Carlos Rocha Gomes

The composites of heteropolyacids (H₃PW₁₂, H₃PMo₁₂) incorporated into amine-functionalized silica materials were used for the first time as heterogeneous catalysts in the valorization of glycerol (a major waste from the biodiesel industry) through acetalization reaction with acetone. The polyoxotungstate catalyst H₃PW₁₂@AptesSBA-15 exhibited higher catalytic efficiency than the phosphomolybdate, achieving 97% conversion and 97% of solketal selectivity, after 60 min at 25 °C, or 91% glycerol conversion and the same selectivity, after 5 min, performing the reaction at 60 °C. A correlation between catalytic performance and catalyst acidity is presented here. Furthermore, the stability of the solid catalyst was investigated and discussed.

The improvement of sustainable chemical processes plays a pivotal role in safe environmental and societal development, for example, by reducing the use of hazardous substances, preventing chemical waste, and improving the efficiency of chemical reactions to obtain added-value compounds. In this context, the porous coordination polymer MOF-808 (MOF, metal–organic framework) was prepared by a straightforward method in water, at room temperature, and was unequivocally characterized by powder X-ray diffraction, vibrational spectroscopy, thermogravimetric analysis, and scanning electron microscopy. MOF-808 material was applied for the first time as catalysts in ring-opening aminolysis reactions of epoxides. It demonstrated high activity and selectivity for reactions of styrene oxide and cyclohexene oxide with aniline, using a very low amount of an eco-sustainable solvent (0.5 mL of EtOH), at 70 °C. Moreover, MOF-808 demonstrated high stability in the catalytic reaction conditions applied, and a notable reuse capacity of up to 20 consecutive reaction cycles, without significant variation in its catalytic performance. In fact, this Zr-based porous coordination polymer prepared by environment-friendly conditions proved to be a novel efficient heterogeneous catalyst, promoting the ring-opening reaction of epoxides under more sustainable conditions, and using a very low amount of catalyst.

The composites of heteropolyacids (H3PW12, H3PMo12) incorporated into amine-functionalized silica materials, were used for the first time as heterogeneous catalysts in the valorisation of glycerol (a large waste from biodiesel industry) by acetalization reaction with acetone. The polyoxotungstate catalyst H3PW12@AptesSBA-15 presented higher catalytic efficiency than the phosphomolybdate, with 97% of conversion with 97% of solketal selectivity, after 60 min at 25 °C, or 91% of glycerol conversion and the same selectivity, after 5 min, performing the reaction at 60 ºC. A relation of catalytic performance and acidity of the catalyst is here presented. Furthermore, the stability of the solid catalyst was investigated and discussed.

The adsorptive performance of mesoporous silica-based materials towards inorganic (metal ions) and organic (dyes) water pollutants was investigated. Mesoporous silica materials with different particle size, surface area and pore volume were prepared and tailored with different functional groups. These materials were then characterised by solid-state techniques, namely vibrational spectroscopy, elemental analysis, scanning electron microscopy and nitrogen adsorption–desorption isotherms, allowing the successful preparation and structural modifications of the materials to be confirmed. The influence of the physicochemical properties of the adsorbents towards the removal of metal ions (Ni²⁺, Cu²⁺ and Fe³⁺) and organic dyes (methylene blue and methyl green) from aqueous solutions was also investigated. The results reveal that the exceptionally high surface area and suitable ζ-potential of the nanosized mesoporous silica nanoparticles (MSNPs) seem to favour the adsorptive capacity of the material for both types of water pollutants. Kinetic studies were performed for the adsorption of organic dyes by MSNPs and large-pore mesoporous silica (LPMS), suggesting that the process follows a pseudo-second-order model. The recyclability along consecutive adsorption cycles and the stability of the adsorbents after use were also investigated, showing that the material can be reused. Current results show the potentialities of novel silica-based material as a suitable adsorbent to remove pollutants from aquatic matrices with an applicability to reduce water pollution.

The aim of the present work was to evaluate the influence of two different pharmaceutical compounds (bezafibrate and paroxetine) on the phytoremediation potential of Phragmites australis in an estuarine medium contaminated by copper. Plants were exposed for seven days to a simplified estuarine medium, elutriate solution, with or without sediment. The medium was doped with copper and bezafibrate or paroxetine. P. australis plants were able to accumulate a significant amount of Cu, particularly in their roots (600 and 250 times increase in copper levels in the absence and presence of sediment, respectively), corroborating the phytostabilization potential of salt marsh plants. Metal uptake and translocation was significantly lower in the presence of sediment (Cu in leaves increased 20 times in the absence and only 4 times in the presence of sediment). An effect of either pharmaceutical compound on metal accumulation was not observed (levels of Cu in plants tissues were in general identical) but, in the presence of sediment, both bezafibrate and paroxetine changed Cu solubility in elutriate solution, either decreasing or increasing it. The current study highlights the possible influence the presence of contaminants of different characteristics (inorganic and organic contaminants) can have on salt marsh phytoremediation potential in the long run, and the effects pollutants might have in the environment.

This study aims to investigate the effect of two different groups of phenolic compounds (the alkylphenols nonylphenol (NP) and octylphenol (OP), and the chlorophenol pentachlorophenol (PCP)) on constructed wetlands (CWs) performance, including on organic matter, nutrients and contaminants removal efficiency, and on microbial community structure in the plant bed substrate. CWs were assembled at lab scale simulating a vertical flow configuration and irrigated along eight weeks with Ribeira de Joane (an urban stream) water not doped (control) or doped with a mixture of NP and OP or with PCP (at a 100 μg·L⁻¹ concentration each). The presence of the phenolic contaminants did not interfere in the removal of organic matter or nutrients in CWs in the long term. Removals of NP and OP were >99%, whereas PCP removals varied between 87% and 98%, mainly due to biodegradation. Microbial richness, diversity and dominance in CWs substrate were generally not affected by phenolic compounds, with only PCP decreasing diversity. Microbial community structure, however, showed that there was an adaptation of the microbial community to the presence of each contaminant, with several specialist genera being enriched following exposure. The three more abundant specialist genera were Methylotenera and Methylophilus (methylophilaceae family) and Hyphomicrobium (hyphomicrobiaceae family) when the systems were exposed to a mixture of NP and OP. When exposed to PCP, the three more abundant genera were Denitromonas (Rhodocyclaceae family), Xenococcus_PCC_7305 (Xenococcaceae family) and Rhodocyclaceae_uncultured (Rhodocyclaceae family). To increase CWs efficiency in the elimination of phenolic compounds, namely PCP which was not totally removed, strategies to stimulate (namely biostimulation) or increase (namely bioaugmentation) the presence of these bacteria should be explore. This study clearly shows the potential of vertical flow CWs for the removal of phenolic compounds, a still little explored subject, contributing to promote the use of CWs as nature-based solutions to remediate water contaminated with different families of persistent and/or emergent contaminants.