Removal of malachite green from water: Comparison of adsorption in a residue-derived AC versus photocatalytic oxidation with TiO2 and study of the adsorption-photocatalysis synergy.

The literature rarely compiles studies devoted to the removal of pollutants in aqueous media comparing adsorption and photocatalytic degradation, and does not pay enough attention to the analysis of combined adsorption-photocatalytic oxidation processes. In the present manuscript, the removal of malachite green (MG) from aqueous solutions has been investigated in three different sustainable scenarios: i) adsorption on activated carbon (AC) derived from a residue, luffa cylindrica, ii) photocatalytic oxidation under simulated solar light using titanium dioxide (TP) and iii) combined adsorption-photocatalytic oxidation using TP-AC (70/30 wt./wt.) under simulated solar light. The study has revealed that in the three scenarios and studied conditions, the total removal of this endocrine-disrupting dye from the solution takes place in the assayed time, 2 h, in some cases just in a few minutes. MG adsorption in the AC is a very fast and efficient removal method. MG photocatalytic oxidation with TP also occurs efficiently, although the oxidized MG is not totally mineralized. MG removal using the TP-AC composite under simulated solar light occurs only slightly faster to the MG adsorption in the AC, being adsorption the dominating MG removal mechanism for TP-AC. Thus, more than 90% of the removed MG with TP-AC under simulated solar light is adsorbed in this carbon-containing composite. The obtained results highlight the interest in adsorption, being the selection of the most suitable removal method dependent on several factors (i.e., the cost of the AC regeneration, for adsorption, or the toxicity of the intermediate oxidation species, for photooxidation). Paying attention to MG photooxidation with TiO2, comparison of two working photodegradation schemes shows that the direct photodegradation of MG from solution, avoiding any initial dark equilibrium period, is more efficient from a time perspective. The use of scavengers has proved that MG photodegradation occurs via an oxidation mechanism dominated by superoxide anion radicals.

A novel approach to the quantitative analysis of the particulate matter in conventional cigarette smoke and heated tobacco product aerosols.

The particulate and soluble matter present in aerosols from combustible cigarettes (CCs) and Heated Tobacco Products (HTPs) was collected in liquid water. These liquids, yellowish in the experiments with cigarettes and colourless after using HTPs, were analysed by Laser Diffraction (LD) and by Transmission Electron Microscopy coupled to Energy Dispersive X-ray spectroscopy (TEM-EDX) to study the amount, size, composition, and other features of the particulate matter (PM) present in the collected aerosols. The particulate matter concentration in HTPs samples is below the limit of quantification for LD, and only samples from cigarettes show a particulate matter concentration above such limit. TEM analysis has revealed that the liquid samples (from both, cigarettes and HTPs experiments) contain particulate matter, mainly composed of carbon (C) and oxygen (O), but also of traces of inorganic elements. The TEM electron beam results in the evaporation of the particulate matter derived from HTPs, but not of that derived from cigarettes, highlighting the different nature of the particulate matter in both systems, i.e. liquid particulate matter present in the HTPs aerosols and solid particulate matter in the cigarettes smoke. A protocol for the quantitative comparison of the particulate matter present in aerosols has been applied over sixteen TEM images for each sample, confirming important differences from the point of view of the amount of particulate matter and particle size ranges. Thus, the amount of particulate matter for HTPs aerosol samples is more than one order of magnitude lower than for cigarettes smoke.

Surface-Enriched Boron-Doped TiO2 Nanoparticles as Photocatalysts for Propene Oxidation.

A series of nanostructured boron-TiO2 photocatalysts (B-X-TiO2-T) were prepared by sol-gel synthesis using titanium tetraisopropoxide and boric acid. The effects of the synthesis variables, boric acid amount (X) and crystallization temperature (T), on structural and electronic properties and on the photocatalytic performance for propene oxidation, are studied. This reaction accounts for the remediation of pollution caused by volatile organic compounds, and it is carried out at low concentrations, a case in which efficient removal techniques are difficult and costly to implement. The presence of boric acid during the TiO2 synthesis hinders the development of rutile without affecting the textural properties. X-ray photoelectron spectroscopy analysis reveals the interstitial incorporation of boron into the surface lattice of the TiO2 nanostructure, while segregation of B2O3 occurs in samples with high boron loading, also confirmed by X-ray diffraction. The best-performing photocatalysts are those with the lowest boron loading. Their high activity, outperforming the equivalent sample without boron, can be attributed to a high anatase and surface hydroxyl group content and efficient photo-charge separation (photoelectrochemical characterization, PEC), which can explain the suppression of visible photoluminescence (PL). Crystallization at 450 °C renders the most active sample, likely due to the development of a pure anatase structure with a large surface boron enrichment. A shift in the wavelength-dependent activity profile (PEC data) and the lowest electron-hole recombination rate (PL data) are also observed for this sample.

Removal of odour-causing compounds using carbonaceous adsorbents/catalysts prepared from sewage sludge.

This paper discusses H(2)S, NH(3) and VOCs removal by sewage-sludge-derived materials with outstanding chemical and textural properties. These materials were obtained from different precursors using different chemical and thermal treatments. Results show that the H(2)S removal process entailed a catalytic conversion of H(2)S to S or SO(4) (2-) species. On the other hand, adsorption is the main mechanism governing the performance of sludge-based materials for NH(3) and VOCs. Retention capacities (x/M values) obtained for some of the sludge-based adsorbents/catalysts are similar to those obtained with commercial activated carbons selected as reference materials.

High surface area materials prepared from sewage sludge-based precursors.

This paper focuses on physical activation (CO2) and chemical activation (H3PO4, NaOH and KOH) of sewage sludge-based precursors. Our results show that (i) a simple acid washing treatment leads to a significant increase in the adsorption capacity of some precursors; (ii) under the experimental conditions tested, CO2 physical activation and chemical activation with H3PO4 were ineffective for an efficient porosity development and (iii) choosing an appropriate protocol, it is possible to obtain highly porous materials (700-1700 m2 g(-1)) by chemical activation of sludge-based precursors with alkaline hydroxides. The efficiency of the chemical activation with NaOH or KOH is very much influenced by the method used for mixing the activating agent and the precursor. The BET values of the materials obtained when physically mixing ground hydroxides with the precursor almost doubled the values obtained if other mixing methods are employed. Increasing the hydroxide:precursor ratio leads to an enhancement of the adsorption capacity of the adsorbents, with BET values ranging from 689 to 1224 m2 g(-1) for NaOH activation and from 853 to 1686 m2 g(-1) for KOH activation.