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Perchloroethylene (PCE) is a pollutant toxic to aquatic life and suspected of being a human carcinogen. It is also recalcitrant to degradation. Therefore remediation of PCE-contaminated groundwater is currently still a challenging task. In this work, the efficiency of a UV-assisted oxidation process exploiting a photocatalyst composed of zero-valent iron supported on commercial zinc sulfide (Fe/ZnS) and incorporated in a highly porous polymer, is investigated. The experimental studies were carried out, for about six months, on a pilot-scale photoreactor operating in continuous mode at the Solofra (Campania, Italy) wastewater plant, to evaluate the effectiveness and stability of the photocatalytic system. The results show that it is possible to reach a PCE degradation in natural groundwater in the range of 85–95%%. Furthermore, a kinetic model is developed and compared with collected experimental data. The mathematical model well describes the experimental data of the photocatalytic system operating both in batch and continuous mode and therefore it can be potentially used for further scale-up of photocatalytic systems devoted to PCE degradation, allowing to estimate the catalyst weight required for total PCE removal as a function of the liquid flow rate to be treated and inlet PCE concentration.

A polymeric composite consisting of Fe-N-codoped TiO2 (Fe-N-TiO2) dispersed into a monolithic syndiotactic polystyrene (sPS) aerogel (Fe-N-TiO2/sPS, 10/90 w/w) was used for the photocatalytic hydroxylation of benzene to phenol in presence of H2O2 to enhance the phenol selectivity and yield compared to Fe-N-TiO2 in powder form. Under UV light, Fe-N-TiO2/sPS composite aerogel showed selectivity to phenol of 43%, one order of magnitude more than the selectivity showed by Fe-N-TiO2 in powder form (4%). Under visible light irradiation Fe-N-TiO2 in powder form did not produce phenol, whereas selectivity to phenol of Fe-N-TiO2/sPS was 16%. The polymeric composite was recycled and reused up to five times without a significant decrease in photocatalytic oxidation activity in terms of benzene conversion and phenol yield, indicating the stability of the catalytic composite. Therefore, it was proved that the obtained photoreactive polymer composite could allow the development of innovative sustainable processes able to realize the selective oxidation reactions of aromatic hydrocarbons under mild conditions.

In this work, P-doped TiO2 (P-TiO2) photocatalyst was prepared by a modified sol-gel method at room temperature and then coated on corona discharge pre-treated polypropylene films (P-TiO2/PP). The obtained photoactive P-TiO2/PP was characterized with different techniques (XRD, SEM and SSA) and the photocatalytic effect under UV and visible light was analyzed in the degradation of methylene blue (MB), used as model organic pollutant. The photocatalytic tests were carried out in a batch photoreactor irradiated by a visible lamp (nominal power of 32 W and wavelength emission > 400 nm). The experimental results showed that the coating of P-TiO2 onto PP films allowed to achieve a MB discoloration of 63% after about 240 min of visible light irradiation.

Today, the increase in agricultural practices leads to pesticide pollution, which has become a threat to both water sources and humans. Various techniques to degrade pesticides have been used, but heterogeneous photocatalysis in presence of semiconductor nanoparticles has proven to be more efficient because it can degrade many persistent organic compounds. However, for practical and industrial applications, it is necessary to immobilize the photocatalyst on the surface or within macroscopic supports to avoid the post-treatment step to separate the photocatalyst in powder form from the treated water at the end of the process. In this work, monolithic polymer/photocatalyst composite aerogels based on syndiotactic polystyrene (sPS) and two different photocatalysts, N-doped TiO2 (NdT) and ZnO/NdT, were prepared to obtain easily recoverable materials for cost-saving processes. The aerogels were tested in the degradation of two target pesticides, atrazine (ATZ) and thiacloprid (THI), using a pilot-scale photoreactor. The experimental data showed a pollutant degradation higher than 90% after 180 min for ATZ and over 90% after 60 min of irradiation for THI. These results indicate that the heterogeneous photocatalytic process based on composite aerogels could be an efficient technology for pesticide degradation.

In recent years, aromatic substances have become the focus of environmental pollution-related concern due to their high stability and mutagenicity. In this regard, researchers have focused their attention on the development of photocatalytic processes to convert nitroaromatic compounds into aniline. In this work, the photocatalytic conversion of nitrobenzene (NB) to aniline (AN) was studied. The photocatalytic reaction was performed using commercial TiO2 (P25) and a photocatalytic aerogel, based on P25 embedded in syndiotactic polystyrene (sPS) aerogel (sPS/P25 aerogel) as photocatalysts. Different alcohols were used as hydrogen sources during the photocatalytic experiments. At the optimized operating conditions (photocatalysts dosage: 0.5 mg/L and 50% (v/v) EtOH%), an AN yield of over 99% was achieved. According to the results, this work could open avenues toward effective production of AN from NB using mild reaction conditions with sPS/P25 aerogel—in view of a possible scale-up of the photocatalytic process.

N-doped TiO2 (N-TiO2) and N-doped ZnO (N-ZnO) were synthesized utilizing ammonia as a dopant source. The chemico-physical characteristics of synthesized samples were studied by Raman spectroscopy, X-ray diffraction, SEM analysis, N2 adsorption–desorption at −196 °C, and diffuse reflectance spectroscopy. Compared to undoped samples, the introduction of nitrogen in the semiconductor lattice resulted in a shift of band-gap energy to a lower value: 3.0 eV for N-ZnO and 2.35 eV for N-TiO2. The photocatalysts were tested for the degradation of Eriochrome Black T (EBT), which was selected as a model azo dye. Both N-doped semiconductors evidenced an improvement in photocatalytic activity under visible light irradiation (62% and 20% EBT discoloration for N-TiO2 and N-ZnO, respectively) in comparison with the undoped samples, which were inactive in the presence of visible light. Different behavior was observed under UV irradiation. Whereas N-TiO2 was more photoactive than commercial undoped TiO2, the introduction of nitrogen in ZnO wurtzite resulted in a drastic reduction in photocatalytic activity, with only 45% EBT discoloration compared to total color removal obtained with the commercial ZnO sample, suggesting intrinsic limitations for doping of this class of semiconductors.

The zinc complexes 1 and 2 bearing chelating phosphorous based pincer ligands were found to catalyze the ring-opening copolymerization of L-lactide and ε-caprolactone in the melt at 110 °C to obtain a series of random copolymers in which the monomer distributions were coherent with the monomer ratio in the feed. All the obtained copolymers showed high molecular masses with monomodal and moderately narrow distributions. The thermal properties of the achieved copolymers (Tg, glass transition temperature, and Tm, melting temperature) were strongly dependent on their composition. A linear dependence of Tg with molar percentage of lactide in the copolymers was observed over a temperature range from -59 °C (pure polycaprolactone) to 55 °C (pure polylactide).

Polymeric films and in particular polypropylene (PP) films could be selected as excellent substrates for photocatalytic applications based on TiO2. However, hydrophobic surface of PP makes very difficult the adhesion of TiO2 particles on its surface. In this work corona pre-treated PP was used as a support for commercial TiO2 in order to remove organic dye methylene blue (MB) from aqueous solution under UV irradiation. In details, the pre-treated polypropylene PP films were coated with TiO2 particles by dip-coating technique. The corona pre-treatment is a practical and effective method to increase the wettability of organic polymers due to the introduction of negative groups (COO- , –O–O- ) onto the surfaces, which results in a better adhesion of the photocatalyst. The obtained coated films were characterized with different techniques sand the photocatalytic effect under UV light was analyzed in the degradation of MB dye. The photocatalytic tests were carried out in a batch photoreactor irradiated by a UV lamp (nominal power of 8 W and wavelength emission 365 nm). The experimental results showed that the coating of TiO2 onto PP films allowed to achieve a MB discoloration of 47% after about 180 min of UV irradiation. In contrast the unfunctionalized PP film did not shown any photocatalytic activity under the same irradiation conditions.

Acid Orange 7 (AO7) is an azo dye present in the effluents coming from the textile industry. It is a coloring agent consisting of an azo group bonded to aromatic rings. This azo dye can react with other chemical substances producing aromatic amines which cause toxic and carcinogenic effects in the environment. For this reason, it is necessary to eliminate this compound from aqueous discharges. Recently, the scientific research has focused the attention on heterogeneous photocatalysis based on semiconductor oxides because it is a technology able to completely degrade many organic pollutants to carbon dioxide and water at ambient temperature under UV/visible light irradiation. In photocatalysis, the most used semiconductor is titanium dioxide (TiO2). TiO2 presents various crystalline phase and a wide band gap (3.2 eV for anatase), therefore, it can be activated only under UV light irradiation. In order to make TiO2 active under visible light, in this work TiO2 doped with metallic (Fe) and non-metallic element (N) was synthetized through sol-gel method. The photocatalytic tests on discoloration of AO7 aqueous solution were carried in a photoreactor surrounded by visible-LEDs strip. To determine the optimum conditions for the photodegradation, the influence of photocatalyst dosage (1.5 - 6 g L-1), initial AO7 concentration (5 - 20 mg L-1), initial pH of the solution (3-8) and the incident visible light intensity (3.25 to 13 mW cm-2) was investigated. It was observed that the Fe-N-TiO2 photocatalyst reached about 90% of AO7 discoloration and 83% of mineralization efficiency under the optimized working conditions, in a very short time (60 min) using a photocatalyst dosage of 3 g L-1 and AO7 initial concentration of 10 mg L-1.

This paper describes the preparation and characterization of poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) highly porous monolithic aerogels with a hydrophobic nanoporous–crystalline phase and a hydrophilic sulfonated amorphous phase. The sulfonated aerogels were obtained by the sulfonation of PPO physical gels, followed by the supercritical CO2 extraction of solvents. WAXD and FTIR analysis showed that the nanoporous–crystalline phase was preserved for a degree of sulfonation up to c.a. 35%, allowing a highly volatile organic compound (VOC) sorption capacity. The sulfonated PPO aerogels exhibited a high water sorption capacity, with a water uptake of up to 500 wt%, and faster VOC sorption kinetics from water with respect to unsulfonated aerogels.

Poly-L-lactic acid (PLLA) aerogel-based scaffolds were obtained from physical PLLA gels containing cyclopentanone (CPO) or methyl benzoate (BzOMe) molecules. An innovative single step method of solvent extraction, using supercritical CO2, was used to achieve cylindrical monolithic aerogels. The pore distribution and size, analyzed by SEM microscopy, were found to be related to the crystalline forms present in the physical nodes that hold the gels together, the stable α’-form and the metastable co-crystalline ε-form, detected in the PLLA/BzOMe and PLLA/CPO aerogels, respectively. A higher mechanical compressive strength was found for the PLLA/CPO aerogels, which exhibit a more homogenous porosity. In vitro biocompatibility tests also indicated that monolithic PLLA/CPO aerogels exhibited greater cell viability than PLLA/BzOMe aerogels. An improved biocompatibility of PLLA/CPO monolithic aerogels was finally observed by coating the surface of the aerogels with polydopamine (PDA) obtained by the in situ polymerization of dopamine (DA). The synergistic effect of biodegradable polyester (PLLA) and the biomimetic interface (PDA) makes this new 3D porous scaffold, with porosity and mechanical properties that are tunable based on the solvent used in the preparation process, attractive for tissue engineering applications.

Different tri-doped TiO2 photocatalysts (Fe-N-P/TiO2, Fe-N-S/TiO2, Fe-Pr-N/TiO2, Pr-N-S/TiO2, and P-N-S/TiO2) were successfully prepared and tested in the photocatalytic removal of thiacloprid (THI) under UV-A, visible, and direct solar light irradiation. The physical-chemical properties of the prepared catalysts were analyzed by different characterization techniques, revealing that dopants are effectively incorporated into the anatase TiO2 lattice, resulting in a decrease of the energy band gap. The reduction of photoluminescence intensity indicates a lower combination rate and longer lifespan of photogenerated carriers of all doped samples in comparison with the un-doped TiO2. The doped photocatalysts not only significantly promote the photodegradation under UV-A light irradiation but also extend the optical response of TiO2 to visible light region, and consequently improve the visible light degradation of THI. Fe-N-P tri-doped TiO2 sample exhibits the highest THI photodegradation degree (64% under UV-A light, 29% under visible light and 73% under solar light).

Crystalline films of syndiotactic polystyrene (s-PS), a commercially available thermoplastic polymer, having a highly hydrophilic amorphous phase, were achieved by using a mild solid-state sulfonation procedure. Despite the used mild process conditions, an easy and uniform sulfonation of the phenyl rings of the amorphous phase is obtained. The crystallinity of the polymer was not affect by the sulfonation degree (S), at least at S less than 20%, and the obtained polymer films show the nanoporous crystalline form of s-PS. As widely reported in literature, the nanoporous nature of the polymer crystalline phase gives to these materials the ability to absorb and release organic molecules of appropriate size and polarity. This property, coupled to transparency, makes these materials potentially useful intraocular lens (IOLs) and contact lens applications. Sulfonation procedure and sulfonated film samples characterization by using wide-angle X-ray diffraction (WAXD), Fourier-transform infrared (FTIR) and ultraviolet-visible (UV-vis) spectroscopy techniques and water sorption tests were reported. Furthermore, the biocompatibility study demonstrated no cytotoxicity and appropriate cell interaction properties for the specific applications.

An effective route for ring-opening copolymerization of β-butyrolactone (BBL) with ε-decalactone (ε-DL) is reported. Microstructures of the block copolymers characterized by 13C NMR spectroscopy revealed syndiotactic-enriched poly(3-hydroxybutyrate) (PHB) blocks. Several di- and triblock copolymers (PDL-b-PHB and PDL-b-PHB-b-PDL, respectively) were successfully synthesized by sequential addition of the monomers using (salan)Y(III) complexes as catalysts. The results from MALDI-ToF mass spectrometry confirmed the presence of the copolymers. Moreover, thermal properties of the block copolymers were also investigated and showed that the microphase separation of PDL-b-PHB copolymers into PHB- and PDL-rich domains has an impact on the glass transition temperatures of both blocks.

Phenol is an important chemical compound since it is a precursor of the industrial production of many materials and useful compounds. Nowadays, phenol is industrially produced from benzene by the multi-step “cumene process”, which is energy consuming due to high temperature and high pressure. Moreover, in the “cumene process”, the highly explosive cumene hydroperoxide is produced as an intermediate. To overcome these disadvantages, it would be useful to develop green alternatives for the synthesis of phenol that are more efficient and environmentally benign. In this regard, great interest is devoted to processes in which the one-step oxidation of benzene to phenol is achieved, thanks to the use of suitable catalysts and oxidant species. This review article discusses the direct oxidation of benzene to phenol in the liquid phase using different catalyst formulations, including homogeneous and heterogeneous catalysts and photocatalysts, and focuses on the reaction mechanisms involved in the selective conversion of benzene to phenol in the liquid phase.

Highly porous monolithic aerogels based on ZnO photocatalyst and syndiotactic polystyrene (s-PS) were obtained by supercritical CO2 treatment of ZnO/s-PS gels. The prepared aerogels were characterized and their photocatalytic activity was evaluated using phenol and toluene as water pollutant models. The s-PS nanoporous crystalline phase, able to absorb pollutant molecules, was proven to be necessary to ensure high photocatalytic efficiency as the aerogel acts not only as a support, but also as pollutant pre-concentrator. The reusability of ZnO/s-PS aerogels is also strong showing no decrease in photocatalytic activity after six consecutive degradation trials. Finally, the aerogel matrix prevents ZnO dissolution occurring under acidic conditions and promotes a selective removal of the pollutants. The synergy between the photocatalyst and the innovative polymeric support provides the composite system with robustness, chemical stability, easy recovery after treatment, high efficiency of pollutant removal with a marked selectivity which make these materials promising for large scale applications.

The synthesis of isotactic poly(N-butenyl-carbazole) (i-PBK) by using homogeneous isospecific Ziegler-Natta catalytic system is reported. The achieved polymer is crystalline and shows, to DSC and X-ray analysis, two distinct crystalline phases. i-PBK FTIR spectrum and X-ray diffraction pattern are compared with those of poly(N-vinylcarbazole) (PVK). The observed differences are tentatively associated with higher flexibility of the i-PBK chains due to the alkylene group connecting the carbazole group to the main chain. i-PBK optical properties are also compared with those of PVK and isotactic poly(N-pentenyl-carbazole) (i-PPK), a higher homologue of i-PBK recently used as emitting layer in organic light emitting diodes (OLEDs) showing white light emission. The close similarity of the fluorescence spectra of i-PBK and i-PPK is a promising basis for optical applications of this polymer.

Chemical sensors are generally based on the integration of suitable sensitive layers and transducing mechanisms. Although inorganic porous materials can be effective, there is significant interest in the use of polymeric materials because of their easy fabrication process, lower costs and mechanical flexibility. However, porous polymeric absorbents are generally amorphous and hence present poor molecular selectivity and undesired changes of mechanical properties as a consequence of large analyte uptake. In this contribution the structure, properties and some possible applications of sensing polymeric films based on nanoporous crystalline phases, which exhibit all identical nanopores, will be reviewed. The main advantages of crystalline nanoporous polymeric materials with respect to their amorphous counterparts are, besides a higher selectivity, the ability to maintain their physical state as well as geometry, even after large guest uptake (up to 10–15 wt%), and the possibility to control guest diffusivity by controlling the orientation of the host polymeric crystalline phase. The final section of the review also describes the ability of suitable polymeric films to act as chirality sensors, i.e., to sense and memorize the presence of non-racemic volatile organic compounds.