Impact of the Precursor on the Physicochemical Properties and Photoactivity of TiO2 Nanoparticles Produced in Supercritical CO2.

The synthesis of TiO2 nanoparticles (NPs) in supercritical media has been reported over the last two decades. However, very few studies have compared the physicochemical characteristics and photoactivity of the TiO2 powders produced from different precursors, and even fewer have investigated the effect of using different ratios of hydrolytic agent/precursor (HA/P) on the properties of the semiconductor. To bridge this knowledge gap, this research focuses on the synthesis and characterization of TiO2 NPs obtained in a supercritical CO2 medium from four different TiO2 precursors, namely diisopropoxytitanium bis (acetylacetonate) (TDB), titanium (IV) isopropoxide (TIP), titanium (IV) butoxide (TBO), and titanium (IV) 2-ethylhexyloxide (TEO). Further, the effect of various HA/P ratios (10, 20, 30, and 40 mol/mol) when using ethanol as a hydrolytic agent has also been analyzed. Results obtained have shown that the physicochemical properties of the catalysts are not significantly affected by these variables, although some differences do exist between the synthesized materials and their catalytic performances. Specifically, photocatalysts obtained from TIP and TEO at the higher HA/P ratios (HA/P = 30 and HA/P = 40) led to higher CO2 photoconversions (6.3-7 µmol·g-1·h-1, Apparent Quantum Efficiency < 0.1%), about three times higher than those attained with commercial TiO2 P-25. These results have been imputed to the fact that these catalysts exhibit appropriate values of crystal size, surface area, light absorption, and charge transfer properties.

Photocatalytic Reduction of CO2 with N-Doped TiO2-Based Photocatalysts Obtained in One-Pot Supercritical Synthesis.

The objective of this work was to analyze the effect of carbon support on the activity and selectivity of N-doped TiO2 nanoparticles. Thus, N-doped TiO2 and two types of composites, N-doped TiO2/CNT and N-doped TiO2/rGO, were prepared by a new environmentally friendly one-pot method. CNT and rGO were used as supports, triethylamine and urea as N doping agents, and titanium (IV) tetraisopropoxide and ethanol as Ti precursor and hydrolysis agent, respectively. The as-prepared photocatalysts exhibited enhanced photocatalytic performance compared to TiO2 P25 commercial catalyst during the photoreduction of CO2 with water vapor. It was imputed to the synergistic effect of N doping (reduction of semiconductor band gap energy) and carbon support (enlarging e--h+ recombination time). The activity and selectivity of catalysts varied depending on the investigated material. Thus, whereas N-doped TiO2 nanoparticles led to a gaseous mixture, where CH4 formed the majority compared to CO, N-doped TiO2/CNT and N-doped TiO2/rGO composites almost exclusively generated CO. Regarding the activity of the catalysts, the highest production rates of CO (8 µmol/gTiO2/h) and CH4 (4 µmol/gTiO2/h) were achieved with composite N1/TiO2/rGO and N1/TiO2 nanoparticles, respectively, where superscript represents the ratio mg N/g TiO2. These rates are four times and almost forty times higher than the CO and CH4 production rates observed with commercial TiO2 P25.

Removal of emerging pollutant dibutylhydroxytoluene from water with CNT/TiO2 catalysts in a visible LED photoreactor.

For the photocatalytic degradation of antioxidant 2,6-di-tert-butyl-hydroxytoluene (BHT), several TiO2-based composites have been prepared in MWCNT from titanium isopropoxide and ethanol via supercritical CO2 synthesis followed by calcination at 400 °C. TEM and XRD showed uniform coverage of CNT by 10 nm TiO2 particles in the anatase form, and spectral analyses revealed the formation of CNT/TiO2 structure. Further, synthesized material displayed significant visible light absorption and absorption edge shifted to longer wavelengths. Once the material was characterized, the effect of adsorption and photochemical degradation of BHT was investigated in the wavelength range from 400 to 700 nm, in batch mode, by monitoring the concentrations of BHT as a function of time. CNT/TiO2 composites were more efficient than commercial TiO2 P25 in the photodegradation of the antioxidant. In particular, CNT50/TiO250, a composite with 50% by weight of CNT, was the best catalyst, stable, and completely degrading BHT within 30 min of exposure to visible light. The role played by different reactive oxidative species (h+, OH ·, 1O2, and [Formula: see text]) in the photocatalytic reaction was also studied by using appropriate radical scavengers that inhibited the corresponding active species. Superoxide radical was found the main oxidizing agent.

Capability of selected crop plants for shoot mercury accumulation from polluted soils: phytoremediation perspectives.

High-biomass crops can be considered as an alternative to hyperaccumulator plants to phytoremediate soils contaminated by heavy metals. In order to assess their practical capability for the absorption and accumulation of Hg in shoots, barley, white lupine, lentil, and chickpea were tested in pot experiments using several growth substrates. In the first experimental series, plants were grown in a mixture of vermiculite and perlite spiked with 8.35 microg g(-1) d.w. of soluble Hg. The mercury concentration of the plants' aerial tissues ranged from 1.51 to 5.13 microg g(-1) d.w. with lentil and lupine showing the highest values. In a second experiment carried out using a Hg-polluted soil (32.16 microg g(-1) d.w.) collected from a historical mining area (Almadén, Spain), the crop plants tested only reached shoot Hg concentration up to 1.13 microg g(-1) d.w. In the third experimental series, the Almadén soil was spiked with 1 microg g(-1) d.w. of soluble Hg; as a result, mercury concentrations in the plant shoots increased approximately 6 times for lupine, 5 times for chickpea, and 3.5 times for barley and lentil, with respect to those obtained with the original soil without Hg added. This marked difference was attributed to the low availability of Hg in the original Almadin soil and its subsequent increase in the Hg-spiked soil. The low mercury accumulation yields obtained for all plants do not make a successful decontamination of the Almadén soils possible byphytoremediation using crop plants. However, since the crops tested can effectively decrease the plant-available Hg level in this soil, their use could, to some extent, reduce the environmental risk of Hg pollution in the area.