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.

A Methodological Framework for Assessing the Sustainability of Solid Biofuels Systems.

This paper introduces a methodological framework for assessing the sustainability of solid biofuels in Mexico. The designed framework comprises 13 normalized indicators and two diagnostic studies, covering the economic, social, environmental, and institutional sustainability dimensions, and their intersections. Indicators are normalized using the concept of load capacity of a system, similarly to the planetary boundaries. Thus, the graphical representation of results facilitates their multidimensional analysis. The framework was applied to three case studies: traditional fuelwood in rural households, charcoal for restaurant grilling, and electricity cogeneration from sugarcane bagasse. This was part of an iterative process of testing and refining the framework and simultaneously demonstrating its application in the Mexican bioenergy context. This led to the conclusion that the resulting framework (a) provides a useful, quantitative, and comprehensive overview of both broad and specific sustainability aspects of the assessed system; (b) requires a balance of accessible but also scattered or sensitive data, similarly to most existing frameworks; (c) is highly flexible and applicable to both modern and traditional solid biofuels; and (d) is simple to communicate and interpret for a wide audience. Key directions for improvement of the framework are also discussed. Supplementary Information: The online version contains supplementary material available at 10.1007/s12155-021-10365-2.

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.