Laser-Treated MXene as an Electrochemical Agent to Boost Properties of Semitransparent Photoelectrode Based on Titania Nanotubes.

In this study, Ti3C2Tx underwent laser treatment to reshape it, resulting in the formation of a TiO2/Ti3C2Tx heterojunction. The interaction with laser light induced the formation of spherical TiO2 composed of an anatase-rutile phase on the Ti3C2Tx surface. Such a heterostructure was loaded over a titania nanotube (TNT) layer, and the surface area was enhanced through immersion in a TiCl4 solution followed by thermal treatment. Consequently, the photon-to-electron conversion efficiency exhibits a 10-fold increase as compared to bare TNT. Moreover, for the sample produced with optimized conditions, five times higher photoactivity is observed in comparison to bare TNT. It was shown that under visible light irradiation the most photoactive heterojunction based on the tubular layer reveals a substantial drop in the charge transfer resistance of about 32% with respect to the dark condition. This can be attributed to the narrower band gaps of the modified material and improvement of the separation efficiency of the photogenerated electron-hole pairs. Overall results suggest that this investigation underscores TiO2/Ti3C2Tx as a promising noble-metal-free material that enhances both the electrochemical and photoelectrochemical performances of electrode materials based on TNT that can be further used in light-harvesting applications.

Laser-Induced Graphitization of Polydopamine on Titania Nanotubes.

Since the discovery of laser-induced graphite/graphene, there has been a notable surge of scientific interest in advancing diverse methodologies for their synthesis and applications. This study focuses on the utilization of a pulsed Nd:YAG laser to achieve graphitization of polydopamine (PDA) deposited on the surface of titania nanotubes. The partial graphitization is corroborated through Raman and XPS spectroscopies and supported by water contact angle, nanomechanical, and electrochemical measurements. Reactive molecular dynamics simulations confirm the possibility of graphitization in the nanosecond time scale with the evolution of NH3, H2O, and CO2 gases. A thorough exploration of the lasing parameter space (wavelength, pulse energy, and number of pulses) was conducted with the aim of improving either electrochemical activity or photocurrent generation. Whereas the 532 nm laser pulses interacted mostly with the PDA coating, the 365 nm pulses were absorbed by both PDA and the substrate nanotubes, leading to a higher graphitization degree. The majority of the photocurrent and quantum efficiency enhancement is observed in the visible light between 400 and 550 nm. The proposed composite is applied as a photoelectrochemical (PEC) sensor of serotonin in nanomolar concentrations. Because of the suppressed recombination and facilitated charge transfer caused by the laser graphitization, the proposed composite exhibits significantly enhanced PEC performance. In the sensing application, it showed superior sensitivity and a limit of detection competitive with nonprecious metal materials.

Texture or Linker? Competitive Patterning of Receptor Assembly toward Ultra-Sensitive Impedimetric Detection of Viral Species at Gold-Nanotextured Titanium Surfaces.

In this work, we study the electrodes with a periodic matrix of gold particles pattered by titanium dimples and modified by 3-mercaptopropionic acid (MPA) followed by CD147 receptor grafting for specific impedimetric detection of SARS-CoV-2 viral spike proteins. The synergistic DFT and MM/MD modeling revealed that MPA adsorption geometries on the Au-Ti surface have preferential and stronger binding patterns through the carboxyl bond inducing an enhanced surface coverage with CD147. Control of bonding at the surface is essential for oriented receptor assembling and boosted sensitivity. The complex Au-Ti electrode texture along with optimized MPA concentration is a crucial parameter, enabling to reach the detection limit of ca. 3 ng mL-1. Scanning electrochemical microscopy imaging and quantum molecular modeling were performed to understand the electrochemical performance and specific assembly of MPA displaying a free stereo orientation and not disturbed by direct interactions with closely adjacent receptors. This significantly limits nonspecific interceptor reactions, strongly decreasing the detection of receptor-binding domain proteins by saturation of binding groups. This method has been demonstrated for detecting the SARS virus but can generally be applied to a variety of protein-antigen systems. Moreover, the raster of the pattern can be tuned using various anodizing processes at the titania surfaces.

Scanning with Laser Beam over the TiO2 Nanotubes Covered with Thin Chromium Layers towards the Activation of the Material under the Visible Light.

This work presents pulsed UV laser treatment (355 nm, 2 Hz) of TiO2 nanotubes decorated with chromium oxides. The modification was performed in a system equipped with a beam homogenizer, and during the irradiation, the samples were mounted onto the moving motorized table. In such a system, both precisely selected areas and any large area of the sample can be modified. Photoelectrochemical tests revealed photoresponse of laser-treated samples up to 1.37- and 18-fold under the illumination with ultraviolet-visible and visible light, respectively, in comparison to bare titania. Optimal beam energy fluence regarding sample photoresponse has been established. Scanning electron microscopy images, X-ray diffraction patterns, along with Raman and X-ray photoelectron spectra, suggest that the enhanced photoresponse results from changes solely induced in the layer of chromium oxides. It is believed that the results of the present work will contribute to a wider interest in laser modification of semiconductors exhibiting improved photoelectrochemical activity.

The Impact of Side-Selective Laser Tailoring of Titania Nanotubes on Changes in Photoelectrocatalytic Activity.

Over the last few decades, titanium(IV) oxide-based materials have gained particular attention due to their stability, corrosion resistance, photocatalytic activity under UV light, and possibilities for modification. Among various structures, TiO2 nanotubes (NTs) grown on Ti foil or glass substrates and obtained through a simple anodization process are widely used as photocatalysts or photoanodes. During the anodization process, the geometry of the nanotubes (length, distribution, diameter, wall thickness, etc.) is easily controlled, though the obtained samples are amorphous. Heat treatment is required to transform the amorphous material into crystalline material. However, instead of time- and cost-consuming furnace treatment, fast and precise laser annealing is applied as a promising alternative. Nonetheless, laser treatment can result in geometry changes of TiO2 NTs, consequently altering, their electrochemical activity. Moreover, modification of the TiO2 NTs surfaces with transition metals and further laser treatment can result in materials with unique photoelectrochemical properties. In this regard, we gathered the latest achievements in the field of laser-treated titania for this review paper. We mainly focused on single structural and morphological changes resulting from pulsed laser annealing and their influence on the electrochemical properties of titania. Finally, the theoretical basis for and combination of laser- and metal-modifications and their impact on the resulting possibilities for electrochemical water splitting are also discussed.

Antibacterial properties of laser-encapsulated titanium oxide nanotubes decorated with nanosilver and covered with chitosan/Eudragit polymers.

To provide antibacterial properties, the titanium samples were subjected to electrochemical oxidation in the fluoride-containing diethylene glycol-based electrolyte to create a titanium oxide nanotubular surface. Afterward, the surface was covered by sputtering with silver 5 nm film, and the tops of the nanotubes were capped using laser treatment, resulting in an appearance of silver nanoparticles (AgNPs) of around 30 nm in diameter on such a modified surface. To ensure a controlled release of the bactericidal substance, the samples were additionally coated with a pH-sensitive chitosan/Eudragit 100 coating, also exhibiting bactericidal properties. The modified titanium samples were characterized using SEM, EDS, AFM, Raman, and XPS techniques. The wettability, corrosion properties, adhesion of the coating to the substrate, the release of AgNPs into solutions simulating body fluids at different pH, and antibacterial properties were further investigated. The obtained composite coatings were hydrophilic, adjacent to the surface, and corrosion-resistant. An increase in the amount of silver released as ions or metallic particles into a simulated body fluid solution at acidic pH was observed for modified samples with the biopolymer coating after three days of exposure avoiding burst effect. The proposed modification was effective against both Gram-positive and Gram-negative bacteria.

Tailoring Diffusional Fields in Zwitterion/Dopamine Copolymer Electropolymerized at Carbon Nanowalls for Sensitive Recognition of Neurotransmitters.

The importance of neurotransmitter sensing in the diagnosis and treatment of many psychological illnesses and neurodegenerative diseases is non-negotiable. For electrochemical sensors to become widespread and accurate, a long journey must be undertaken for each device, from understanding the materials at the molecular level to real applications in biological fluids. We report a modification of diamondized boron-doped carbon nanowalls (BCNWs) with an electropolymerized polydopamine/polyzwitterion (PDA|PZ) coating revealing tunable mechanical and electrochemical properties. Zwitterions are codeposited with PDA and noncovalently incorporated into a structure. This approach causes a specific separation of the diffusion fields generated by each nanowall during electrochemical reactions, thus increasing the contribution of the steady-state currents in the amperometric response. This phenomenon has a profound effect on the sensing properties, leading to a 4-fold enhancement of the sensitivity (3.1 to 14.3 µA cm-2 µM-1) and a 5-fold decrease of the limit of detection (505 to 89 nM) in comparison to the pristine BCNWs. Moreover, as a result of the antifouling capabilities of the incorporated zwitterions, this enhancement is preserved in bovine serum albumin (BSA) with a high protein concentration. The presence of zwitterion facilitates the transport of dopamine in the direction of the electrode by intermolecular interactions such as cation-π and hydrogen bonds. On the other hand, polydopamine units attached to the surface form molecular pockets driven by hydrogen bonds and π-π interactions. As a result, the intermediate state of dopamine-analyte oxidation is stabilized, leading to the enhancement of the sensing properties.

The Anodization of Thin Titania Layers as a Facile Process towards Semitransparent and Ordered Electrode Material.

Photoanodes consisting of titania nanotubes (TNTs) grown on transparent conductive oxides (TCO) by anodic oxidation are being widely investigated as a low-cost alternative to silicon-based materials, e.g., in solar light-harvesting applications. Intending to enhance the optical properties of those photoanodes, the modification of the surface chemistry or control of the geometrical characteristics of developed TNTs has been explored. In this review, the recent advancement in light-harvesting properties of transparent anodic TNTs formed onto TCO is summarized. The physical deposition methods such as magnetron sputtering, pulsed laser deposition and electron beam evaporation are the most reported for the deposition of Ti film onto TCO, which are subsequently anodized. A concise description of methods utilized to improve the adhesion of the deposited film and achieve TNT layers without cracks and delamination after the anodization is outlined. Then, the different models describing the formation mechanism of anodic TNTs are discussed with particular focus on the impact of the deposited Ti film thickness on the adhesion of TNTs. Finally, the effects of the modifications of both the surface chemistry and morphological features of materials on their photocatalyst and photovoltaic performances are discussed. For each section, experimental results obtained by different research groups are evoked.

Nanostructure of the laser-modified transition metal nanocomposites for water splitting.

Although hydrogen is considered by many to be the green fuel of the future, nowadays it is primarily produced through steam reforming, which is a process far from ecological. Therefore, emphasis is being put on the development of electrodes capable of the efficient production of hydrogen and oxygen from water. To make the green alternative possible, the solution should be cost-efficient and well processable, generating less waste which is a huge challenge. In this work, the laser-based modification technique of the titania nanotubes containing sputtered transition metal species (Fe, Co, Ni, and Cu) was employed. The characteristics of the electrodes are provided both for the hydrogen and oxygen evolution reactions, where the influence of the laser treatment has been found to have the opposite effect. The structural and chemical analysis of the substrate material provides insight into pathways towards more efficient, low-temperature water splitting. Laser-assisted integration of transition metal with the tubular nanostructure results in the match-like structure where the metal species are accumulated at the head. The electrochemical data indicates a significant decrease in material resistance that leads to an overpotential of only +0.69 V at 10 mA cm-2for nickel-modified material.

Simple synthesis route for fabrication of protective photo-crosslinked poly(zwitterionic) membranes for application in non-enzymatic glucose sensing.

This work focuses on the fabrication of non-enzymatic glucose sensing materials based on laser-formed Au nanoparticles embedded in Ti-textured substrates. Those materials possess good catalytic activity toward glucose oxidation in 0.1 × phosphate buffered saline as well as resistance to some interferants, such as ascorbic acid, urea, and glycine. The electrodes are further coated with three different polymers, that is, Nafion, photo-crosslinked poly(zwitterions) based on sulfobetaine methacrylate, and a hybrid membrane consisting of both polymers. Both the optimal integrity of the material and its catalytic activity toward glucose oxidation were maintained by the hybrid membranes with a large excess of poly(zwitterions) (mass ratio 20:1). The chemical structures of the as-formed membranes are confirmed by Fourier transform infrared spectroscopy. Due to the zwitterionic nature of the coating, the electrodes are resistant to biofouling and maintain electrochemical activity toward glucose for 4 days. Moreover, due to the synergistic effect of both Nafion and poly(zwitterions), the interference from the two compounds, namely, from acetylsalicylic acid and acetaminophen, was diminished. Besides the presence of polymer membranes, the electrode possesses a sensitivity of 36.8 µA cm-2  mM-1 in the linear range of 0.4-12 mM, while the limit of detection was estimated to be 23 µM. Finally, the electrodes are stable, and their response is not altered even by 1,000 bending cycles.

Influence of Annealing Atmospheres on Photoelectrochemical Activity of TiO2 Nanotubes Modified with AuCu Nanoparticles.

In this article, we studied the annealing process of AuCu layers deposited on TiO2 nanotubes (NTs) conducted in various atmospheres such as air, vacuum, argon, and hydrogen in order to obtain materials active in both visible and UV-vis ranges. The material fabrication route covers the electrochemical anodization of a Ti plate, followed by thin AuCu film magnetron sputtering and further thermal treatment. Scanning electron microscopy images confirmed the presence of spherical nanoparticles (NPs) formed on the external and internal walls of NTs. The optical and structural properties were characterized using UV-vis, X-ray diffraction, and X-ray photoelectron spectroscopies. It was proved that thermal processing under the argon atmosphere leads to the formation of a CuAuTi alloy in contrast to materials fabricated in air, vacuum, and hydrogen. The electrochemical measurements were carried out in NaOH using cyclic voltammetry, linear voltammetry, and chronoamperometry. The highest photoactivity was achieved for materials thermally treated in the argon atmosphere. In addition, the Mott-Schottky analysis was performed for bare TiO2 NTs and TiO2 NTs modified with gold copper NPs indicating a shift in the flatband potential. Overall, thermal processing resulted in changes in optical and structural properties as well as electrochemical and photoelectrochemical activities.

Enzyme Immobilization on Gold Nanoparticles for Electrochemical Glucose Biosensors.

More than 50 years have passed since Clark and Lyon developed the concept of glucose biosensors. Extensive research about biosensors has been carried out up to this day, and an exponential trend in this topic can be observed. The scope of this review is to present various enzyme immobilization methods on gold nanoparticles used for glucose sensing over the past five years. This work covers covalent bonding, adsorption, cross-linking, entrapment, and self-assembled monolayer methods. The experimental approach of each modification as well as further results are described. Designated values of sensitivity, the limit of detection, and linear range are used for the comparison of immobilization techniques.

Formation of the hollow nanopillar arrays through the laser-induced transformation of TiO2 nanotubes.

In the following article, we present a simple, two-step method of creating spaced, hollow nanopillars, from the titania nanotube arrays via pulsed laser-treatment. Due to the high ordering of the structure, the prepared material exhibits photonic properties, which has been shown to increase the overall photoefficiency. The optical and morphological changes in the titania nanotubes after pulsed laser-treatment with 532, 355, and 266 nm wavelengths in the 10-50 mJ/cm2 fluence range are studied. The investigation reveals, that by using appropriate wavelength and energy, the number of surface defects, geometrical features, or both can be tailored.

Anodic titania nanotubes decorated with gold nanoparticles produced by laser-induced dewetting of thin metallic films.

Herein, we combine titania layers with gold species in a laser-supported process and report a substantial change of properties of the resulting heterostructures depending on the major processing parameters. Electrodes were fabricated via an anodisation process complemented with calcination to ensure a crystalline phase, and followed by magnetron sputtering of metallic films. The obtained TiO2 nanotubes with deposited thin (5, 10 nm) Au films were treated with a UV laser (355 nm) to form Au nanoparticles on top of the nanotubes. It was proven that selected laser working parameters ensure not only the formation of Au nanoparticles, but also simultaneously provide preservation of the initial tubular architecture, while above-threshold laser fluences result in partial destruction (melting) of the top layer of the nanotubes. For almost all of the samples, the crystalline phase of the nanotubes observed in Raman spectra was maintained independently of the laser processing parameters. Enhanced photoresponse up to ca 6 mA/cm2 was demonstrated by photoelectrochemical measurements on samples obtained by laser annealing of the 10 nm Au coating on a titania support. Moreover, a Mott-Schottky analysis indicated the dramatically increased (two orders of magnitude) concentration of donor density in the case of a laser-treated Au-TiO2 heterojunction compared to reference electrodes.

The Effect of Laser Re-Solidification on Microstructure and Photo-Electrochemical Properties of Fe-Decorated TiO2 Nanotubes.

Fossil fuels became increasingly unpleasant energy source due to their negative impact on the environment; thus, attractiveness of renewable, and especially solar energy, is growing worldwide. Among others, the research is focused on smart combination of simple compounds towards formation of the photoactive materials. Following that, our work concerns the optimized manipulation of laser light coupled with the iron sputtering to transform titania that is mostly UV-active, as well as exhibiting poor oxygen evolution reaction to the material responding to solar light, and that can be further used in water splitting process. The preparation route of the material was based on anodization providing well organized system of nanotubes, while magnetron sputtering ensures formation of thin iron films. The last step covering pulsed laser treatment of 355 nm wavelength significantly changes the material morphology and structure, inducing partial melting and formation of oxygen vacancies in the elementary cell. Depending on the applied fluence, anatase, rutile, and hematite phases were recognized in the final product. The formation of a re-solidified layer on the surface of the nanotubes, in which thickness depends on the laser fluence, was shown by microstructure studies. Although a drastic decrement of light absorption was recorded especially in UV range, laser-annealed samples have shown activity under visible light even 20 times higher than bare titania. Electrochemical analysis has shown that the improvement of photoresponse originates mainly from over an order of magnitude higher charge carrier density as revealed by Mott-Schottky analysis. The results show that intense laser light can modulate the semiconductor properties significantly and can be considered as a promising tool towards activation of initially inactive material for the visible light harvesting.

Laser-Assisted Synthesis and Oxygen Generation of Nickel Nanoparticles.

Nowadays, more than ever, environmental awareness is being taken into account when it comes to the design of novel materials. Herein, the pathway to the creation of a colloid of spherical, almost purely metallic nickel nanoparticles (NPs) through pulsed laser ablation in ethanol is presented. A complex description of the colloid is provided through UV-vis spectroscopy and dynamic light scattering analysis, ensuring insight into laser-induced nanoparticle homogenization and size-control of the NPs. The transmission electron spectroscopy revealed spherical nanoparticles with a narrow size distribution, whereas the energy-dispersive X-ray spectroscopy accompanied by the X-ray photoelectron spectroscopy revealed their metallic nature. Furthermore, an example of the application of the colloidal nanoparticles is presented, where a quick, five-min ultrasound modification results in over an order of magnitude higher current densities in the titania-based electrode for the oxygen evolution reaction.

Novel approach to interference analysis of glucose sensing materials coated with Nafion.

We focus here on a novel approach to analysing the mechanisms of interference phenomena in glucose sensing, taking into account the changes within the Nafion layer deposited on the active surface. Several electrochemical techniques were used to verify the sustainability of catalytic properties of the electrode material after exposure to different compounds, i.e. ascorbic acid (AA), glycine, urea, acetylsalicylic acid (AsA), and acetaminophen (AAp). Through analysis of impedance data, we concluded that AAp and AsA were trapped permanently in the Nafion membrane, which significantly affected results repeatability. These observations were also confirmed by FT-IR investigations of the membrane after its immersion in solutions containing different interfering species. Moreover, after exposure to AsA and, unexpectedly, large concentrations of urea, the catalytic properties were completely lost, which, in consequence, make sensor reuse impossible. Such behaviour was justified by the chain reorganisation and swelling. Mechanisms involving adsorption onto the interphase and absorption in the membrane were proposed as key factors responsible for deterioration of membrane functionality and were confronted with FT-IR investigations. Following that, application of Nafion for non-invasive glucose sensor protection is unsatisfactory and cannot be considered for multiple detection procedures, especially taking into account biological fluids full of different interfering species.

Modified Manganese Phosphate Conversion Coating on Low-Carbon Steel.

Conversion coatings are one of the primary types of galvanic coatings used to protect steel structures against corrosion. They are created through chemical reactions between the metal surface and the environment of the phosphating. This paper investigates the impact that the addition of new metal cations to the phosphating reaction environment has on the quality of the final coating. So far, standard phosphate coatings have contained only one primary element, such as zinc in the case of zinc coatings, or two elements, such as manganese and iron in the case of manganese coatings. The structural properties have been determined using a scanning electron microscope (SEM), X-ray diffraction (XRD), and electrochemical tests. New manganese coatings were produced through a reaction between the modified phosphating bath and the metal (Ba, Zn, Cd, Mo, Cu, Ce, Sr, and Ca). This change was noticeable in the structure of the produced manganese phosphate crystallites. A destructive effect of molybdenum and chromium was demonstrated. Microscopic analysis, XRD analysis and electrochemical tests suggest that the addition of new metal cations to the phosphating bath affects the corrosion resistance of the modified coating.

The In-Depth Studies of Pulsed UV Laser-Modified TiO2 Nanotubes: The Influence of Geometry, Crystallinity, and Processing Parameters.

The laser processing of the titania nanotubes has been investigated in terms of morphology, structure, and optical properties of the obtained material. The length of the nanotubes and crystallinity, as well as the atmosphere of the laser treatment, were taken into account. The degree of changes of the initial geometry of nanotubes were checked by means of scanning electron microscopy, which visualizes both the surface and the cross-section. The phase conversion from the amorphous to anatase has been achieved for laser-treated amorphous material, whereas modification of calcined one led to distortion within the crystal structure. This result is confirmed both by Raman and grazing incident XRD measurements. The latter studies provided an in-depth analysis of the crystalline arrangement and allowed also for determining the propagation of laser modification. The narrowing of the optical bandgap for laser-treated samples has been observed. Laser treatment of TiO2 nanotubes can lead to the preparation of the material of desired structural and optical parameters. The usage of the motorized table during processing enables induction of changes in the precisely selected area of the sample within a very short time.

Free-standing TiO2 nanotubes decorated with spherical nickel nanoparticles as a cost-efficient electrocatalyst for oxygen evolution reaction.

Here, we report significant activity towards the oxygen evolution reaction (OER) of spherical nickel nanoparticles (NPs) electrodeposited onto free-standing TiO2 nanotubes (TNT) via cyclic voltammetry. It has been shown that simple manipulation of processing parameters, including scan rate and number of cycles, allows for formation of the NPs in various diameters and amounts. The polarization data with respect to transmission electron microscopy (TEM) allowed for determination of the diameter and propagation depth of the Ni NPs leading to the highest activity towards the OER with an overpotential of 540 mV at +10 mA cm-2 and Tafel slope of 52 mV per decade. X-ray photoelectron spectroscopy (XPS) indicates the presence of structure defects within Ni NPs whereas Mott-Schottky analysis provides information on the anodically shifted flat band potential and highly increased donor density. The obtained results along with literature studies allowed a proposal of the origin of the enhancement towards the OER. We believe that combination of transition metal-based NPs and TNT provides valuable insight on efficient and low-cost electrocatalysts.