanostructures with a simpler and more cost-effective process when compared with existing methods. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were used to characterize the samples, which indicated the presence of phosphorous. X-ray photoelectron spectroscopy (XPS) confirmed the formation of gallium oxide, along with a minor amount of phosphorus-containing compounds. Structural analysis using X-ray diffraction (XRD) revealed the formation of a monoclinic ß-polymorph of Ga2O3. We also measured the band gap of the materials using reflection electron energy loss spectroscopy (REELS), and found that the band gap increased with higher nanostructure formation, reaching 6.2 eV for the optimized sample. Furthermore, we observed a change in the heterojunction alignment, which we attribute to the change in the oxidation of the samples. Our results demonstrate the potential of ULPING as a novel, simple, and cost-effective method for fabricating Ga2O3 nanostructures with tunable optical properties. The ULPING method offers a green alternative to existing fabrication methods, making it a promising technology for future research in the field of Ga2O3 nanostructure fabrication.

Protocol for fabricating pseudocapacitor electrodes using ultra-short laser pulses for in situ nanostructure generation.

Ultra-short laser pulses for in situ nanostructure generation (ULPING) enable the production of high-performance capacitive electrodes for pseudocapacitors, opening avenues for optimal electrode design. Here, we present a protocol for fabricating pseudocapacitor electrodes using ULPING. We describe steps for electrode fabrication, coin cell assembly, material characterization, and electrochemical analysis. Additionally, we present strategies for generating data and constructing machine learning algorithms to predict the electrochemical properties of the fabricated electrodes. For complete details on the use and execution of this protocol, please refer to Khosravinia et al. (2023).1.

Optimizing the Ultrashort Laser Pulses for In Situ Nanostructure Generation Technique for High-Performance Supercapacitor Electrodes Using Artificial Neural Networks and Simulated Annealing Algorithms.

Transition metals (TMs) are being investigated as electrodes for pseudocapacitors, where an oxide layer is necessary to allow for rapid redox reactions. In this work, we utilized an in situ, rapid, binder-free, and green method for the fast fabrication of pseudocapacitor electrodes called ultrashort laser pulses for in situ nanostructure generation (ULPING) to form oxide layers on a titanium sheet. By utilizing this fabrication technique on a titanium sheet, a specific areal capacitance of 0.3579 mF cm-2 was achieved at a current density of 0.25 mA cm-2. However, the laser fabrication parameters were selected experimentally and resulted in low performance of pseudocapacitors. Therefore, one of the main objectives of this study was to find the optimal laser fabrication parameters to achieve the highest specific areal capacitance. A large dataset was generated to find the relationship between the laser fabrication parameters and the electrochemical behavior performance (impedance and specific areal capacitance) of the fabricated electrodes by using an artificial neural network (ANN). We used an optimization algorithm (simulated annealing-SA) to overlook the trained ANN model as a black box and try to maximize the objective function, which in our case is a specific capacitance value, to find the most optimal laser fabrication parameters. Using SA, optimal laser fabrication parameters were found, which increased the specific areal capacitance to 0.9999 mF cm-2 at a current density of 0.25 mA cm-2. The results demonstrated that the conducted study has the potential to introduce effective techniques for utilizing ULPING to produce nanoscale structures on TMs. These structures have the potential to be employed as electrodes in pseudocapacitors. Additionally, the research underscores the significance of employing data-driven approaches in electrode design procedures.

Binder-free NiO/CuO hybrid structure via ULPING (Ultra-short Laser Pulse for In-situ Nanostructure Generation) technique for supercapacitor electrode.

Developing a cost-effective pseudocapacitor electrode manufacturing process incorporating binder-free, green synthesis methods and single-step fabrication is crucial in advancing supercapacitor research. This study aims to address this pressing issue and contribute to the ongoing efforts in the field by introducing ULPING (Ultra-short Laser Pulse for In-situ Nanostructure Generation) technique for effective design. Laser irradiation was conducted in ambient conditions to form a CuO/NiO hybrid structure providing a synergistic contribution to the electrical behavior of the electrode. Mainly, the effects of surface morphology and electrochemical surface because of tuning laser intensity were analyzed. The samples demonstrated high oxide formation, fiber generation, excellent porosity, and ease of ion accessibility. Owing to a less than 10-min binder-free fabrication method, the electrochemical performance of the as-fabricated electrode was 25.8 mC cm-2 at a current density of 1 mA cm-2 proved to be excellent. These excellent surface properties were possible by the simple working principle of pulsed laser irradiation in ambient conditions and smart tuning of the important laser parameters. The CuO/NiO electrode demonstrates excellent conductivity and rewarding cyclic stability of 83.33% after 8000 cycles. This study demonstrates the potential of the ULPING technique as a green and simple method for fabricating high-performance pseudocapacitor electrodes.

Unlocking pseudocapacitors prolonged electrode fabrication via ultra-short laser pulses and machine learning.

Pseudocapacitors outperform lithium-ion batteries in terms of charging rate and power density. However, their electrode manufacturing procedures are prolonged and environmentally unfriendly, posing a research challenge. To address this issue, the one-step synthesis approach of ultra-short laser pulses for in situ nanostructure generation (ULPING) has been proposed. The generated nanostructures on the substrate through ULPING depend on the laser parameters, which leaves room for improvement in this field. The present study aims to build a theoretical bridge between the laser parameters used in the fabrication of pseudocapacitors and their electrochemical performance through machine learning approaches. Gaussian process regression (GPR), random forest (RF), and artificial neural network (ANN) have been employed to mimic the electrochemical behavior of pseudocapacitors, demonstrating the potential of ULPING in generating nanostructures on transition metals that can serve as pseudocapacitor electrodes. This research presents a promising method for producing binder-free and carbon-free pseudocapacitor electrodes efficiently and sustainably.

Gallium Oxide Nanostructures: A Review of Synthesis, Properties and Applications.

Gallium oxide, as an emerging semiconductor, has attracted a lot of attention among researchers due to its high band gap (4.8 eV) and a high critical field with the value of 8 MV/cm. This paper presents a review on different chemical and physical techniques for synthesis of nanostructured ß-gallium oxide, as well as its properties and applications. The polymorphs of Ga2O3 are highlighted and discussed along with their transformation state to ß-Ga2O3. Different processes of synthesis of thin films, nanostructures and bulk gallium oxide are reviewed. The electrical and optical properties of ß-gallium oxide are also highlighted, based on the synthesis methods, and the techniques for tuning its optical and electrical properties compared. Based on this information, the current, and the possible future, applications for ß-Ga2O3 nanostructures are discussed.

Tracking the Evolution of Metastasis with Self-Functionalized 3D Nanoprobes.

Despite recent advances in cancer treatment, metastasis is the cause of mortality in 90% of cancer cases. It has now been well-established that dissemination of cancer cells to distant sites occurs very early during tumorigenesis, resulting in the minimal effect of surgical or chemotherapeutic treatments after the detection of metastasis. The underlying reason for this challenge is mostly due to the limited understanding of molecular mechanisms of the metastasis cascade, particularly related to metastatic traits. Therefore, there is an urgent need to investigate this currently invisible evolution of metastasis. The tracking of metastasis evolution has not been addressed yet. Here, we introduce, for the first time, a synchronous approach to unveil the molecular mechanisms of the metastasis cascade. As cancer stem cells (CSCs) demonstrate cancer initiation, drug resistance, metastasis, and tumor relapse and can exist in a quasi-intermediate epithelial-mesenchymal transition state, the tumor-initiating events during a CSCs metamorphosis were monitored with single-cell sensitivity. Because of the invasive and resistive properties of the metastable intermediate CSCs, investigation of the molecular profiles of the quasi-intermediate CSCs was necessary for the detection of metastasis dissemination. For this purpose, the ultrasensitive technique of surface-enhanced Raman scattering (SERS) was adopted. Titanium-based, biocompatible three-dimensional (3D) nanoprobes that were synthesized for multiphoton ionization achieved a substantial SERS enhancement of ∼80-fold due to the oxygen vacancy-enriched composition of the nanoprobes. The 3D interconnected complex nanoarchitecture of the nanoprobes enabled us to entrap the nonadherent CSCs of three metastatic cancer cell lines (triple negative breast adenocarcinoma (MDAMB231), human Caucasian colon adenocarcinoma (COLO 205), and cervical adenocarcinoma (HeLa)─all very aggressive forms of cancer). The nanoprobes not only promoted the CSC proliferation to successfully attain the quasi-intermediate states but also monitored its reprogramming into a cancer cell state. The nanoprobes substantially amplified weak intracellular Raman signals to capture the molecular events during a CSC transformation. The detection of cancer was achieved with 100% accuracy. We experimentally demonstrated that the molecular signatures of CSC reprogramming are cancer-type specific. This observation enabled us to identify the origin of metastasis with 100% accuracy, providing more clarity on the relatively unknown quasi-intermediate states. This first demonstration of CSC-based tracking of metastasis evolution has the potential to provide an insightful perspective of tumorigenesis that could be useful in cancer diagnosis and prognosis as well as in the monitoring of therapeutic interventions.

Design of advanced siRNA therapeutics for the treatment of COVID-19.

COVID-19 is a newly emerged viral disease that is currently affecting the whole globe. A variety of therapeutic approaches are underway to block the SARS-CoV-2 virus. Among these methods, siRNAs could be a safe and specific option, as they have been tested against other viruses. siRNAs are a class of inhibitor RNAs that act promisingly as mRNA expression blockers and they can be designed to interfere with viral mRNA to block virus replication. In order to do this, we designed and evaluated the efficacy of six highly specific siRNAs, which target essential viral mRNAs with no predicted human genome off-targets. We observed a significant reduction in the copy number viral mRNAs after treatment with the siRNAs, and are expected to inhibit virus replication. We propose siRNAs as a potential co-therapy for acute SARS-CoV-2 infection.

Electrochemical Performance of Titania 3D Nanonetwork Electrodes Induced by Pulse Ionization at Varied Pulse Repetitions.

Pulse ionized titania 3D-nanonetworks (T3DN) are emerging materials for fabricating binder-free and carbon-free electrodes for electrochemical energy storage devices. In this article, we investigate the effect of the one of the most important fabrication parameters, pulse frequency, for optimizing supercapacitor efficiency. A series of coin cell batteries with laser-induced electrodes was fabricated; the effect of pulse frequency on oxidation levels and material properties was studied using both experimental and theoretical analysis. Also, detailed electrochemical tests including cyclic voltammetry (CV), charge/discharge, and electrochemical impedance spectroscopy (EIS) were conducted to better understand the effect of pulse frequency on the electrochemical performance of the fabricated devices. The results show that at a frequency of 600 kHz, more T3DN were observed due to the higher temperature and stabler formation of the plasma plume, which resulted in better performance of the fabricated supercapacitors; specific capacitances of samples fabricated at 600 kHz and 1200 kHz were calculated to be 59.85 and 54.39 mF/g at 500 mV/s, respectively.

Design of hydrogel-based scaffolds for the treatment of spinal cord injuries.

Spinal cord injury (SCI) is a traumatic lesion that diminishes sensory and/or motor neuronal functionality, directly affecting the quality of the patient's life. Due to the central nervous system's (CNS) inhibitory microenvironment that presents challenges in neuron repair and regeneration, tissue engineering strategies have received significant attention to improve the quality of a patient's life. In this regard, hydrogels are attractive SC scaffolds as they can provide not only an adjustable physiologically native-like microenvironment but also an appropriate matrix for cell delivery, drug delivery, and other bioactive molecule delivery at the lesion site. This systematic review characterizes the widely used biomaterials including natural polymers; protein- and polysaccharide-based synthetic polymers; methacrylate- and polyethylene glycol-based, and self-assembling (SA) peptides. In addition, synthesis routes of hydrogels are investigated. This review is complemented by the discussion of the various techniques utilized for hydrogel scaffold designs with their in vitro and in vivo outcomes and clinical trials. The existing challenges and opportunities for SC hydrogel scaffolds are mentioned towards the end of this review.

3D Titania Nanofiber-Like Webs Induced by Plasma Ionization: A New Direction for Bioreactivity and Osteoinductivity Enhancement of Biomaterials.

In this study, we describe the formation method of web-like three-dimensional (3-D) titania nanofibrous structures coated on transparent substrate via a high intensity laser induced reverse transfer (HILIRT) process. First, we demonstrate the mechanism of ablation and deposition of Ti on the glass substrates using multiple picosecond laser pulses at ambient air in an explicit analytical form and compare the theoretical results with the experimental results of generated nanofibers. We then examine the performance of the developed glass samples coated by titania nanofibrous structures at varied laser pulse durations by electron microscopy and characterization methods. We follow this by exploring the response of human bone-derived mesenchymal stem cells (BMSCs) with the specimens, using a wide range of in-vitro analyses including MTS assay (colorimetric method for assessing cell metabolic activity), immunocytochemistry, mineralization, ion release examination, gene expression analysis, and protein adsorption and absorption analysis. Our results from the quantitative and qualitative analyses show a significant biocompatibility improvement in the laser treated samples compared to untreated substrates. By decreasing the pulse duration, more titania nanofibers with denser structures can be generated during the HILIRT technique. The findings also suggest that the density of nanostructures and concentration of coated nanofibers play critical roles in the bioreactivity properties of the treated samples, which results in early osteogenic differentiation of BMSCs.

Laser processing of thin-film multilayer structures: comparison between a 3D thermal model and experimental results.

In this research, a numerical model is introduced for simulation of laser processing of thin film multilayer structures, to predict the temperature and ablated area for a set of laser parameters including average power and repetition rate. Different thin-films on Si substrate were processed by nanosecond Nd:YAG laser pulses and the experimental and numerical results were compared to each other. The results show that applying a thin film on the surface can completely change the temperature field and vary the shape of the heat affected zone. The findings of this paper can have many potential applications including patterning the cell growth for biomedical applications and controlling the grain size in fabrication of polycrystalline silicon (poly-Si) thin-film transistors (TFTs).

Synthesis of Electrical Conductive Silica Nanofiber/Gold Nanoparticle Composite by Laser Pulses and Sputtering Technique.

Biocompatible-sensing materials hold an important role in biomedical applications where there is a need to translate biological responses into electrical signals. Increasing the biocompatibility of these sensing devices generally causes a reduction in the overall conductivity due to the processing techniques. Silicon is becoming a more feasible and available option for use in these applications due to its semiconductor properties and availability. When processed to be porous, it has shown promising biocompatibility; however, a reduction in its conductivity is caused by its oxidization. To overcome this, gold embedding through sputtering techniques are proposed in this research as a means of controlling and further imparting electrical properties to laser induced silicon oxide nanofibers. Single crystalline silicon wafers were laser processed using an Nd:YAG pulsed nanosecond laser system at different laser parameters before undergoing gold sputtering. Controlling the scanning parameters (e.g., smaller line spacings) was found to induce the formation of nanofibrous structures, whose diameters grew with increasing overlaps (number of laser beam scanning through the same path). At larger line spacings, nano and microparticle formation was observed. Overlap (OL) increases led to higher light absorbance's by the wafers. The gold sputtered samples resulted in greater conductivities at higher gold concentrations, especially in samples with smaller fiber sizes. Overall, these findings show promising results for the future of silicon as a semiconductor and a biocompatible material for its use and development in the improvement of sensing applications.

Mammalian fibroblast cells avoid residual stress zone caused by nanosecond laser pulses.

This study investigates the effects of laser irradiation on crystalline silicon and its application in biomaterials. We used an analytical model to predict the ablation depth and pit size resulting from laser exposure of silicon samples. The temperatures generated are predicted correlate with laser power, and to result in the formation of a residual stress zone bordering the ablated groove. Different crystal orientations found in the substrate confirm that there was crystal distortion, which consequently induces these residual stress zones. Mouse embryonic fibroblasts avoid the stress areas and accumulate outside of these zones. Higher laser power results in broader residual stress zone and a larger zone of cellular exclusion. We argue that residual stress resulting from high-energy laser ablation of silicon may be a promising avenue to explore as a method for patterning cell growth on these materials.

Mammalian fibroblast cells show strong preference for laser-generated hybrid amorphous silicon-SiO2 textures.

BACKGROUND: In this study, we investigated a method to produce bioactive hybrid amorphous silicon and silicon oxide patterns using nanosecond laser pulses. METHODS: Microscale line patterns were made by laser pulses on silicon wafers at different frequencies (25, 70 and 100 kHz), resulting in ablation patterns with frequency-dependent physical and chemical properties. RESULTS: Incubating the laser-treated silicon substrates with simulated body fluid demonstrated that the physicochemical properties of the laser-treated samples were stable under these conditions, and favored the deposition of bone-like apatite. More importantly, while NIH 3T3 fibroblasts did colonize the untreated regions of the silicon wafers, they showed a strong preference for the laser-treated regions, and further discriminated between substrates treated with different frequencies. CONCLUSIONS: Taken together, these data suggest that laser materials processing of silicon-based devices is a promising avenue to pursue in the production of biosensors and other bionic devices.

Mouse embryonic fibroblasts accumulate differentially on titanium surfaces treated with nanosecond laser pulses.

Biomaterial engineering, specifically in bone implant and osseointegration, is currently facing a critical challenge regarding the response of cells to foreign objects and general biocompatibility of the materials used in the production of these implants. Using the developing technology of the laser surface treatment, this study investigates the effects of the laser repetition rate (frequency) on cell distribution across the surface of the titanium substrates. The main objective of this research is building a fundamental understanding of how cells interact with treated titanium and how different treatments affect cell accumulation. Cells respond differently to surfaces treated with different frequency lasers. The results of this research identify the influence of frequency on surface topography properties and oxidation of titanium, and their subsequent effects on the pattern of cell accumulation on its surface. Despite increased oxidation in laser-treated regions, the authors observe that fibroblast cells prefer untreated titanium to laser-treated regions, except the regions treated with 25 kHz pulses, which become preferentially colonized after 72 h.

Bioactivity enhancement of titanium induced by Nd:Yag laser pulses.

PURPOSE: In this research, the effect of laser properties such as laser power and laser dwell time on the surface morphology and oxidizing of titanium have been investigated in order to enhance the bioactivity of laser textured titanium sheets. METHODS: The Ti samples were irradiated with nanosecond pulses to create the predetermined point patterns on the surface of sample sheets with specific laser parameters. Final bioactivity of the treated samples were evaluated through the use of simulated body fluid (SBF), followed by material characterization techniques such as X-ray diffraction (XRD) and energy dispersive (EDX). RESULTS: It was observed that by increasing the roughness of the titanium surface samples using a range of dwelling time, and with different powers, titania with higher levels of surface energy in micro/sub-micro scales are produced. The use of laser results in a one-step heat increase and the oxidation of titanium, which results in creation of titania with higher cell adhesion abilities. CONCLUSIONS: It was concluded that the variation of the surface roughness, surface morphology, and oxidation level of the material has a direct effect on the cell adhesion rate to the surface of the titanium. Upon completion of the analysis, it is concluded that using a higher power and a lower dwelling time results in better bioactivity improvement than using higher dwelling times and lower powers.

Optical absorption enhancement in 3D nanofibers coated on polymer substrate for photovoltaic devices.

Recent research in the field of photovoltaics has shown that polymer solar cells have great potential to provide low-cost, lightweight and flexible electronic devices to harvest solar energy. In this paper, we propose a new method for the generation of three-dimensional nanofibers coated on polymer substrate induced by femtosecond laser pulses. In this new method, a thin layer of polymer is irradiated by megahertz femtosecond laser pulses under ambient conditions, and a thin fibrous layer is generated on top of the polymer substrate. This method is single step; no additional materials are added, and the layers of the three-dimensional (3D) polymer nanofibrous structures are grown on top of the substrate after laser irradiation. Light spectroscopy results show significant enhancement of light absorption in the generated 3D nanofibrous layers of polymer. Finally, we suggest how to maximize the light trapping and optical absorption of the generated nanofiber cells by optimizing the laser parameters.

Optical absorption enhancement in 3D silicon oxide nano-sandwich type solar cell.

Recent research in the field of photovoltaic and solar cell fabrication has shown the potential to significantly enhance light absorption in thin-film solar cells by using surface texturing and nanostructure coating techniques. In this paper, for the first time, we propose a new method for nano sandwich type thin-film solar cell fabrication by combining the laser amorphization (2nd solar cell generation) and laser nanofibers generation (3rd solar cell generation) techniques. In this novel technique, the crystalline silicon is irradiated by megahertz frequency femtosecond laser pulses under ambient conditions and the multi-layer of amorphorized silicon and nano fibrous layer are generated in the single-step on top of the silicon substrate. Light spectroscopy results show significant enhancement of light absorption in the generated multi layers solar cells (Silicon Oxide nanofibers / thin-film amorphorized silicon). This method is single step and no additional materials are added and both layers of the amorphorized thin-film silicon and three-dimensional (3D) silicon oxide nanofibrous structures are grown on top of the silicon substrate after laser irradiation. Finally, we suggest how to maximize the light trapping and optical absorption of the generated nanofibers/thin-film cells by optimizing the laser pulse duration.