Cork-derived hierarchically porous hydroxyapatite with different stoichiometries for biomedical and environmental applications

Hierarchically porous hydroxyapatite derived from cork powder shows excellent performance in biomedicine (low cytotoxicity) and environmental remediation (high Pb2+ removal)

Carbon-modified titanium oxide materials for photocatalytic water and air decontamination

Titanium oxide-based materials with different physical and chemical features were synthetized aiming at removing organic pollutants from both water and air media. The materials were produced employing two different heating methodologies (thermal, T and hydrothermal, H) at distinct temperatures resulting in porous materials. These materials were also modified with either graphene oxide (GO) or carbon nanotubes (CNT), using an in-situ approach. All materials were tested as photocatalysts using ultra-violet (UV), visible (Vis) and solar radiation. Rhodamine B (RhB) and benzene were used as representative pollutants in water and air, respectively. The addition of carbon to the catalysts improved the removal of both pollutants. In the case of the photocatalytic degradation of rhodamine B, under both UV and Vis light, it was found that, the materials containing carbon nanostructures allowed the highest degradation degree, while the photosensitisation phenomenon became negligible. The best catalyst is the one containing CNT (2.98 wt% of C) and thermally treated at 300 °C (T300_CNT). This material showed higher degradation ability than the commercial TiO2 nanopowder Degussa P25 (P25) under Vis light. Regarding benzene removal, the samples thermally treated at 300 °C and modified with CNT and GO (T300_CNT and T300_GO, respectively) outperformed Degussa P25. The former material was successfully reused in the photocatalytic degradation of benzene over 6 consecutive cycles.publishe

Enhancement of thermoelectric performance of donor-doped ZnO ceramics by involving an In situ aluminothermic reaction during processing

This work explores the possibility of involving aluminothermy in processing donor-doped zinc oxide-based thermoelectrics by relying on local, strong exothermic effects developed during sintering, with a potential positive impact on the electrical and thermal transport properties. The strategy was exemplified by using aluminium as a dopant, due to its recognized ability to generate additional, available charge carriers in ZnO, and by using two different metallic Al powders and conventional Al2O3 as precursors. Nanosized aluminium powder was involved in order to evaluate the possible desirable effects of the particles size, as compared to aluminium micropowder. A significant enhancement of the electrical and thermoelectric performance of the samples prepared via metallic Al precursors was observed and discussed in terms of the potential impacts provided by the aluminothermic reaction on the microstructure, charge carrier concentration and mobility during sintering. Although the presented results are the first to show evidence of how aluminothermic reactions can be used for boosting the thermoelectric performance of zinc oxide materials, the detailed mechanisms behind the observed enhancements are yet to be understood.publishe

High colouring efficiency, optical density and inserted charge in sol–gel derived electrochromic titania nanostructures

A pure TiO2 thin film (100–120 nm) was made from a green aqueous sol–gel precursor on FTO glass and calcined at 430 °C. It was a mix of amorphous, anatase, rutile and brookite TiO2 phases, and exhibited very good electrochromic properties over visible and NIR wavelengths with an applied bias of +0.1 V to −1.5 V. It was highly transparent showing excellent coloration with applied voltage, with transmittance modulation (ΔT) = 69.7% at 550 nm, 86% at 700 nm and an overall ΔT between 400–1650 nm of 60%, giving a very large change in optical density (ΔOD) of 1.4 at 550 nm and 2.4 at 700 nm. Cyclic voltammograms had typical peaks for TiO2 at −1.3 V for colouration and −0.9 V for bleaching, with a high separation of 0.37 V between peaks, and a charge density after charging for 25 min of Qc = 50 mC cm−2. After only 60 s and 120 s at −1.5 V, inserted charge values of 17.6 and 22 mC cm−2 were observed, leading to a high colouration efficiency (CE) of 55.9 cm2 C−1 at 550 nm. These ΔOD, ΔT, Qc and CE values are superior to any previously reported for crystalline sol–gel TiO2 films. They also possessed rapid switching times for bleaching and colouring of τb90% = 10 s and τc90% = 55 s, comparable to the best previously reported sol–gel anatase-based TiO2 films. This makes this nanomaterial an excellent candidate for smart windows and other electrochromic devices and applications

Sol gel graphene/TiO2 nanoparticles for the photocatalytic-assisted sensing and abatement of NO2

Abstract Human exposure to volatile organic compounds and NO2 can lead to health problems, therefore strategies to mitigate against the risks are required. Abatement and sensing are approaches which could both neutralise and monitor these species thus providing a safer environment and warning occupants of harmful levels. This paper presents pure TiO2 and TiO2/graphene hybrids synthesized through a sol-gel route. Electron optical, helium ion microscopy, X-ray diffraction and spectroscopic methods have been applied to elucidate the physical and chemical behaviour. NO2 sensing properties of TiO2/graphene hybrids formed by the addition of graphene to the reaction vessel prior to initiating the sol gel reaction followed by annealing (GTiO2S), and an alternative manufacturing method involving the addition of graphene to TiO2 nanoparticles which had already been annealed (GTiO2M) were compared and evaluated. A conductometric sensor based on TiO2/graphene prepared using material GTiO2S showed a higher response to NO2 compared to sensors based on pure TiO2 and TiO2/graphene prepared with material GTiO2M. Under UV irradiation generated by a low power LED, the sensor showed a remarkably enhanced response to 1750 ppb NO2, about double the response in the dark, and a limit of detection of about 50 ppb of NO2 (Signal/Noise = 3). Photocatalytic tests to assess the degradation of NOx showed that TiO2/graphene hybrids using material GTiO2S were the most active amongst the whole series of TiO2-based materials. Our data highlights the unique characteristics of material GTiO2S TiO2/graphene and the suitability for multi-purpose applications in the field of environmental monitoring and remediation. The capability of the material for both sensing and abatement of NOx could be exploited to offer a safer environment through providing a warning of the presence of NOx whilst also reducing levels

Synergistic effects of zirconium- and aluminum co-doping on the thermoelectric performance of zinc oxide

This work aims to explore zirconium as a possible dopant to promote thermoelectric performance in bulk ZnO-based materials, both within the single-doping concept and on simultaneous co-doping with aluminum. At 1100–1223 K mixed-doped samples demonstrated around ∼2.3 times increase in ZT as compared to single-doped materials, reaching ∼0.12. The simultaneous presence of aluminum and zirconium imposes a synergistic effect on electrical properties provided by their mutual effects on the solubility in ZnO crystal lattice, while also allowing a moderate decrease of the thermal conductivity due to phonon scattering effects. At 1173 K the power factor of mixed-doped Zn0.994Al0.003Zr0.003O was 2.2–2.5 times higher than for single-doped materials. Stability tests of the prepared materials under prospective operation conditions indicated that the gradual increase in both resistivity and Seebeck coefficient in mixed-doped compositions with time may partially compensate each other to maintain a relatively high power factorpublishe

Exploring tantalum as a potential dopant to promote the thermoelectric performance of zinc oxide

Zinc oxide (ZnO) has being recognised as a potentially interesting thermoelectric material, allowing flexible tuning of the electrical properties by donor doping. This work focuses on the assessment of tantalum doping effects on the relevant structural, microstructural, optical and thermoelectric properties of ZnO. Processing of the samples with a nominal composition Zn1-xTaxO by conventional solid-state route results in limited solubility of Ta in the wurtzite structure. Electronic doping is accompanied by the formation of other defects and dislocations as a compensation mechanism and simultaneous segregation of ZnTa2O6 at the grain boundaries. Highly defective structure and partial blocking of the grain boundaries suppress the electrical transport, while the evolution of Seebeck coefficient and band gap suggest that the charge carrier concentration continuously increases from x = 0 to 0.008. Thermal conductivity is almost not affected by the tantalum content. The highest ZT~0.07 at 1175 K observed for Zn0.998Ta0.002O is mainly provided by high Seebeck coefficient (-464 µV/K) along with a moderate electrical conductivity of ~13 S/cm. The results suggest that tantalum may represent a suitable dopant for thermoelectric zinc oxide, but this requires the application of specific processing methods and compositional design to enhance the solubility of Ta in wurtzite lattice

Photocatalytic removal of benzene over Ti3C2Tx MXene and TiO2–MXene composite materials under solar and NIR irradiation

MXenes, a family of two-dimensional (2D) transition metal carbides, nitrides and carbonitrides based on earth-abundant constituents, are prospective candidates for energy conversion applications, including photocatalysis. While the activity of individual MXenes towards various photocatalytic processes is still debatable, these materials were proved to be excellent co-catalysts, accelerating the charge separation and suppressing the exciton recombination. Titanium-containing MXenes are well compatible with the classical TiO2 photocatalyst. The TiO2 component can be directly grown on MXene sheets by in situ oxidation, representing a mainstream processing approach for such composites. In this study, an essentially different approach has been implemented: a series of TiO2-MXene composite materials with controlled composition and both reference end members were prepared, involving two different strategies for mixing sol-gel-derived TiO2 nanopowder with the Ti3C2Tx component, which was obtained by HF etching of self-propagating high-temperature synthesis products containing modified MAX phase Ti3C2Alz (z > 1) with nominal aluminium excess. The prospects of such composites for the degradation of organic pollutants under simulated solar light, using benzene as a model system, were demonstrated and analysed in combination with their structural, microstructural and optical properties. A notable photocatalytic activity of bare MXene under near infrared light was discovered, suggesting further prospects for light-to-energy harvesting spanning from UV-A to NIR and applications in biomedical imaging and sensors.publishe

Photocatalytic Lime Render for Indoor and Outdoor Air Quality Improvement

This article reports a novel photocatalytic lime render for indoor and outdoor air quality improvement that is composed of a lime binder and doped TiO2 (KRONOClean 7000®) nanoparticles. These nanoparticles were distributed throughout the bulk of the finishing render, instead of as a thin coating, thus ensuring the durability of the photocatalytic properties upon superficial damage. The physical properties of these renders were not affected by the addition of nanoparticles except in the case of surface area, which increased significantly. In terms of their photocatalytic activity, these novel lime renders were shown to degrade up to 12% NOx under UV light and up to 11% formaldehyde under visible light.This research was funded by the European Union’s Seventh Framework Programme for research, technological development, and demonstration under the Grant Agreement No. 609234 related to the ECO-SEE project: “Eco-innovative, Safe and Energy Efficient wall panels and materials for a healthier indoor environment” This work was partly developed within the scope of the project CICECO–Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. David Maria Tobaldi is overly grateful to Portuguese national funds (OE), through FCT, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree-Law 57/2016, of 29 August, changed by Law 57/2017, of 19 July

Dielectrical Properties of CeO2 Nanoparticles at Different Temperatures

A template-free precipitation method was used as a simple and low cost method for preparation of CeO2 nanoparticles. The structure and morphology of the prepared nanoparticle samples were studied in detail using X-ray diffraction, Raman spectroscopy and Scanning Electron Microscopy (SEM) measurements. The whole powder pattern modelling (WPPM) method was applied on XRD data to accurately measure the crystalline domain size and their size distribution. The average crystalline domain diameter was found to be 5.2 nm, with a very narrow size distribution. UV-visible absorbance spectrum was used to calculate the optical energy band gap of the prepared CeO2 nanoparticles. The FT-IR spectrum of prepared CeO2 nanoparticles showed absorption bands at 400 cm(-1) to 450 cm(-1) regime, which correspond to CeO2 stretching vibration. The dielectric constant (er) and dielectric loss (tan delta) values of sintered CeO2 compact consolidated from prepared nanoparticles were measured at different temperatures in the range from 298 K (room temperature) to 623 K, and at different frequencies from 1 kHz to 1 MHz