By employing model semiconductor composite system n-type Bi₂S₃/n-type Bi₂O₃, and the concept of semiconductor electrochemistry, basic principles for the design of (photo)catalyst materials with application in energy conversion and advanced wastewater treatment processes, were analyzed and discussed. Absolute energy values of conduction band edge, E_CB, and valence band edge, E_VB, were correlated with the semiconductor's stability against decomposition and competitive redox reactions of free radical species formation. The energy-band diagrams were constructed for the proposed photocatalytic system. The E_CB position was determined from the flatband potential, E_FB, derived from Mott-Schottky analysis taking into account an additional potential drop in the Helmholtz layer due to the adsorption of potential determining ions on the semiconductor surface. Special attention was given to the accuracy of E_FB calculation due to the frequency dispersion of the capacitance.

Calcium phosphate-based (CaP) bioceramic materials are widely used in the field of bone regeneration, both in orthopaedics and in dentistry, due to their good biocompatibility, osseointegration and osteoconduction. The formation of CaP coatings on high-strength implant materials such as titanium alloys combines the superior mechanical properties of metals with the osteoconductive properties of CaP materials. In this work, the electrochemically assisted deposition of CaP coatings on the titanium alloy, TiAlNb, which is commonly used commercially as an implant material in orthopaedic devices, was examined. The barrier properties (electronic properties) of unmodified and CaP-modified titanium alloy were tested in situ in a simulated physiological solution, Hanks’ solution, under in vitro conditions of real implant applications using electrochemical impedance spectroscopy (EIS). The morphology and microstructure of the obtained CaP deposit were characterised by scanning electron microscopy (SEM) and chemical composition was assessed by energy dispersive X-ray spectroscopy (EDS) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The aim was to investigate the effect of calcium phosphate CaP coating on the corrosion resistance of the titanium TiAlNb alloy and to understand better the deposition process in the production of bioactive functional coatings on metallic implant materials.

In recent years, extensive studies have been continuously undertaken on the design of bioactive and biomimetic dental implant surfaces due to the need for improvement of the implant–bone interface properties. In this paper, the titanium dental implant surface was modified by bioactive vitamin D3 molecules by a self-assembly process in order to form an improved anticorrosion coating. Surface characterization of the modified implant was performed by field emission scanning electron microscopy (FE-SEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and contact angle measurements (CA). The implant’s electrochemical stability during exposure to an artificial saliva solution was monitored in situ by electrochemical impedance spectroscopy (EIS). The experimental results obtained were corroborated by means of quantum chemical calculations at the density functional theory level (DFT). The formation mechanism of the coating onto the titanium implant surface was proposed. During a prolonged immersion period, the bioactive coating effectively prevented a corrosive attack on the underlying titanium (polarization resistance in order of 10⁷ Ω cm²) with ~95% protection effectiveness.

Nitinol, as a shape memory alloy, is attractive material for medical implants and devices. Contrary to titanium, corrosion by releasing Ni₂₊ ions occurs during a long-term contact of Nitinol with (physiological) solutions containing Cl₋ ions. In order to develop chemically/electrochemically stable surfaces and interfaces, Nitinol was modified by dodecylphosphonate (−OH and −CH₃ terminated) self-assembled monolayers (SAMs), which were characterized by XPS, PM-IRRAS and contact angle measurements. Strongly bounded well-ordered films of high homogeneity and resistance were synthesized. An innovative method that allows in situ study of influence of thermal annealing, following SAM formation, on their protecting properties in simulated (physiological) solutions is presented. Changes of structural sensitive impedance parameters were correlated with the changes in the interfacial layer. Effective thermal annealing greatly enhances the quality of the self-assembled alkyl-phosphonate films, which behave as non-ideal dielectrics, i.e., the solid|liquid interfaces formed represent the blocking contact preventing charge-transfer reactions.

TiO₂-SnS₂ composite semiconducting photocatalysts with different building component ratios were prepared by hydrothermal synthesis (TiO₂-SnS₂-HT) and by immobilization of commercial TiO₂ and SnS₂ particles (TiO₂-SnS₂-COMM). The band gap values, which determine the catalysts’ photoactivity, were examined by diffuse reflectance spectroscopy and Kubelka–Munk transformations. The catalysts’ surface properties: specific surface area, charge and adsorption capacitance at the solid–solution interface were characterized using BET analysis, potentiometric titration and electrochemical impedance spectroscopy, respectively. The electronic band structure of TiO₂-SnS₂ photocatalyst, as the key property for the solar-driven photocatalysis, was deduced from the thermodynamic data and the semiconducting parameters (type of semiconductivity, concentration of the charge carriers, flat band potential) obtained by Mott–Schottky analysis. The photoactivity of both composites was studied in photocatalytic treatment of diclofenac (DCF) under simulated solar irradiation and was compared to the benchmark photocatalyst (TiO₂ P25) activity. The influence of process parameters, such as pH, H₂O₂, and composite formulation on the effectiveness of DCF removal and conversion was investigated and discussed by employing response surface modeling (RSM) approach. The photocatalytic efficiency of both composite materials was discussed on the basis of the hetereojunction formation that facilitated the photoelectron transfer, promoting more efficient photocatalytic degradation of DCF.

This study was focused on the synthesis and characterization of Si/Zr-based hybrid sol-gel coatings with and without the addition of cerium(III) ions. The coatings were deposited on aluminum aiming to act as an effective and ecologically harmless alternative to toxic chromate coatings. The chemical composition, structure, thermal properties and porosity of the non-doped and Ce-doped coatings containing various Zr contents were examined by Raman spectroscopy and photothermal beam deflection spectroscopy. The corrosion properties of the coated aluminum substrates were studied using AC and DC electrochemical methods in 0.1 M NaCl electrolyte solution. Barrier and protecting properties of the coatings were monitored upon long-term immersion in chloride solution using electrochemical impedance spectroscopy. The effect of cerium ions was two-fold: on the formation of a more condensed Si−O−Zr network structure and on the formation of Ce-based deposits, which diminish the rate of cathodic reaction at the coating/metal interface. These effects acted synergistically and resulted in the creation of the coatings with effective barrier and active corrosion protection.