Autor Mária Čaplovičová

ZnO nanoparticles as photodegradation agent controlled by morphology and boron doping

ZnO nanoparticles as photodegradation agent controlled by morphology and boron doping

Daniel Furka, Samuel Furka, Mira Naftaly, Erik Rakovský, Mária Čaplovičová, Marián Janek

Catal. Sci. Technol., 2021,11, 2167-2185


Photolytic degradation of model dyes on pure and boron-doped zinc oxide (ZnO) nanoparticles with pseudohexagonal or elongated spindle-like morphology was investigated. ZnO nanoparticles were prepared by spray-assisted co-precipitation solvothermal synthesis. The bandgap (Eg) of pure ZnO was decreased by boron doping. The prepared nanoparticles were tested for their photocatalytic activity by decomposition of different organic dyes, using phloxine, oxazine and rhodamine as test substances simulating environmental pollutants. The photolysis experiments were done in a 3D printed photoreactor using a photodiode with a wavelength of 365 ± 5 nm as a narrow-line radiation source. The observed first-order reaction kinetics revealed that higher reaction rates were achieved on pseudohexagonal nanoparticles. Increasing the boron content led to accelerated photolysis rates. A significant linear correlation was observed between the optical bandgap energy Eg and the residual dye concentration remaining after 6 hours from the start of the reaction. It was found that ZnO particles with pseudohexagonal morphology decompose organic dyes faster than elongated spindle-like particles, indicating dependence on the surface area as determined by BET analysis. Interestingly, the residual dye concentration varied more strongly with doping when elongated spindle-like nanoparticles were used. It was shown that the efficiency of a photolysis reaction occurring on a solid oxide/solution interface is affected by the crystallographic plane on which it takes place.

Dehydroaromatization of methane over Mo/ZSM-5 zeolites: influence of aluminum distribution in the crystals

HORŇÁČEK, Michal – HUDEC, Pavol – JORÍK, Vladimír – ČAPLOVIČOVÁ, Mária – ČAPLOVIČ, Ľubomír – KALIŇÁK, Michal – SMIEŠKOVÁ, Agáta

In Reaction Kinetics Mechanisms and Catalysis. Vol. 131, iss. 2 (2020)


Mo/ZSM-5 type catalysts based on two ZSM-5 zeolites with comparable crystal morphology, shape and size, Si/Al in bulk (22–23), acidity and amount of Mo (~ 4.7 wt.%) but having a different (homogeneous and non-homogeneous) Al distribution in particles and different acid sites type distribution were investigated in methane dehydroaromatization. From the results follows that Mo is associated with both BAS and LAS in the samples with almost homogenous Al distribution (MoZSM-5/AH). In the case of both samples with non-homogenous Al distribution (MoZSM-5/BH and MoZSM-5/BNH4) Mo preferably associates with BAS. Evidently lower activity and selectivity of Mo/ZSM-5/AH catalyst in methane transformation compared with Mo/ZSM-5/BH we attribute to the fact that from Mo species which interact with Lewis acid sites in sample ZSM-5/AH less active carburized species are formed as from the Mo associated with Brønsted sites in sample ZSM-5/BH.

Green synthesis of stable nanocolloids of monodisperse silver and gold nanoparticles using natural polyphenols from fruits of Sambucus nigra L


In Applied Nanoscience. Vol. 10, iss. 12 (2020)


In the present work, we report, for the first time, the production of stable nanocolloids of highly monodisperse silver and gold nanoparticles (AgNPs and AuNPs) using phytosynthesis approach. With the aim to eliminate misinterpretations associated with the use of usually applied crude plant extracts, the presented study was focused on the use of polyphenolic fraction isolated from elderberry fruits (Sambucus nigra L.) for the synthesis. Obtained AgNPs and AuNP were characterized by UV–Vis and FTIR spectroscopy, DLS and TEM. We observed unexpectedly high capability of the natural polyphenols not only to form monodisperse nanoparticles but also to stabilise the concentrated nanocolloids (539 mg/L AgNPs and 739 mg/L AuNPs) for at least two years. Moreover, AgNPs showed strong antibacterial properties against pathogenic bacterial strains Staphylococcus aureus and Escherichia coli (inhibited after 15 min and totally stopped growth after 3 and 5 h at 3.125 mg/L concentration).

Ni-mediated reactions in nanocrystalline diamond on Si substrates: the role of the oxide barrier

TULIČ, Semir – WAITZ, Thomas – ROMANYUK, Oleksandr – VARGA, Marián – ČAPLOVIČOVÁ, Mária – HABLER, Gerlinde – VRETENÁR, Viliam – KOTLÁR, Mário – KROMKA, Alexander – REZEK, Bohuslav – SKÁKALOVÁ, Viera

In RSC Advances. Vol. 10, iss. 14 (2020)


Nanocrystalline diamond (NCD) films grown on Si substrates by microwave plasma enhanced chemical vapor deposition (MWPECVD) were subjected to Ni-mediated graphitization to cover them with a conductive layer. Results of transmission electron microscopy including electron energy-loss spectroscopy of cross-sectional samples demonstrate that the oxide layer on Si substrates (∼5 nm native SiO2) has been damaged by microwave plasma during the early stage of NCD growth. During the heat treatment for graphitizing the NCD layer, the permeability or absence of the oxide barrier allow Ni nanoparticles to diffuse into the Si substrate and cause additional solid-state reactions producing pyramidal crystals of NiSi2 and SiC nanocrystals. The latter are found impinged into the NiSi2 pyramids but only when the interfacial oxide layer is absent, replaced by amorphous SiC. The complex phase morphology of the samples is also reflected in the temperature dependence of electrical conductivity, where multiple pathways of the electronic transport dominate in different temperature regions. We present models explaining the observed cascade of solid-state reactions and resulting electronic transport properties of such heterostructures.

Ti3+ doped anodic single-wall TiO2 nanotubes as highly efficient photocatalyst

MOTOLA, Martin – ČAPLOVIČOVÁ, Mária – KRBAL, Miloš – SOPHA, Hannah – THIRUNAVUKKARASU,  Guru Karthikeyan – GREGOR, Maroš – PLESCH, Gustáv – MACAK, Jan M.

In Electrochimica Acta. Vol. 331, (2020)


In this work, a two-step treatment of TiO2 nanotube (TNT) layers towards enhanced photocatalytic performance is presented. TNT layers with a thickness of ∼7 μm and an average inner diameter of ∼190 nm were prepared via electrochemical anodization of Ti foil in a fluoride containing ethylene glycol-based electrolyte. To improve the photocatalytic activity of the produced TNT layers a two-step post-treatment was conducted. First, the inner shell of the native double-wall TNT layers was removed via a mild pre-annealing followed by a selective etching treatment of the inner shell in piranha solution yielding single-wall TNT layers. Second, reduction via annealing in H2/Ar atmosphere was performed. The resulting Ti3+ doped single-wall TNT layers possess 100% enhancement of photocatalytic activity compared to their non-treated counterparts.

Changes in microstructure of ledeburitic tool steel due to vacuum austenitizing and quenching, sub-zero treatments at – 140° and tempering


In Vacuum. Vol. 170, (2019)


The microstructure of Vanadis 6 ledeburitic steel subjected to sub-zero treatments at −140 °C for different durations followed by various tempering regimes was investigated. The obtained results infer that: i) retained austenite amount is fivefold reduced by this treatment, and compressive stresses higher than 1500 MPa are generated in this phase, ii) martensite is refined due to SZT, and it contains enhanced number of crystal defects, iii) great number of “extra” cementitic carbides is formed during the sub-zero period; this number is higher than what is achieved by sub-zero treatments at −196 °C, iv) the number of “extra” carbides decreases with tempering, however, it remains higher than after in both the conventionally quenched and sub-zero treated at −196 °C steel, v) sub-zero treatments at −140 °C modify the precipitation behaviour substantially; coherent nano-sized ε-carbides and cementite were found already prior tempering the steel, and besides the cementite also M7C3 phase was detected after tempering treatment.

Tuning the orientation of few-layer MoS2 films using one-zone sulfurization

SOJKOVÁ, Michaela – VÉGSÖ, Karol – MRKYVKOVA, Naďa – HAGARA, Jakub – HUTÁR, Peter – ROSOVÁ, Alica – ČAPLOVIČOVÁ, Mária – LUDACKÁ, Uršula – SKÁKALOVÁ, Viera – MAJKOVÁ, Eva – ŠIFFALOVIČ, Peter

In RSC Advances. Vol. 9, iss. 51 (2019)


Few-layer MoS2 films are promising candidates for applications in numerous areas, such as photovoltaics, photocatalysis, nanotribology, lithium batteries, hydro-desulfurization catalysis and dry lubricants, especially due to their distinctive electronic, optical, and catalytic properties. In general, two alignments of MoS2 layers are possible – the horizontal and the vertical one, having different physicochemical properties. Layers of both orientations are conventionally fabricated by a sulfurization of pre-deposited Mo films. So far, the Mo thickness was considered as a critical parameter influencing the final orientation of MoS2 layers with horizontally and vertically aligned MoS2 grown from thin (1 nm) and thick (3 nm) Mo films, respectively. Here, we present a fabrication protocol enabling the growth of horizontally or vertically aligned few-layer MoS2 films utilizing the same Mo thickness of 3 nm. We show that the sulfur vapor is another parameter influencing the growth mechanism, where a sulfurization with higher sulfur vapor pressure leads to vertical MoS2 layers and slow sulfur evaporation results in horizontally aligned layers for a thicker Mo starting layer.

Stoichiometry, structure and mechanical properties of co-sputtered Ti 1-x Ta x B 2±Δ coatings

GRANČIČ, B. – PLEVA, Milan – MIKULA, M. – ČAPLOVIČOVÁ, Mária – SATRAPINSKYY, L – ROCH, Tomáš – TRUCHLÝ, M. – SAHUL, Martin – GREGOR, M. – ŠVEC, Peter, Sr. – ZAHORAN, Miroslav – KÚŠ, Peter

In Surface & Coatings Technology. Vol. 367, June (2019)


Magnetron co-sputtering from TiB2 and TaB2 stoichiometric targets is used to prepare AlB2-prototype ternary Ti1-xTaxB2±Δ solid solution, with x in the range from 0 to 1. Using this technique, the boron-to-metal ratio (B/Me) varies with the actual Ti and Ta content. The boron-to‑tantalum ratio can be increased by decreasing the TaB2 target voltage, which has a considerable effect on the coating structure. Coatings with B/Me > 2 reveal highly textured nanocolumnar structure, while the coatings with B/Me < 2 tend to be nanocrystalline (without any preferred crystallite orientation) or amorphous. All the deposited coatings have a hardness higher than 32 GPa. The under-stoichiometric (B/Me < 2) coatings show material pile-up around the cube-corner indent edges, an indication for plastic flow and increased ductility.