Autor Mária Čaplovičová

Core-shell nanofibers of ZnFe2O4/ZnO for enhanced visible-light photoelectrochemical performance

Andrii Lys, Viktor Zabolotnii, Mária Čaplovičová, Iryna Tepliakova, Agris Berzins, Martin Sahul, Ľubomír Čaplovič, Alexander Pogrebnjak, Igor Iatsunskyi, Roman Viter

In: Journal of Alloys and Compounds,Volume 984, 2024, 173885


Recent research places significant importance on the development of innovative nanocomposites for photoelectrochemical applications. This paper presents the fabrication, characterization, and possible photoelectrochemical applications of novel ZnFe2O4/ZnO core-shell nanofibers. These core-shell nanofibers were fabricated through co-axial electrospinning using PVP solutions containing iron and zinc nitrate precursors for the core and shell. The structural and optical properties of ZnFe2O4/ZnO core-shell nanofibers were examined through TEM, SEM, XRD, FTIR, Raman spectroscopy, and diffuse reflectance spectroscopy. This comprehensive analysis unveiled that the development of core and shell characteristics was notably influenced by the interdiffusion of [Fe]/[Zn] during the annealing process. The photoelectrochemical properties of ZnFe2O4/ZnO core-shell nanofibers were assessed through electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), and the Mott-Schottky method. These core-shell nanofibers demonstrated a robust electrochemical response to visible light. Photocurrent and photoconversion efficiency of the core-shell nanofibers were calculated and compared with the corresponding values for core-shell nanoparticles. The mechanisms underlying the structural, optical, and photoelectrochemical properties of ZnFe2O4/ZnO core-shell nanofibers were discussed. These advanced nanofibers hold potential applications in photocatalysis, photovoltaics, and energy storage, making this research timely and crucial for advancing sustainable energy technologies and environmental remediation efforts.

Effect of bias voltage on the structural properties of WN/NbN nanolayer coatings deposited by cathodic-arc evaporation

K. Smyrnova, M. Sahul, M Haršáni, Ľ. Čaplovič, V. Beresnev, Mária Čaplovičová, M. Kusy and A. Pogrebnjak

In: J. Phys.: Conf. Ser. 2712 012014, 2024


In this work, WN/NbN nanolaminate coatings were synthesized by cathodic-arc physical vapor deposition (CA-PVD) technique on a stainless-steel substrate. The paper reports the microstructure, cross-sectional morphology, surface roughness, and adhesion strength changes caused by variations in the absolute values of the negative substrate bias voltage, Us, in the 50-200 V range. Synthesized coatings were analyzed by Grazing incidence X-ray diffraction (GI-XRD), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM), laser scanning confocal microscopy (LSCM), and Daimler-Benz test. The phase analysis revealed that multilayer coatings had complex polycrystalline microstructure. They consisted of face-cantered cubic (fcc) β-W2N, fcc δ-NbN, and hexagonal ε-NbN phases. The total thickness and surface roughness had a descending trend with an increase in the absolute value of the negative bias voltage. Moreover, the WN/NbN coating deposited at Us = -50 V demonstrated the best adhesion strength to the substrate, suitable for protective coatings.

Influence of process and heat input on the microstructure and mechanical properties in wire arc additive manufacturing of hot work tool steels

Florian Pixner, Ricardo Buzolin, Fernando Warchomicka, Mária Dománková, Mária Čaplovičová, Florian Riedlsperger, Sebastian Fritsche, Marta Orłowska, Josef Domitner, Michael Lasnik, Norbert Enzinger

In: Materials Science and Engineering: A, Volume 888, 17 November 2023, 145799


The present study demonstrates the suitability of wire arc additive manufacturing (AM) for hot work tool steel processing. Different arc welding techniques and energy inputs were applied and systematically compared to determine the deposition characteristics, microstructure and mechanical properties. All AM deposits show a sound visual appearance and full density without macroscopic imperfections, i.e. cracking. By adhering to a pre-defined interpass strategy, the cold metal transfer process can be used to achieve higher weld beads with lower dilution and faster build-up rates than the metal active gas process. The microstructure of the AM parts is comparable for all process configurations and consists of an α/α′-matrix with a finely dispersed vermicular and polygonal δ-ferrite network; no notable amount of retained austenite could be measured, but it could be observed by transmission electron microscopy embedded within the laths. Intensive precipitation of multiple molybdenum-based precipitates is observed along the interface matrix to δ-ferrite. In contrast, iron-based precipitates are predominantly found inside and at the boundaries of the laths of the matrix. Similarities are also evident in the mechanical properties, resulting in an average hardness of 380–390 HV1 and absorbed impact energy of 10–12 J at room temperature. High yield strength values of 1000–1100 MPa and ultimate tensile strength of 1200–1400 MPa were obtained. No significant differences in the measured mechanical properties could be noted regarding the specimen orientation, indicating the isotropy of the properties.

Ag2O nanocrystals prepared by mechanochemical decomposition of Ag7O8NO3

Martin Škrátek, Mária Čaplovičová, Ľubomír Čaplovič, Patrícia Petrisková, Erik Šimon, Erik Rakovský, Peter Billik

In: Materials Letters. Vol. 348, (2023)


Our work focuses on the preparation of nanocrystalline Ag2O (n-Ag2O) by mechanochemical decomposition (MCD) of a paramagnetic compound of an empirical formula Ag7O8NO3. Electrochemically prepared millimetre-long needles of Ag7O8NO3 were high-energy ball milled (HEM) for 1 min, 3 min and 5 min. A gradual decomposition of Ag7O8NO3 to n-Ag2O and AgNO3 was observed. Ag2O nanocrystals form in an aggregated and spherical morphology with crystallite sizes ranging from ∼10 – 30 nm. n-Ag2O displayed weak ferromagnetism with the saturation magnetisation of 5×10–3 emu/g. The MCD of Ag7O8NO3 can be estimated as follows: 2Ag7O8NO3 → 6Ag2O + 2AgNO3 + 5O2.

Application of MXene for remediation of low-level radioactive aqueous solutions contaminated with 133Ba and 137Cs

Vipul Vilas Kusumkar, Shalu Atri, Süleyman İnan, Maros Gregor, Tomas Roch, Hryhorii Makarov, Maria Caplovicova, Michal Galambos, Eva Viglasova, Gustav Plesch and Olivier Monfort

In: Chem. Commun., 2023,59, 12007-12010


MXene is an innovative multilayered material that has been prepared by an acid-salt (HCl + NH4F) etching route and tested for the removal of 133Ba and 137Cs in radioactive conditions for the first time. MXene has exhibited high uptake capacity of about 154.9 and 121.5 mg g−1 for 133Ba and 137Cs, respectively, in 0.01 mol L−1 solution and using 5 g L−1 of adsorbent at natural pH.

GaAs ablation with ultrashort laser pulses in ambient air and water environments

Edgaras Markauskas,  Laimis Zubauskas, Arnas Naujokaitis, Bronislovas Čechavičius, Martynas Talaikis, Gediminas Niaura, Mária Čaplovičová, Viliam Vretenár, Tadas Paulauskas

In: Journal of Applied Physics. Vol. 133, iss. 23 (2023)


Water-assisted ultrashort laser pulse processing of semiconductor materials is a promising technique to diminish heat accumulation and improve process quality. In this study, we investigate femtosecond laser ablation of deep trenches in GaAs, an important optoelectronic material, using water and ambient air environments at different laser processing regimes. We perform a comprehensive analysis of ablated trenches, including surface morphological analysis, atomic-resolution transmission electron microscopy imaging, elemental mapping, photoluminescence, and Raman spectroscopy. The findings demonstrate that GaAs ablation efficiency is enhanced in a water environment while heat-accumulation-related damage is reduced. Raman spectroscopy reveals a decrease in the broad feature associated with amorphous GaAs surface layers during water-assisted laser processing, suggesting that a higher material quality in deep trenches can be achieved using a water environment.

Polycaprolactone–MXene Nanofibrous Scaffolds for Tissue Engineering

Kateryna Diedkova, Alexander D. Pogrebnjak, Sergiy Kyrylenko, Kateryna Smyrnova, Vladimir V. Buranich, Pawel Horodek, Pawel Zukowski, Tomasz N. Koltunowicz, Piotr Galaszkiewicz, Kristina Makashina, Vitaly Bondariev, Martin Sahul, Mária Čaplovičová, Yevheniia Husak, Wojciech Simka, Viktoriia Korniienko, Agnieszka Stolarczyk, Agata Blacha-Grzechnik, Vitalii Balitskyi, Veronika Zahorodna, Ivan Baginskiy, Una Riekstina, Oleksiy Gogotsi, Yury Gogotsi, and Maksym Pogorielov

In: ACS Applied Materials & Interfaces. Vol. 15, iss. 11 (2023)


New conductive materials for tissue engineering are needed for the development of regenerative strategies for nervous, muscular, and heart tissues. Polycaprolactone (PCL) is used to obtain biocompatible and biodegradable nanofiber scaffolds by electrospinning. MXenes, a large class of biocompatible 2D nanomaterials, can make polymer scaffolds conductive and hydrophilic. However, an understanding of how their physical properties affect potential biomedical applications is still lacking. We immobilized Ti3C2Tx MXene in several layers on the electrospun PCL membranes and used positron annihilation analysis combined with other techniques to elucidate the defect structure and porosity of nanofiber scaffolds. The polymer base was characterized by the presence of nanopores. The MXene surface layers had abundant vacancies at temperatures of 305–355 K, and a voltage resonance at 8 × 104 Hz with the relaxation time of 6.5 × 106 s was found in the 20–355 K temperature interval. The appearance of a long-lived component of the positron lifetime was observed, which was dependent on the annealing temperature. The study of conductivity of the composite scaffolds in a wide temperature range, including its inductive and capacity components, showed the possibility of the use of MXene-coated PCL membranes as conductive biomaterials. The electronic structure of MXene and the defects formed in its layers were correlated with the biological properties of the scaffolds in vitro and in bacterial adhesion tests. Double and triple MXene coatings formed an appropriate environment for cell attachment and proliferation with mild antibacterial effects. A combination of structural, chemical, electrical, and biological properties of the PCL–MXene composite demonstrated its advantage over the existing conductive scaffolds for tissue engineering.

Fe3O4-PEI Nanocomposites for Magnetic Harvesting of Chlorella vulgaris, Chlorella ellipsoidea, Microcystis aeruginosa, and Auxenochlorella protothecoides

GERULOVÁ, Kristína – KUCMANOVÁ, Alexandra – SANNY, Zuzana – GARAIOVÁ, Zuzana – SEILER, Eugen – ČAPLOVIČOVÁ, Mária – ČAPLOVIČ, Ľubomír – PALCUT, Marián

In Nanomaterials. Vol. 12, iss. 11 (2022)


Magnetic separation of microalgae using magnetite is a promising harvesting method as it is fast, reliable, low cost, energy-efficient, and environmentally friendly. In the present work, magnetic harvesting of three green algae (Chlorella vulgaris, Chlorella ellipsoidea, and Auxenochlorella protothecoides) and one cyanobacteria (Microcystis aeruginosa) has been studied. The biomass was flushed with clean air using a 0.22 μm filter and fed CO2 for accelerated growth and faster reach of the exponential growth phase. The microalgae were harvested with magnetite nanoparticles. The nanoparticles were prepared by controlled co-precipitation of Fe2+ and Fe3+ cations in ammonia at room temperature. Subsequently, the prepared Fe3O4 nanoparticles were coated with polyethyleneimine (PEI). The prepared materials were characterized by high-resolution transmission electron microscopy, X-ray diffraction, magnetometry, and zeta potential measurements. The prepared nanomaterials were used for magnetic harvesting of microalgae. The highest harvesting efficiencies were found for PEI-coated Fe3O4. The efficiency was pH-dependent. Higher harvesting efficiencies, up to 99%, were obtained in acidic solutions. The results show that magnetic harvesting can be significantly enhanced by PEI coating, as it increases the positive electrical charge of the nanoparticles. Most importantly, the flocculants can be prepared at room temperature, thereby reducing the production costs.

Contribution of photocatalytic and Fenton-based processes in nanotwin structured anodic TiO2 nanotube layers modified by Ce and V

THIRUNAVUKKARASU,  Guru Karthikeyan – GOWRISANKARAN, Sridhar – ČAPLOVIČOVÁ, Mária – SATRAPINSKYY, Leonid – GREGOR, Maroš – LAVRIKOVA, Aleksandra Y. – GREGUŠ, Ján – HALKO, Radoslav – PLESCH, Gustav – MOTOLA, Martin – MONFORT, Olivier

In Dalton Transactions. Vol. 51, iss. 28 (2022)


In the present work, nanotwin structured TiO2 nanotube (TNT) layers are prepared by the electrochemical anodization technique to form the anatase phase and by surface modification via spin-coating of Ce and V precursors to form Ce-TNT and V-TNT, respectively. The surface and cross-sectional images by SEM revealed that the nanotubes have an average diameter of ∼130 nm and a length of ∼14 μm. In addition, the TEM images revealed the nanotwin structures of the nanotubes, especially the anatase (001) and (112) twin surfaces, that increase the transport of photogenerated charges. The photoinduced degradation of caffeine (CAF) by TNT, Ce-TNT, and V-TNT led to a degradation extent of 16%, 26% and 33%, respectively, whereas it increased to 26%, 38%, and 46% in the presence of H2O2, owing to the involvement of Fenton-based processes (in addition to photocatalysis). The effect of the Fenton-based processes accounts for about 10% of the total degradation extent of CAF. Finally, the mechanism of the photoinduced degradation of CAF was investigated. The main oxidative species were the hydroxyl radicals, and the better efficiency of V-TNT over Ce-TNT and TNT was ascribed to its negative surface, thus improving the interactions with CAF.

Effect of Multiply Twinned Ag(0) Nanoparticles on Photocatalytic Properties of TiO2 Nanosheets and TiO2 Nanostructured Thin Films.

BAKARDJIEVA, Snejana – MAREŠ, Jakub – KOCI, Eva – TOLASZ, Jakub – FAJGAR, Radek – RYUKHTIN, Vasyl – KLEMENTOVÁ, Mariana – MICHNA, Štefan – BIBOVÁ, Hana – HOLMESTAD, Randi – TITORENKOVA, Rositsa – ČAPLOVIČOVÁ Mária

In Nanomaterials. Vol. 12, iss. 5 (2022)


Ag-decorated TiO2 nanostructured materials are promising photocatalysts. We used non-standard cryo-lyophilization and ArF laser ablation methods to produce TiO2 nanosheets and TiO2 nanostructured thin films decorated with Ag nanoparticles. Both methods have a common advantage in that they provide a single multiply twinned Ag(0) characterized by {111} twin boundaries. Advanced microscopy techniques and electron diffraction patterns revealed the formation of multiply twinned Ag(0) structures at elevated temperatures (500 °C and 800 °C). The photocatalytic activity was demonstrated by the efficient degradation of 4-chlorophenol and Total Organic Carbon removal using Ag-TiO2 nanosheets, because the multiply twinned Ag(0) served as an immobilized photocatalytically active center. Ag-TiO2 nanostructured thin films decorated with multiply twinned Ag(0) achieved improved photoelectrochemical water splitting due to the additional induction of a plasmonic effect. The photocatalytic properties of TiO2 nanosheets and TiO2 nanostructured thin films were correlated with the presence of defect-twinned structures formed from Ag(0) nanoparticles with a narrow size distribution, tuned to between 10 and 20 nm. This work opens up new possibilities for understanding the defects generated in Ag-TiO2 nanostructured materials and paves the way for connecting their morphology with their photocatalytic activity.