ENVIRONMENTALLY SUSTAINABLE CERAMICS FOR APPLICATIONS AS MULTIFUNCTIONAL PHOTOCATALYST

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Oxygen vacancies, the optical band gap (Eg) and photocatalysis ofhydroxyapatite: Comparing modelling with measured data

Publication . Bystrov, V. S.; Piccirillo, C.; Tobaldi, D. M.; Castro, P. M. L.; Coutinho, J.; Kopyl, S.; Pullar, R.

Hydroxyapatite (Ca10(PO4)6(OH)2, HAp) is a calcium phosphate employed both in biomedicine and forenvironmental remediation. It is known that HAp can also be photocatalytic under UV light, probablydue to oxygen deficiencies, but the mechanism is unclear, and reported optical band gap energies varygreatly. For the first time we propose the mechanisms and precise kinds of vacancies which may causethe photocatalytic activity of HAp, and compare these theoretical data with our measured data on bothsamples of marine origin and commercial HAp powders. Density functional theory (DFT) (from firstprinciples calculations and Density of States (DOS) modelling) was used to calculate the optical bandgap energy (Eg) created by various possible oxygen vacancies in the HAp lattice: O from PO4, O fromOH, the loss of an entire OH group, or the simultaneous loss of O from PO4and an entire OH group. Themodelled values match the measured values very closely, suggesting that in non-photocatalytic HAp, ifany vacancies exist, they are O atoms from the OH group, resulting in a band gap of ∼5 eV in the UVCregion (not present in solar light at the Earth’s surface). However, in photocatalytic HAp, reduction fromthe combustion of an organic component at 1000◦C led to oxygen deficiency in the phosphate groups,probably in the O15 position, giving an Egof ∼3.45 eV, in the UVA region (present in sunlight). HeatingHAp with no organic component to 1200◦C also led to vacancies, of both an entire OH group and oxygenfrom PO4groups, which led to an intermediate Egvalue of ∼4 eV, on the boundary of the UVA-UVB regions.Absorption peaks were also predicted in the visible-light region with some types of vacancy.

2016Journal article

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Effects of Cu, Zn and Cu-Zn addition on the microstructure and antibacterial and photocatalytic functional properties of Cu-Zn modified TiO2 nano-heterostructures

Publication . Tobaldi, D. M.; Piccirillo, C.; Rozman, N.; Pullar, R. C.; Seabra, M. P.; Škapin, A. Sever; Castro, Paula M. L.; Labrincha, J. A.

Titanium dioxide (TiO2) is well established as one of the most common photocatalysts used for many environmental, anti-pollution and antibacterial applications. However, in this work, novel photocatalytic TiO2 nanopowders were modified with additions of 1 mol% copper, zinc or copper + zinc (with various Cu: Zn ratios). These were prepared via a green sol–gel route and thermally treated at 450 C. For the first time, a direct comparison of the effects of these two modifying agents was performed, both as single and co-substitution. The compounds were thoroughly characterised by means of advanced X-ray diffraction (Whole Powder Pattern Modelling, WPPM) and spectroscopic methods (Raman and UV–vis). For functional properties, the photocatalytic activity in the gas-solid phase (nitrous oxides (NOx) and isopropanol degradation (VOCs)) was tested under UV and visible light, and antibacterial activity against Gram positive and Gram negative bacterial strains was also investigated. Neither copper nor zinc entered into the TiO2 structure, but nucleated as oxides at the surface of titania nanoparticles, thus creating a nano-heterojunction between the semiconductor materials; this also retarded the anatase-to-rutile phase transition. When comparing and contrasting their functional properties, it was found that Zn modification gave greater photocatalytic activity than that with Cu. On the contrary, for antibacterial activity, copper was shown to be a better additive. Co-modification with both metals did not improve the antibacterial behaviour, but did lead to an increase in photocatalytic activity in some cases.

2016Journal article

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Surface modified hydroxyapatites with various functionalized nanostructures: computational studies of the vacancies in HAp

Publication . Bystrova, V. S.; Paramonova, E. V.; Bystrova, A. V.; Pullar, R. C.; Kopyl, S.; Tobaldi, D. M.; Piccirillo, C.; Avakyan, L. A.; Coutinho, J.

Hydroxyapatite (HAp) has structural features that define its basic physical properties, which have an important role at the surface, and it is one of the most used materials in bone implants. In this work, we present a density functional modeling (DFT) study of HAp both as bulk and with special HAp models with various defects, especially oxygen vacancies in HAp surface layers, which can also determine photocatalytic properties, confirmed experimentally. The first-principles calculations of bulk and modified HAp were carried out using local basis (AIMPRO) and plane-wave (VASP) codes. Data obtained are analyzed using both approaches, and compared.

2017Journal article

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Effect of preparation and processing conditions on UV absorbing properties of hydroxyapatite-Fe2O3 sunscreen

Publication . Teixeira, M. A. C.; Piccirillo, C.; Tobaldi, D. M.; Pullar, R. C.; Labrincha, J. A.; Ferreira, M. O.; Castro, Paula M. L.; Pintado, M. M. E.

The development of innovative, safe and non-photocatalytic sunscreens is urgently needed, as it is essential to have sunscreen filters offering appropriate UV protection without damaging the environment and/or generating free radicals when in contact with the skin. Hydroxyapatite (Ca-10(PO4)(6)(OH)(2), HAp) when substituted with iron has UV protection properties and is not photocatalytic; HAp was used to make a sunscreen filter by treating cod fish bones in an iron-containing solution, and then calcining them at 700 degrees C. Here we present a systematic and advanced study on this material, to obtain a sunscreen with improved UV absorbing properties, Bones were treated with three different iron salts - Fe(II) chloride, Fe(II) lactate and Fe(III) nitrate - under various pH conditions. Results showed that Fe(II) chloride in basic pH led to the most effective iron inclusion, High energy ball milling or ultrasound were investigated to increase surface area and corresponding UV absorption; high energy ball milling treatment led to the best optical properties. The optimum powders were used to formulate UV protection creams, which showed Sun Protection Factor (SPF) values significantly superior to the control cream (up to 4.1). Moreover the critical wavelength (lambda(crit)) was >370 nm (388-389 nm) and UVA/UVB ratios were very close to 1. With these properties these sunscreens can be classified as broad UV protectors. Results also showed that combining these powders with other sunscreens (i.e. titanium dioxide), a synergic effect between the different components was also observed. This investigation showed that HAp-based sunscreens of marine origin are a valid alternative to commercial products, safe for the health of the customers and, being non-photocatalytic, do not pose a threat to the environment.

2017Journal article

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Silver-containing calcium phosphate materials of marine origin with antibacterial activity

Publication . Piccirillo, C.; Pullar, R. C.; Tobaldi, D. M.; Castro, Paula M. L.; Estevez Pintado, M. M.

Hydroxyapatite (Ca10(PO4)6(OH)2 – HAp) is a common material for bone replacement in artificial implants and prostheses, due to its high biocompatibility. In this work we report about the preparation of HAp-based materials of marine origin with antibacterial properties. Bones from cod fish (Gadhus morua) were treated with a dilute AgNO3 solution, to obtain HAp-containing samples with silver as a minor component. The samples were characterised by XRD, FT-IR spectroscopy and SEM, indicating the presence of HAp, β–TCP and some metallic silver. The determination of unit cell parameters, however, indicated that the majority of silver is substituted in the β-TCP lattice in ionic form. The antibacterial activity of these materials was tested towards both Gram-positive and Gram-negative bacterias; results showed that the material is very effective with Gram-negative strains such as Escherichia coli (inactivation rates of 99.82% and 99.999% after 2 and 5 h, respectively) and had a smaller but still significant effect on Gram-positive MRSA (91% inactivation rate). These results show the potentials of these samples as infection-resistant bone replacement materials.

2015Journal article

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