High-Efficiency Photo-Assisted Large Current-Density Water Splitting with Mott-Schottky Heterojunctions.

The development of bifunctional photogenerated carrier-assisted electrocatalytic (PCA-EC) electrodes that operate with stability at large current-density remains a significant challenge. Herein, we demonstrate a simple sputtering-deposition process to synthesize a novel MnWO4/FeCoNi Mott-Schottky heterojunction coating and deposit it on a pure Ti substrate to prepare high-performance PCA-EC electrodes, which exhibits enhanced light absorption range/intensity and rapidly separated photogenerated electron-hole pairs. This design allows photogenerated electrons to directly participate in the hydrogen evolution reaction (HER), while the strong oxidation of photogenerated holes significantly reduces the defect formation energy of active metals, thereby facilitating the rapid reconstruction of highly active Ni(FeCo)OOH/MnOOH species for the oxygen evolution reaction (OER). As expected, the as-prepared electrode demonstrates the overpotentials of 64 mV for the HER and 204 mV for the OER at 10 mA cm-2 under illumination. Benefiting from the stable interface with Fe/Co/Ni-O-Mn/W bonding units, the dual-electrode photoassisted electrolytic cell achieves long-term stability at current densities of 500 and 1000 mA cm-2. This work provides detailed insights into the enhancement mechanism of PCA-EC and contributes to the development of photo-assisted water splitting electrodes for large current-density applications.

Rapid Defect Engineering in FeCoNi/FeAl2O4 Hybrid for Enhanced Oxygen Evolution Catalysis: A Pathway to High-Performance Electrocatalysts.

Rational modulation of surface reconstruction in the oxygen evolution reaction (OER) utilizing defect engineering to form efficient catalytic activity centers is a topical interest in the field of catalysis. The introduction of point defects has been demonstrated to be an effective strategy to regulate the electronic configuration of electrocatalysts, but the influence of more complex planar defects (e.g., twins and stacking faults), on their intrinsic activity is still not fully understood. This study harnesses ultrasonic cavitation for rapid and controlled introduction of different types of defects in the FeCoNi/FeAl2O4 hybrid coating, optimizing OER catalytic activity. Theoretical calculations and experiments demonstrate that the different defects optimize the coordination environment and facilitate the activation of surface reconstruction into true catalytic activity centers at lower potentials. Moreover, it demonstrates exceptional durability, maintaining stable oxygen production at a high current density of 300 mA cm-2 for over 120 hours. This work not only presents a novel pathway for designing advanced electrocatalysts but also deepens our understanding of defect-engineered catalytic mechanisms, showcasing the potential for rapid and efficient enhancement of electrocatalytic performance.

Hybrid Metal/Spinel Oxide Coating with Microcone Arrays to Stimulate a Photothermal-Augmented Oxygen Evolution Reaction.

To boost the kinetic process of the oxygen evolution reaction (OER), hybrid CoNiFe/Fe(Fe,Mo,Al)2 O4 coatings are deposited on pure Ti substrates (namely, CoNiFe/Fe(Fe,Mo,Al)2 O4 /Ti electrodes). This new coating features a dense inner layer together with an outer layer of microcone arrays (MCAs). The electrochemical surface area of the electrodes is modulated by controlling the geometrical factors of the MCAs. For the OER in 1.0 m KOH, the electrodes require minimum overpotentials of 245 and 333 mV to realize current densities of, respectively, 10 and 100 mA cm-2 . Furthermore, the high aspect ratio of the MCAs enables the electrodes to exhibit strong sunlight capture. Under 10 min of simulated 1.0 sun illumination, the electrode's temperature can rise by up to 108.2 °C. The number of active sites and the OER reaction rate of the electrodes are further increased by photoassistance, with only 234 and 296 mV overpotentials, respectively, needed to generate current densities of 10 and 100 mA cm-2 with a Tafel slope as low as 40.9 mV dec-1 . Therefore, the application of this composite coating, which exhibits photothermal effects with respect to conventional Ti electrodes, provides an inspiration for further improvement of OER catalytic efficiency.

A Superhydrophilic, Light/Microwave-Absorbing Coating with Remarkable Antibacterial Efficacy.

Driven by the overuse of antibiotics, pathogenic infections, dominated by the rapid emergence of antibiotic resistant bacteria, have become one of the greatest current global health challenges. Thus, there is an urgent need to explore novel strategies that integrate multiple antibacterial modes to deal with bacterial infections. In this work, a Co(Ni,Ag)/Fe(Al,Cr)2O4 composite duplex coating was fabricated using template-free sputtering deposition technology. The phase constitution of the coating was estimated to be 79 wt % Fe(Al,Cr)2O4 phase and 21 wt % of an Ag-containing metallic phase. The composite coating consisted of a ∼10 µm-thick porous outer-layer and a ∼6 µm-thick compact inner-layer, in which the outer-layer is composed of a densely stacked array of microscale cones. After exposure to ambient air for 14 days, the composite coating showed a wettability transition from a superhydrophilic nature to exhibit adhesive superhydrophobic behavior with a water contact angle of 142° ± 2.8°, but it reverted to its initial superhydrophilic state after annealing in air at 200 °C for 5 h. The absorption rate of the as-received composite coating exceeds 99% in a broad band spanning both the visible and NIR regions and showed a high photothermal efficiency to convert photon energy into heat. Similarly, the composite coating showed microwave absorption behavior with a minimum reflection loss value of 38 dB at 4.4 GHz. In vitro antibacterial tests were used to determine the antibacterial behavior of the composite coating against Escherichia coli and Staphylococcus aureus after 60 min of visible light irradiation. After this exposure, the as-prepared composite coating exhibited nearly 100% bactericidal efficiency against these bacteria. The antibacterial behavior of the coating was attributed to the synergistic effects of the superhydrophilic surface, the release of Ag+ ions, and the photothermal effect. Therefore, this composite coating may be a promising candidate to efficiently combat medical device-associated infections.

The influence of semiconducting properties of passive films on the cavitation erosion resistance of a NbN nanoceramic coating.

To alleviate the cavitation damage of metallic engineering components in hydrodynamic systems operating in marine environments, a NbN nanoceramic coating was synthesized on to a Ti-6Al-4V substrate via a double cathode glow discharge technique. The microstructure of the coating consisted of a ~13 µm thick deposition layer of a hexagonal δ'-NbN phase and a diffusion layer ~2 µm in thickness composed of face-centered cubic (fcc) B1-NaCl-structured (Ti,Nb)N. The NbN coating not only exhibited higher values of H/E and H2/E than those measured from NbN coatings deposited by other techniques, but also possessed good adhesion to the substrate. The cavitation erosion resistance of the NbN coating in a 3.5 wt% NaCl solution was investigated using an ultrasonic cavitation-induced apparatus combined with a range of electrochemical test methods. Potentiodynamic polarization measurements demonstrated that the NbN coated specimens demonstrated both a higher corrosion potential (Ecorr) and lower corrosion current density (icorr) than the uncoated substrate. Mott-Schottky analysis, combined with the point defect model (PDM), revealed that, for a given cavitation time, the donor density (ND) of the passive film on the NbN coating was reduced by 1 ~ 2 orders of magnitude relative to the uncoated Ti-6Al-4V, and the diffusivity of the point defects (D0) in the passive film grown on the NbN coating was nearly one order of magnitude lower than that on the uncoated substrate. In order to better understand the experimental observations obtained from Mott-Schottky analysis and double-charge layer capacitance measurements, first-principles density-functional theory was employed to calculate the energy of vacancy formation and the adsorption energy for chloride ions for the passive films present on both the NbN coating and bare Ti-6Al-4V.

Remarkable bactericidal traits of a metal-ceramic composite coating elated by hierarchically structured surface.

A ceramic-based coating with a hierarchical surface structure was synthesized via solid-state reaction enabled by a double cathode glow discharge technique. This innovative coating comprises two distinct layers, specifically an outer layer with a well-aligned micro-pillar array and a dense inner layer. Both are composed of a face-centered cubic Cu(Co,Ni,Fe) solid solution phase together with a spinel-type Fe(Al,Cr)2O4 oxide. This coating exhibits superhydrophobicity and, yet, a very strong adhesion to water, i.e., the so-called "rose petal effect". This coating also exhibits highly efficient antibacterial ability against both Staphylococcus aureus and Escherichia coli bacteria under both dark and visible light conditions. The excellent antibacterial property originates from the synergistic effects through the release of Cu ions coupled with photothermal activity upon light activation.

Enhancing the cavitation erosion resistance of D8m-Ta5Si3 nanocrystalline coatings through Al alloying.

To investigate the effects of Al alloying on the erosion-corrosion resistance of ß-Ta5Si3, both a ß-Ta5Si3 coating and an Al-alloyed ß-Ta5(Si0.83Al0.17)3 coating were synthesized on a 316 substrate by the double cathode glow discharge technique. The phase constitution, composition and microstructure of the two coatings were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The two coatings were composed of nearly rounded D8m-ß-Ta5Si3 grains with an average size of ∼4 nm, and after the addition of Al, the preferred growth orientation for the ß-Ta5Si3 coating changed from (4 0 0) to (0 0 2). The hardness, elastic modulus and contact damage resistance of the coatings were measured using a nanoindentation tester. The results showed that Al alloying improved the contact damage resistance of ß-Ta5Si3 with only a slight decrease in hardness. The erosion-corrosion behavior of the two coatings was performed in a 3.5 wt% NaCl solution containing a 12 wt% concentration of silica sand under two phase slurry flow condition and in a 3.5 wt% NaCl solution under ultrasonic cavitation erosion conditions. This revealed that the Al alloyed ß-Ta5Si3 has a higher resistance to both erosion-corrosion and ultrasonic cavitation erosion as compared to the binary ß-Ta5Si3 coating.

Effect of Al alloying on cavitation erosion behavior of TaSi2 nanocrystalline coatings.

To broaden the scope of non-aerospace applications for titanium-based alloys, both hexagonal C40 binary TaSi2 and ternary Al alloyed TaSi2 nanocrystalline coatings were exploited to enhance the cavitation erosion resistance of Ti-6Al-4V alloy in acidic environments. To begin with, the roles of Al addition in influencing the structural stability and mechanical properties of hexagonal C40 Ta(Si1-xAlx)2 compounds were modelled using first-principles calculations. The calculated key parameters, such as Pugh's index (B/G ratio), Poisson's ratio, and Cauchy pressures, indicated that there was a threshold value for Al addition, below which the increase of Al content would render the Ta(Si1-xAlx)2 compounds more ductile, but above which no obvious change would occur. Subsequently, the TaSi2 and Ta(Si0.875Al0.125)2 coatings were prepared and their microstructure and phase composition were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Both the two coatings exhibited a uniform thickness of 15 µm and a densely packed structure mainly composed of spherically shaped nanocrystallites with an average diameter of about 5 nm. Nanoindentation measurements revealed that Al alloying reduced the hardness (H) and elastic modulus (E) values of the TaSi2 coating. Ultrasonic cavitation erosion tests were carried out by immersing coated and uncoated samples in a 0.5 M HCl solution. The cavitation-erosion analysis of the tested samples was investigated by various electrochemical techniques, mass loss weight and SEM observation. The results suggested that both coated samples provided a better protection for Ti-6Al-4V against the cavitation-erosion damage in acidic environments, but the addition of Al further improved the cavitation-erosion resistance of the TaSi2 coating.

Electrochemical Properties of a Novel ß-Ta2O5 Nanoceramic Coating Exposed to Simulated Body Solutions.

To enhance the corrosion resistance, biocompatibility and mechanical durability of biomedical titanium alloys, a novel ß-Ta2O5 nanoceramic coating was developed using a double glow discharge plasma technique. The surface morphology, phase composition and microstructure of the as-deposited coating were examined by atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The coating exhibits a striated structural pattern along the growth direction, which consists of equiaxed ß-Ta2O5 grains, 15-20 nm in diameter in cross-section, showing a strong (001) preferred orientation. The mechanical properties and contact damage resistance of the ß-Ta2O5 coating were evaluated by nanoindentation. Additionally, scratch tests were performed to evaluate the adhesion strength between the ß-Ta2O5 coating and the Ti-6Al-4V substrate. The ß-Ta2O5 coating shows high hardness combined with good resistance to both indentation and scratch damage, thus favoring it for long-term load-bearing application in the human body. Electrochemical behavior of the coating was analyzed in both a 0.9 wt % NaCl solution and Ringer's solution at 37 °C, by various electrochemical analytical techniques, including potentiodynamic polarization, electrochemical impedance spectroscopy, potential of zero charge and Mott-Schottky analysis. Compared with uncoated Ti-6Al-4V and commercially pure tantalum, the ß-Ta2O5 coating possesses a more positive Ecorr and lower icorr in both aqueous solutions, which is attributed to the thicker and denser ß-Ta2O5 coating that provides more effective protection against corrosive attack. In addition, the ß-Ta2O5 coating shows stable impedance behavior over 5 days immersion under both simulated body solutions, corroborated by the capacitance and resistance values extracted from the EIS data. Mott-Schottky analysis reveals that the ß-Ta2O5 coating shows n-type semiconductor behavior and its donor density is independent of immersion time in both aqueous solutions. Its donor density is of the order of 1 × 1019 cm-3, which is an order of magnitude less than that of the passive films formed on either commercially pure Ta or uncoated Ti-6Al-4V. Moreover, according to the differences between corrosion potential and potential of zero charge, the ß-Ta2O5 coating exhibits a greater propensity to repulse chloride ions than both commercially pure Ta and uncoated Ti-6Al-4V. Therefore, the newly developed coating could be used to protect the surface of biomedical titanium alloys under harsh conditions.

Electrochemical Corrosion Behavior of Nanocrystalline ß-Ta Coating for Biomedical Applications.

To explore its potential as a highly corrosion-resistant coating for biomedical titanium alloys, a novel ß-Ta nanocrystalline coating, composed of equiaxed ß-Ta grains with an average grain size ∼22 nm, was deposited onto Ti-6Al-4V substrate using a double glow discharge plasma technique. The newly developed coating exhibited an extremely dense and homogeneous microstructure, exhibiting a strong (002) preferred orientation. The electrochemical behavior and semiconducting properties, such as donor density, flat-band potential, and diffusivity of point defects (Do), of the passive film formed on the ß-Ta coating were compared to those for both uncoated Ti-6Al-4V and commercially pure Ta in Ringer's physiological solution at 37 °C, using an array of complementary electrochemical techniques. The results showed that the ß-Ta coating not only provided Ti-6Al-4V with good corrosion protection but also endowed a higher resistance to corrosive attack than commercially pure Ta in Ringer's physiological solution at 37 °C. Mott-Schottky analysis revealed that the passive film formed on the ß-Ta coating had a lower donor density and flat-band potential than commercially pure Ta. The calculated values of Do for the ß-Ta coating (1.45 × 10-16cm2/s) are comparable to that for commercially pure Ta (1.13 × 10-16 cm2/s), both of which are 1 order of magnitude lower than that for uncoated Ti-6Al-4V (2.73 × 10-15 cm2/s). Compared with commercially pure Ta, the higher corrosion resistance of the ß-Ta coating results from its nanosized grains and crystallographic orientation, which promotes the rapid formation of a robust passive film with a more compact structure.

Promoting bone-like apatite formation on titanium alloys through nanocrystalline tantalum nitride coatings.

The study aims to advance the applicability of titanium alloys as bone implant materials by tackling some important aspects of surface robustness and bioactivity. To do so, biologically active Ta-N nanocrystalline coatings were engineered on Ti-6Al-4V alloy substrates by reactive sputter deposition using a double glow discharge plasma technique. The surface morphology, phase composition and structure of the coatings were characterized using atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The newly developed coatings are extremely dense, adherent and composed of a cubic TaN phase and a minor fraction of hexagonal Ta2N phase. The microstructure of Ta-N coatings consists of nanocrystallites of about 15-20 nm in diameter, having a strong TaN(200)-oriented texture. Moreover, the coatings exhibit a uniform nanopillar structure on the surface, critical for the observed bioactivity. Scratching tests were performed to evaluate the adhesion strength between the Ta-N coatings and Ti-6Al-4V alloy substrates. The Ta-N coatings were found to exhibit a high scratch resistance and are thus suitable for load-bearing applications. The apatite-inducing ability of the coatings was evaluated in vitro using a simulated body fluid (SBF) that has almost equal compositions of inorganic ions to human blood plasma. After soaking in the solution for up to 14 days, only a few apatite particulates were observed on the surface of untreated Ti-6Al-4V alloy. By contrast, the surface of the Ta-N coatings was completely covered by a compact, AB-type apatite layer free of micro-cracks. High resolution transmission electron microscopy (HRTEM) observations reveal that after soaking for 14 days, the apatite layer, formed through a biomimetic process, comprises closely packed, needle-shaped apatite crystals of 34.5 ± 12.4 nm in length and 6.0 ± 0.2 nm in width. Moreover, nanotwins were identified in apatite, reminiscent of those found in bone minerals. The negatively-charged surface, combined with a unique surface structure of the Ta-N nanoceramic coatings, is believed to be responsible for the formation of a homogenous, compact bone-like apatite layer. The Ta-N nanoceramic coatings are expected to find applications as an integral part of biomaterials used in bone repair and replacement.

Electrochemical behavior of (Ti 1-x Nb x)5Si3 nanocrystalline films in simulated physiological media.

In this paper, (Ti1-xNbx)5Si3 nanocrystalline films were synthesized and their potential as highly corrosion-resistant coatings for the biomedical alloy Ti-6Al-4V was explored. To assess the electrochemical behavior of the as-deposited films, the samples were immersed in Ringer's solution open to air at 37°C. The processes that govern the electrochemical reactions at the film surface were analyzed using a combination of complementary electrochemical measurement techniques such as potentiodynamic polarization, electrochemical impedance spectroscopy and Mott-Schottky analysis. The results show that the (Ti1-xNbx)5Si3 nanocrystalline films offer Ti-6Al-4V a strong shield from corrosive attack and the addition of Nb in the films greatly enhances their resistance to corrosion, and in so doing, minimizes metal ion release. Collectively, our data suggest that (Ti1-xNbx)5Si3 nanocrystalline films as supreme coatings with anti-corrosive properties have potential to improve the performance and extend the service life of orthopedic and cochlear implants.

Construction and biomechanical properties of polyaxial self-locking anatomical plate based on the geometry of distal tibia.

In order to provide scientific and empirical evidence for the clinical application of the polyaxial self-locking anatomical plate, 80 human tibias from healthy adults were scanned by spiral CT and their three-dimensional images were reconstructed using the surface shaded display (SSD) method. Firstly, based on the geometric data of distal tibia, a polyaxial self-locking anatomical plate for distal tibia was designed and constructed. Biomechanical tests were then performed by applying axial loading, 4-point bending, and axial torsion loading on the fracture fixation models of fresh cadaver tibias. Our results showed that variation in twisting angles of lateral tibia surface was found in various segments of the distal tibia. The polyaxial self-locking anatomical plate was constructed based on the geometry of the distal tibia. Compared to the conventional anatomical locking plate, the polyaxial self-locking anatomical plate of the distal tibia provides a better fit to the geometry of the distal tibia of the domestic population, and the insertion angle of locking screws can be regulated up to 30°. Collectively, this study assesses the geometry of the distal tibia and provides variable locking screw trajectory to improve screw-plate stability through the design of a polyaxial self-locking anatomical plate.