Solar photocatalytic degradation of polyethylene terephthalate nanoplastics: Evaluation of the applicability of the TiO2/MIL-100(Fe) composite material

For the first time, TiO2/MIL-100(Fe) photocatalysts supported on perlite mineral particles prepared by the solvothermal/microwave methods and post-annealing technique were tested in the degradation of polyethylene terephthalate nanoplastics (PET NPs). Powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, UV–vis diffuse reflectance spectroscopy, N2 physisorption, photoluminescence emission spectroscopy, photocurrent response, and electrochemical impedance spectroscopy were used to characterize the as-prepared materials. The response surface methodology approach was used to study the effects: pH of the NPs suspension and incorporated amount of MIL-100(Fe) on the TiO2/MIL-100(Fe) catalyst to optimize the photocatalytic degradation of the PET NPs under simulated solar light. The degradation of the PET NPs was evaluated by measuring turbidity and carbonyl index (FTIR) changes. The total organic carbon (TOC) in the solution during the degradation of the PET NPs was assessed to measure NPs oxidation into water-soluble degradation by-products. The active species involved in the photocatalytic degradation of PET NPs by the TiO2/MIL-100(Fe) composite was further examined based on trapping experiments. The use of 12.5 wt% TiO2/MIL-100(Fe) catalyst showed improved photocatalytic efficacy in the oxidation of PET NPs at pH 3 under simulated sunlight compared to bare TiO2. The increase in the carbonyl index (CI = 0.99), the reduction in the turbidity ratio (0.454), and the increase in the content of TOC released (3.00 mg/L) were possible with 12.5 wt% TiO2/MIL-100(Fe) material. In contrast, the PET NPs were slowly degraded by TiO2-based photocatalysis (CI = 0.96, turbidity ratio = 0.539, released TOC = 2.12 mg/L). The mesoporous TiO2/MIL-100(Fe) composites with high specific surface area, capacity to absorb visible light, and effective separation of photogenerated electron-hole charges clearly demonstrated the enhancement of the photocatalytic performance in the PET NPs degradation under simulated solar light

Corrosion resistance of anodic layers grown on 304L stainless steel at different anodizing times and stirring speeds

Different chemical and physical treatments have been used to improve the properties and functionalities of steels. Anodizing is one of the most promising treatments, due to its versatility and easy industrial implementation. It allows the growth of nanoestructured oxide films with interesting properties able to be employed in different industrial sectors. The present work studies the influence of the anodizing time (15, 30, 45 and 60 min), as well as the stirring speed (0, 200, 400, and 600 rpm), on the morphology and the corrosion resistance of the anodic layers grown in 304L stainless steel. The anodic layers were characterized morphologically, compositionally, and electrochemically, in order to determine the influence of the anodization parameters on their corrosion behavior in a 0.6 mol L-1 NaCl solution. The results show that at 45 and 60 min anodizing times, the formation of two microstructures is favored, associated with the collapse of the nanoporous structures at the metal-oxide interphace. However, both the stirring speed and the anodizing time have a negligeable effect on the corrosion behavior of the anodized 304L SS samples, since their electrochemical values are similar to those of the non-anodized ones

Highly reflective engobes for ink-jet printed coloured porcelain stoneware tiles (CO-2:L05)

Ink-jet decoration is a technology suitable for designing ceramic tiles with solar reflectance (SR) properties. SR is the ratio between the solar energy reflected by a surface and the total incident energy. If incorporated into the cities' building envelope, solar reflective tiles mitigate the Urban Heat Island (UHI) phenomenon, which makes urban centres hotter than rural areas. Even if many efforts have been conducted to develop solar reflective surfaces, little research has been conducted for the development of coloured tiles suitable to be fabricated by ink-jet technology, where the inks tend to counteract the effect of the reflective engobes. To overcome such an issue, the fabrication of solar reflective ink-jet decorated tiles using a reflective engobe was investigated. The engobe was prepared using an industrial CZAS (CaO–ZrO2–Al2O3–SiO2) frit and a ZrSiO4 pigment. The engobe prepared with such frit presented a high SR value (0.918 ± 0.002) and was able to develop ink-jet printed coloured tiles (cool colors) using both white and red porcelain stoneware supports. Overall, it was found that using high engobe thicknesses, white porcelain stoneware supports, and light colour inks allows the fabrication of cool color ink-jet printed tiles. Most of those tiles present solar reflective properties higher than those reported in previous works, even for dark inks that usually tend to counteract the effect of solar reflective engobes

Solar reflective properties of porcelain tiles for UHI mitigation: effect of highly reflective frits in the engobe's formulation

The 2030 Agenda for Sustainable Development charts the course for transforming the world socially, economically, and environmentally by 2030. Cities represent a critical issue in this transformation: the population growth and the intense anthropogenic activity make them centers of strong environmental impact. For instance, cities have become Urban Heat Islands (UHIs) due to the significant increase in temperatures caused by pollution and heat produced by human activities. The urgency to make cities sustainable from an environmental point of view urges the search for innovative solutions to counter this phenomenon. One of those solutions is reflective tiles, as they absorb less heat and stay cooler than traditional materials and are considered an effective mitigation technique against the UHI phenomenon. This study investigated the obtaining of solar reflective ceramic tiles through the modification of the engobe's formulation. To achieve this goal, a glass-ceramic frit with high solar reflectance (SR) property (0.95) was incorporated into the formulation of a commercially available ceramic engobe. To verify whether the modified engobe can be used to prepare solar reflective cool color ceramic tiles, the tiles were decorated in quadrichromy by ink-jet printing according to the four-color CMYK color model. The Gray Scale (GS) printing system was used to investigate five different printing intensities. The results suggest that when a glass-ceramic frit with a high intrinsic SR value is incorporated into the formulation of an industrial engobe, it can raise its SR value, passing from 0.69 to 0.75. However, the productive process used to obtain ceramic tiles limits the SR values due to crystallization. It was also found that ink-jet decoration negatively affects the solar reflective property of the tiles prepared with the new engobe due to its coverage by the inks and their mineralogical composition. Thus, the results presented in this work evidence that changing the engobe's formulation is not enough to obtain ceramic tiles with high solar reflective properties

Solar reflective ink-jet printed porcelain stoneware tiles as an alternative for Urban Heat Island mitigation

Digital ink-jet printing is a decoration system for ceramic tiles that requires the application of engobes with high whiteness and opacity, characteristics that can be used to design solar reflective ink-jet decorated tiles. These materials can help to mitigate Urban Heat Island (UHI) phenomenon. Here, the fabrication of ink-jet printed solar reflective tiles using an engobe with high solar reflectance was investigated. Two printing modalities (binary (BIN) and grayscale (GS)), five printing intensities, and four colours were tested. It was found that some of the prepared tiles can be used for mitigating the UHI phenomenon. The solar reflective properties were mainly derived from the reflective engobe, and in some grade, from the mineral composition of the inks. The colour and roughness measurements revealed that the GS modality could prepare ink-jet decorated tiles with good solar reflective properties with a smaller quantity of inks and good soiling resistance

First insights into photocatalytic degradation of HDPE and LDPE microplastics by a mesoporous N-TiO2 coating: Effect of size and shape of microplastics

Microplastics (MPs), which are small plastic debris of ≤5 mm size, are polluting the oceans with negative consequences for their biota. In this work, visible-light photocatalysis of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) MPs in aqueous medium using a mesoporous N-TiO2 coating is proposed as an alternative for fighting MP pollution. Spherical primary HDPE MPs were extracted from commercially available facial scrubs, while film-shaped secondary LDPE MPs were obtained from a plastic bag. For each plastic, two different sizes were tested. Degradation was measured by mass-loss and carbonyl-index (CI) calculation. The results obtained reveal that the photocatalytic degradation of HDPE and LDPE MPs using an N-TiO2 coating was affected by the size and shape of the MPs. Smaller MPs led to higher degradation, while film-shaped MPs led to lower degradation that was related to a poorly illuminated and oxygenated reaction medium. These results set the basis for further investigation on the on the design of more effective photocatalytic-reaction systems for decreasing MP inputs to the environment

Degradation of primary nanoplastics by photocatalysis using different anodized TiO2 structures

In recent years, plastic pollution has become an environmental problem requiring urgent attention. Recently, the release of nano-sized plastics (<1 µm) into the environment has raised concern due to the possible adverse effects that their small size can have on the trophic web. Advanced oxidation processes are efficient at removing organic pollutants such as dyes and pharmaceuticals, making them a viable approach for treating these hazardous materials. This study proposes the use of photocatalysis as an alternative for removing polystyrene nanoparticles (PS-NPs) from aqueous media. A comparative study was carried out to determine the photocatalytic activity of three different TiO2 photocatalysts synthesized by anodization. Elimination and degradation were monitored by turbidimetry, TOC, FTIR, and GC/MS, and the presence of carbonyl groups and intermediate products was recorded to confirm PS-NP degradation. Statistical analysis revealed that PS-NP elimination using TiO2/T and TiO2/M as photocatalysts was more efficient than with photolysis. The results indicate that the mixed structure (nanotubes/nanograss) reduces the concentration of PS-NPs in dispersion 2 times more efficiently than photolysis with UV light does. Despite the challenges posed by nanoplastic contamination, this study provides a useful remediation approach; a technique that, to date, has received little attention

Boosting visible-light photocatalytic degradation of polystyrene nanoplastics with immobilized CuxO obtained by anodization

Plastics composed mainly of polystyrene polymer have become widely used materials in different industries. The poor disposition of these products and their interaction with the environment has caused their fragmentation into particles that reach a nanometric scale (≤1 µm), called nanoplastics (NPs), considered pollutants due to their effects on human health and capacity to absorb toxic-bioaccumulative substances. Currently, advanced oxidation processes have shown efficiency in removing emerging pollutants, making them promising alternatives to treat NPs. This study proposes photocatalytic degradation with visible light irradiation to mitigate the contamination produced by polystyrene nanoplastics (PS-NPs). Therefore, PS particles of ~ 350 nm were degraded using immobilized copper oxide semiconductors grown by the anodizing process for the first time. The anodization process considered two growth media (NH4F and NaOH), obtaining immobilized Cu2O/CuO semiconductors with different morphologies and a bandgap between 1.6 and 2 eV. The degradation of the nanoplastics was examined using several analytical methods such as TOC, ATR-FTIR, turbidity, and gas chromatography showing the presence of intermediates compounds with the carbonyl group, confirming the degradation of PS-NPs. The results showed that photocatalysis in visible light with copper oxide semiconductors promotes polymer chain scissions and reduces the concentration of PS-NPs up to 23%, representing six times more than the reductions achieved by photolysis. In addition, mineralization of up to 15% was achieved. Although contamination by nanoplastics involves many challenges, this study provides the basis for an alternative process that allows the mitigation of these nanoplastics using visible light

The role of the reactive species involved in the photocatalytic degradation of hdpe microplastics using c,n-tio2 powders

Microplastics (MPs) are distributed in a wide range of aquatic and terrestrial ecosystems throughout the planet. They are known to adsorb hazardous substances and can transfer them across the trophic web. To eliminate MPs pollution in an environmentally friendly process, we propose using a photocatalytic process that can easily be implemented in wastewater treatment plants (WWTPs). As photocatalysis involves the formation of reactive species such as holes (h+), electrons (e−), hydroxyl (OH•), and superoxide ion (O2•−) radicals, it is imperative to determine the role of those species in the degradation process to design an effective photocatalytic system. However, for MPs, this information is limited in the literature. Therefore, we present such reactive species’ role in the degradation of high-density polyethylene (HDPE) MPs using C,N-TiO2. Tert-butanol, isopropyl alcohol (IPA), Tiron, and Cu(NO3)2 were confirmed as adequate OH•, h+, O2•− and e− scavengers. These results revealed for the first time that the formation of free OH• through the pathways involving the photogenerated e− plays an essential role in the MPs’ degradation. Furthermore, the degradation behaviors observed when h+ and O2•− were removed from the reaction system suggest that these species can also perform the initiating step of degradation