Aero-TiO2 three-dimensional nanoarchitecture for photocatalytic degradation of tetracycline | Scientific Reports

Feb 21, 2025

Scientific Reports volume 14, Article number: 31215 (2024) Cite this article

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One of the biggest issues of wide bandgap semiconductor use in photocatalytic wastewater treatment is the reusability of the material and avoiding the contamination of water with the material itself. In this paper, we report on a novel TiO2 aeromaterial (aero-TiO2) consisting of hollow microtetrapods with Zn2Ti3O8 inclusions. Atomic layer deposition has been used to obtain particles of unique shape allowing them to interlock thereby protecting the photocatalyst from erosion and damage when incorporated in active filters. The performance of the aero-TiO2 material was investigated regarding photocatalytic degradation of tetracycline under UV and visible light irradiation. Upon irradiation with a 3.4 mW/cm2 UV source, the tetracycline concentration decreases by about 90% during 150 min, while upon irradiation with a Solar Simulator (87.5 mW/cm2) the concentration of antibiotic decreases by about 75% during 180 min. The experiments conducted under liquid flow conditions over a photocatalyst fixed in a testing cell have demonstrated the proper reusability of the material.

Pharmaceutical industries contribute significantly to water pollution through the discharge of various chemical compounds, including antibiotics1,2. Tetracycline, a widely used antibiotic in both human and veterinary medicine, is among the pharmaceutical compounds frequently detected in aquatic environments, especially in highly populated areas. Conventional wastewater treatment methods often fail to completely remove these compounds, leading to their accumulation in the environment and potential ecological disruptions3. Therefore, there is an urgent need for efficient and sustainable strategies to diminish antibiotic pollution in wastewaters.

Various nanomaterials have been explored for photocatalytic degradation of antibiotics. These include but are not limited to zinc oxide (ZnO)4 and other metal oxides5,6, graphene-based materials7, and doped semiconductors8. Each nanomaterial exhibits unique properties and photocatalytic mechanisms, offering a diverse toolkit for addressing antibiotic pollution in wastewaters.

Among the various nanomaterials, titanium dioxide (TiO2) has attracted significant attention for its exceptional photocatalytic properties, which enable the degradation of organic pollutants under UV or visible light irradiation9. The unique structural and physico-chemical properties of TiO2 make it an ideal candidate for photocatalytic applications, including wastewater treatment10.

The widespread use of TiO2 for a variety of applications including photocatalysis can lead to increased effects on organisms and the environment. However, despite the enormous efforts undertaken in recent years to determine the real risk, the results achieved do not speak clearly and the technological advantages of using TiO2 outweigh11.

While TiO2-based nanomaterials have demonstrated promising results in photocatalytic degradation of antibiotics, several challenges remain to be addressed. Doping or functionalization with various elements12 or creating a mixture phase between TiO2 and other compounds13,14,15 could influence the photocatalysis process. Variations in the physicochemical properties of TiO2 nanoparticles, such as crystalline phase, particle size, and surface morphology, can significantly influence their photocatalytic performance. TiO2 can be fabricated at the nanoscale in various shapes and crystalline structures by different techniques16, each of them having advantages and disadvantages. TiO2 nanotubes fabricated by simple electrochemical etching of Ti foils were successfully used for the degradation of dyes such as Methylene Blue or Rhodamine B17,18. The tubular shape at the nanoscale can also add other functionalities to its photocatalytic properties. This shape enables its use as nanoengines activated by UV external light, making them suitable for applications such as water purification, drug delivery systems and others19,20.

In this paper, we report on a novel nanomaterial composed of TiO2 hollow microtetrapods fabricated by Atomic Layer Deposition (ALD) technique using a sacrificial ZnO template. While TiO2-based nanomaterials are extensively used for photocatalytic degradation, the hollow microtetrapod design provides a unique morphology not previously explored in the context of antibiotic degradation. The high surface area and tubular geometry enhance contact with pollutants, while the interconnected structure is advantageous in dynamic systems, as it provides mechanical stability. Furthermore, the material’s reusability in continuous flow reactors addresses a major challenge in scaling photocatalytic systems for industrial applications. Through these innovations, this work contributes with a durable and efficient approach for reducing antibiotic contamination in wastewater, combining material stability with effective photocatalytic degradation under visible and UV light irradiation. The importance of aero-TiO2 as a photocatalytic material resides also in its great potential to be used in self-propelled microengines20,21, which will open the way to novel applications in microfluidics.

The morphology of the hollow TiO2 microtetrapods is illustrated in Fig. 1. The dimensions of the arms of aero-TiO2 microtetrapods vary in the range from 20 to 40 µm in length and 1 to 3 µm in diameter. The wall thickness of the TiO2 microtubes is around 50 nm.

(a, b) SEM images of the aero-TiO2 material consisting of hollow microtetrapods, and (c) the schematic route of the aeromaterial preparation, starting with initial ZnO microtetrapods, atomic layer deposition of TiO2 on their surface (also illustrated in cross section) and, finally, removal of sacrificial ZnO substrate in the presence of HCl and H2 gases at 800 °C.

The XRD pattern shown in Fig. 2a demonstrates the presence of the rutile phase TiO2 (JCPDS 00–021-1276) and the ternary compound Zn2Ti3O8 (JCPDS 01–073-0579). All diffraction lines of the TiO2 and Zn2Ti3O8 were indexed by tetragonal TiO2 with the space group P42/mnm(136) and cubic Zn2Ti3O8 with the space group Fd-3 m(227).

XRD pattern (a) and Raman spectrum (b) of the fabricated aero-TiO2 material.

The sizes of crystallites were determined considering the main peaks of the compounds and were found to be 50 nm for rutile TiO2 and 36 nm for Zn2Ti3O8, which were determined by the Scherrer equation (Eq. 1):

where, λ is the wavelength (Co Kα, λ = 1.7903 Å), β is the full width at the half-maximum (FWHM) and θ is the diffraction angle.

It was found previously that aero-TiO2 can be obtained in a mixture of anatase–rutile compound with Zn2TiO4 inclusions by using the same ALD process with subsequent selective wet chemical etching of ZnO sacrificial template13. Higher annealing temperature and the different approach we used for the ZnO removal allowed one to obtain a composite consisting of rutile phase TiO2 and cubic Zn2Ti3O8.

The XRD data are corroborated by the Raman scattering analysis (Fig. 2b). The rutile structure of TiO2 belongs to the space group \(D\genfrac{}{}{0pt}{}{14}{4h}\) and it has four Raman active vibrations: A1g + B1g + B2g + Eg. The observed peaks at 447 cm−1 and 612 cm−1 are attributed to the Eg, and A1g modes, respectively. Second order scattering features can also be visible in the spectrum, the most intensive one being at 238 cm−1 22.

By using the Kubelka–Munk equation (Eq. 2), the optical band gap of the sample was determined from the diffuse reflectance spectrum:

where α is the optical absorption coefficient, hν is the photon energy, A is a constant of proportionality, and exponent p is determined by the transition type of the material: p = 2 for direct allowed transitions, p = 2/3 for direct forbidden transition, p = 1/2 for indirect allowed transitions, and p = 1/3 for indirect forbidden transitions.

Since TiO2 rutile phase is known as a direct transition semiconductor, the function used for plotting was

The optical band gap energy of the material was determined by the extrapolation of the slope to F(R) → 0 from the plot [F(R)·hν]2 vs. hν, as shown in Fig. 3.

Optical bandgap determined from UV–visible diffuse reflectance spectrum.

According to the modified Kubelka–Munk function, the UV–visible diffuse reflectance spectra show that TiO2 hollow microtetrapods have the bandgap of 3.12 eV. For the purpose of comparison one can note that anatase and rutile phases of TiO2 have a bandgap of around 3.0 eV and 3.2 eV, respectively23, while Zn2Ti3O8 has a calculated bandgap of 3.55 eV 24.

Photoluminescence (PL) measurements were performed to evaluate the presence of defects in the synthesized samples. The PL spectra from Fig. 4a span a broad energy range from 2.0 to 3.5 eV. Notably, as the temperature rises from 10 K to room temperature, the intensity of the high-energy band decreases more significantly than that of the low-energy band.

PL spectra of aero-TiO2 at 10 K and 300 K (a) and the deconvoluted spectrum of PL recorded at 10 K (b).

The deconvolution of the PL spectrum presented in Fig. 4b reveals that it comprises three distinct energy bands: one green band and two violet bands. The green band is centered at 2.5–2.6 eV, while the first and second violet bands are located respectively at 2.9–3.0 eV and 3.15 eV.

One can assign the high-energy emission band at 3.15 eV to near-bandgap transitions, while the violet PL band at 2.9 eV may be associated with an unidentified defect. The green band has previously been linked to the recombination of self-trapped excitons formed from carrier polarons25. It is suggested that oxygen vacancies facilitate effective trapping of carriers or polarons and, simultaneously, the efficient charge separation allows for electron and hole accumulation or trapping at distinct sites, potentially on the surface. Given the extensive surface areas of aeromaterials, one may expect surfaces to play a major role in their photoluminescence behavior.

The kinetics of the tetracycline photodegradation was fitted according to the pseudo-first-order model (Eq. 4):

where, C0 and Ct represent the concentrations of tetracycline in solutions at irradiation time t = 0 min and t, respectively, and k represents the degradation rate (min-1).

Without the photocatalyst, the tetracycline concentration in the solution is not significantly influenced by irradiation with visible or UV light. When aero-TiO2 is added to the solution (Fig. 5e), the concentration of tetracycline decreases by about 75% when irradiated with visible light for 180 min. Upon irradiation with UV light, the photocatalysis process is faster, and the tetracycline concentration decreases by about 90% during 150 min (Fig. 5a). The degradation rates of tetracycline were estimated to be about 0.0064 min-1 and 0.0120 min-1 upon irradiation with visible and UV light, respectively, as shown in Figs. 5b.

Photocatalysis performance of aero-TiO2 for the degradation of tetracycline under visible or UV (a) and under UV light irradiation in the continuous solution flow conditions (c) and their degradation rates (b, d); the schematics of the experimental setup for the photocatalysis tests (e, f).

Previously, Wu et al. have demonstrated that TiO2 P25 nanoparticles with the surface area of about 55 m2/g are able to degrade tetracycline with a ratio of about 0.038 min-1 under 350 nm irradiation, and the photocatalytic efficiency decreases with the increase of the wavelength irradiation source, down to 0.00055 min-1 at 850 nm 26. Despite the differences in testing conditions, these results still can be roughly compared with those from our work. The observed enhanced photocatalytic performance of aero-TiO2 can be attributed to the presence in the nanocomposite structure of Zn2Ti3O8 inclusions decreasing the rate of recombination of photogenerated electron–hole pairs, thus allowing them to reach the photocatalyst surface27,28,29.

Table 1 provides a summary of the existing knowledge on tetracycline photodegradation using various structures of TiO2 photocatalysts, emphasizing the performance of these materials and reaction parameters.

There are three main types of active species which mainly contribute to the photocatalytic degradation of tetracycline, namely ·O2−, ·OH and h+ as was previously observed by other authors37. ·O2− and h+ species have a major role in the photocatalysis under UV and only ·O2− becomes important under visible light irradiation38. The electrons from the valence band are excited to the conduction band, reacting with O2, leading to the formation of ·O2− species, which further react with the adsorbed tetracycline molecules at the material surface, while h+ species directly contribute to the oxidation of tetracycline39.

Previous studies have demonstrated that during photocatalytic oxidation reactions, oxygen vacancy defects in ZnO-TiO2 nanocomposite materials serve as active sites for capturing photoinduced electrons, significantly enhancing photocatalytic efficiency. Additionally, oxygen vacancies facilitate the adsorption of environmental oxygen onto the sample, leading to strong interactions between the photoexcited electrons captured by these vacancies and the adsorbed oxygen molecules40.

The ability to fabricate nanocomposites with precise control opens new pathways for bandgap engineering, enabling alignment of the conduction and valence bands of composite materials with the HOMO and LUMO molecular orbitals of organic compounds targeted for photocatalytic degradation. Under these conditions, photogenerated electrons transfer from the conduction band of one component to that of another, while photogenerated holes similarly move between valence bands. Additionally, transition of the excited electrons from organic molecules to the conduction bands of the nanocomposite components generate reactive species that drive chemical reactions41. Given the substantial specific surface area of the synthesized aeromaterials, it is also likely that surface states play a critical role in modulating the valence band edge, thereby enhancing photocatalytic properties under visible-light irradiation, including those relevant to water splitting.

In the experiment performed under continuous liquid flow conditions using UV light with a density of 3.2 mW/cm2 (see Fig. 5f), the concentration of tetracycline decreases by about 65% during seven hours of irradiation with a degradation rate of 0.0022 min-1 (Fig. 5c and d). After the full degradation of tetracycline, the material was repeatedly used in three more consecutive tests. It was observed that the degradation performance was not influenced, thus demonstrating the reusability of the material. Hence, the 3D shape of our material with 2D features, such as the wall thickness of about 50 nm, makes it suitable for incorporation in active filters for water treatment without the risk of water contamination with the active material.

Aero-titania was obtained by growing thin layers of TiO2 using the ALD technique on a substrate consisting of sacrificial templates of ZnO microtetrapods. Flame Transport Synthesis approach was used to obtain ZnO microtetrapods42 which were kindly provided by Prof. Rainer Adelung from Kiel University, Germany. First, pellets with dimensions of 10 × 10 × 4 mm3 consisting of ZnO microtetrapods were fabricated in a steel mold under pressure, with a controlled density and porosity of the material. Then, TiO2 was deposited using a thermal ALD reactor (Veeco Savannah S200 from Veeco Instruments Inc., Plainview, New York, NY, USA), utilizing TiCl4 as Ti precursor and deionized water as oxygen source. The deposition process was performed at 150 °C. High purity nitrogen was used as carrier gas at a flow rate of 20 sccm. The pulse and purge times were 0.2/120/0.015/120 s (TiCl4/N2/H2O/N2) for a single ALD deposition cycle. The growth rate was determined to be about 0.16 nm/cycle and the final thickness of the deposited TiO2 was about 50 nm. Thickness measurements were performed on reference Si wafers located close to the sample using a spectroscopic ellipsometer (SENpro, SENTECH Instruments GmbH, Berlin, Germany). ZnO sacrificial material was etched in a Hydride Vapor Phase Epitaxy (HVPE) system using HCl gas and H2 at 800 °C.

The morphology of the materials was investigated by a scanning electron microscope Tescan TS5130 at 10 kV accelerating voltage. For the crystalline quality investigation, a Rigaku Miniflex-600 powder diffractometer equipped with a Co Kα source radiation (λ = 1.7903 Å) operating at 40 kV and an emission current of 15 mA was used. The measurements were performed from 20 to 90° at a scanning speed of 6°/min. The photocatalytic performance was investigated by the changes in the absorption spectra of the solution containing tetracycline by using a PerkinElmer 1050 UV/Vis spectrophotometer, from which the concentration in % was determined. The Raman spectra were recorded at room temperature using a Nicolet DXR system with an excitation laser beam of 532 nm. UV–Vis diffuse reflectance spectroscopy (DRUV-Vis) in the range from 265 to 800 nm was performed by a modular fiber spectrometer AvaSpec 2048–2 (Avantes, The Netherlands).

The tetracycline used in the experiments was acquired from Sigma Aldrich (CAS #60548). Prior to mixing the aero-TiO2 in the solution, the material was thermally treated at 300 °C in air for one hour to change its surface properties from hydrophobic to hydrophilic. The photocatalytic investigations were performed under both UV and visible light in two different configurations. In the first case, 5 mg of aero-TiO2 was mixed with 10 ml of tetracycline solution with a concentration of 10 mg/L. The solution was continuously mixed with a stirrer at 250 rpm while being irradiated laterally with visible light from a Solar Simulator Pico Solar G2V using the standard Solar Spectrum AM1.5 g with a power density of 87.5 mW/cm2, or irradiated from the top with a Focused UV lamp type C-10A-HE with power density of 3.4 mW/cm2. 1 ml of solution was extracted every 30 min, centrifuged to avoid the presence of the material in the suspension and then the absorbance spectra were collected. In the second configuration, the tetracycline degradation was investigated under liquid flow conditions. For this, a testing cell was fabricated from an opened tube with Whatman filter at the bottom, which allowed solution flow in a second tank from which it was recirculated by a peristaltic pump with the set flow condition of 2.5 ml/min. 5 mg of material was initially mixed with 5 ml of water and poured on the Whatman filter, forming a layer of tetrapods after sedimentation or leading to impregnation into the filter in case of smaller tetrapods or broken arms of the tetrapods.

A UV lamp (λ = 365 nm), with power density of 3.2 mW/cm2 was used as an irradiation source (see Fig. 5e). A total amount of 50 ml of solution was used in the experiment. 1 ml solution was collected every 60 min from the underneath reservoir and the concentration of tetracycline was determined from the absorption spectra by investigating the intensity decrease of the peak at 270 nm. The absorption spectra were recorded in PMMA cuvettes.

The novel aeromaterial fabricated by the ALD technique, composed of hollow microtetrapods of TiO2 with a wall thickness of 50 nm, proved to be efficient for photocatalytic degradation of tetracycline under UV or visible light irradiation. The UV/Vis spectroscopy confirmed a decrease in tetracycline concentration by about 90% under UV and about 75% under visible light irradiation within three hours, showing degradation rates of about 0.0120 min-1 and 0.0064 min-1, respectively. The fabricated material consists of TiO2 rutile phase with Zn2Ti3O8 inclusions according to XRD analysis and has an optical bandgap of 3.12 eV according to diffuse reflectance measurements. These features make it comparable with the performance of other TiO2 based nanostructures reported in the literature. However, the added value of this novel material is its micrometric size scale and morphological suitability for incorporating the hollow microtetrapods in textile supports, thus opening the possibility of using the material fixed on a solid substrate in a continuous flow photoreactor which imparts the reusability and excludes the contamination of water with TiO2 nanoparticles.

The corresponding author (V.C.) can provide the datasets presented in this study upon reasonable request.

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This work was financially supported by the Ministry of Foreign Affairs of the Czech Republic — 23-PKVV-UM-7, the Romanian Ministry of Research, Innovation and Digitalization, project no. PNRRIII-C9-2023-I8-161, contract no. 760285/27.03.2024, within the National Recovery and Resilience Plan and by the National Agency for Research and Development of the Republic of Moldova “Young Researchers” project #24.80012.5007.12TC. The authors from Tomas Bata University in Zlín also acknowledge the support from the Ministry of Education, Youth and Sports of the Czech Republic within the framework of DKRVO (project no. RP/CPS/2024-28/007).

Centre of Advanced Research in Bionanoconjugates and Biopolymers, “Petru Poni” Institute of Macromolecular Chemistry, 41A, Grigore Ghica Voda Alley, 700487, Iasi, Romania

Vladimir Ciobanu, Tudor Braniste & Ion Tiginyanu

National Centre for Materials Study and Testing, Technical University of Moldova, 168, Stefan Cel Mare Av, 2004, Chisinau, Moldova

Vladimir Ciobanu, Tatiana Galatonova, Tudor Braniste & Ion Tiginyanu

Centre of Polymer Systems, Tomas Bata University in Zlin, 5678, tr. Tomase Bati , CZ 76001, Zlin, Czech Republic

Pavel Urbanek, Barbora Hanulikova, Ivo Kuritka & Vladimir Sedlarik

Institute for Metallic Materials (IMW), Leibniz Institute of Solid State and Materials Research (IFW Dresden), 20, Helmholtzstrasse , 01069, Dresden, Germany

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Conceptualization, V.C., T.B., I.K., I.T.; methodology, V.C., P.U., T.B., I.K.; validation, I.K.; formal analysis, V.C.; investigations, V.C., T.G., B.H., S.L., P.U., resources, K.N., V.S., I.T.; visualization, P.U., I.K.; data curation, V.C., T.G.; writing—original draft preparation, V.C.; writing—review and editing, all authors; supervision, I.K., I.T.; project administration, V.S., I.K., I.T.; funding acquisition, V.S., I.T.

Correspondence to Vladimir Ciobanu or Ion Tiginyanu.

The authors declare no competing interests.

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Ciobanu, V., Galatonova, T., Braniste, T. et al. Aero-TiO2 three-dimensional nanoarchitecture for photocatalytic degradation of tetracycline. Sci Rep 14, 31215 (2024). https://doi.org/10.1038/s41598-024-82574-6

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Received: 13 October 2024

Accepted: 06 December 2024

Published: 28 December 2024

DOI: https://doi.org/10.1038/s41598-024-82574-6

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