Catalytic Strategies for the Upcycling of Polyolefin Plastic Waste.

Chemical upgrading of waste plastics is currently one of the most important methods for addressing plastic pollution. In comparison to the current methods of incineration or landfill, chemical upgrading enables the utilization of carbon and hydrogen elements in waste plastics as resources. This process strongly relies on efficient catalysts and reaction systems. Through catalyst design, waste plastics can be converted into fuels or chemicals under the optimized reaction conditions, extending their life cycles. In this review, we systematically discuss various chemical conversion methods for polyolefin waste plastics, which account for a large proportion of waste plastics. We further explore the remaining challenges and future development trends in this field, including improving product value through product engineering and shifting research perspectives to exploring the tolerance of catalysts toward impurities in practical waste plastic waste rather than using pure plastic feedstock.

The application value of lung ultrasound scoring in assessing disease severity: Evaluation of small-scale outbreaks of COVID-19.

PURPOSE: This study explored the use of transthoracic lung ultrasound for evaluating COVID-19 patients, compared it with computed tomography (CT), and examined its effectiveness using 8 and 12 lung regions. METHODS: A total of 100 patients with COVID-19 and 40 healthy volunteers were assessed using 12 regions (bilateral upper/lower regions of the anterior/lateral/posterior chest) and simplified 8 zones (bilateral upper/lower regions of the anterior/lateral chest) transthoracic lung ultrasound. The relationships between ultrasound, CT, and clinical indicators were analyzed to evaluate the diagnostic value of ultrasound scores in COVID-19. RESULTS: Increased disease severity correlated with increased 8- and 12-zone ultrasound and CT scores (all p < 0.05). The modified 8-zone method strongly correlated with the 12-zone method (Pearson's r = 0.908, p < 0.05). The 8- and 12-zone methods correlated with CT scoring (correlation = 0.568 and 0.635, respectively; p < 0.05). The intragroup correlation coefficients of the 8-zone, 12-zone, and CT scoring methods were highly consistent (intragroup correlation coefficient = 0.718, p < 0.01). The 8-zone ultrasound score correlated negatively with oxygen saturation (rs = 0.306, p < 0.05) and Ca (rs = 0.224, p < 0.05) and positively with IL-6 (rs = 0.0.335, p < 0.05), erythrocyte sedimentation rate (rs = 0.327, p < 0.05), alanine aminotransferase (rs = 0.230, p < 0.05), and aspartate aminotransferase (rs = 0.251, p < 0.05). The 12-zone scoring method correlated negatively with oxygen saturation (rs = 0.338, p < 0.05) and Ca (rs = 0.245, p < 0.05) and positively with IL-6 (rs = 0.354, p < 0.05) and erythrocyte sedimentation rate (rs = 0.495, p < 0.05). CONCLUSION: Lung ultrasound scores represent the clinical severity and have high clinical value for diagnosing COVID-19 pneumonia. The 8-zone scoring method can improve examination efficiency and reduce secondary injuries caused by patient movement.

Islet hypoplasia of adult offspring rats caused by intrauterine chronic hypoxia is compensated by up-regulation of INS and PDX-1.

BACKGROUND: Intrauterine chronic hypoxia (ICH) can lead to pancreatic dysmetabolism in offspring. This study aimed to determine the changes in islet function of offspring through a rat ICH model and detect the factors affecting islet function. METHODS: Twenty couples of healthy Sprague - Dawley adult rats were randomly mated, and the pregnant rats were randomly allocated to ICH and normal control (NC) groups. Pregnant rats in the ICH group were placed in a hypoxic chamber with 13% oxygen concentration for hypoxia treatment twice a day for 4 h until delivery at 21 days. NC group is inlet with normal air from beginning to end. After delivery, blood was taken from the heart of pregnant rats for blood gas analysis. The weight of the offspring rats was measured at 12 h after birth and 16 weeks after birth. At 16 weeks, the immunohistochemical results of ß-cell total, islet area, insulin (INS), and glucose transporter 2 (GLUT2) proteins were obtained from the islets. The mRNA data of INS and pancreatic and duodenal homeobox 1 (PDX-1) genes were obtained from pancreas. RESULTS: We found the ß-cell total, islet area, and the positive cell area of INS and GLUT2 of offspring rats in ICH group were lower than those of NC group, while the levels of INS and PDX-1 genes were higher in ICH group than in NC group. CONCLUSIONS: ICH can lead to islet hypoplasia in adult male offspring rats. However, this is within the compensatory range.

Synergistic enhanced activation of peroxymonosulfate by heterojunction Co3O4-CuO@CN for removal of oxytetracycline: Performance, mechanism, and stability.

Metal-organic frameworks (MOFs) as precursors for catalysts has drawn growing attentions. In this study, heterojunction Co3O4-CuO doped carbon materials (noted as Co3O4-CuO@CN) were prepared by direct carbonization of CuCo-MOF in air. It was found that the Co3O4-CuO@CN-2 exhibited excellent catalytic activity with the highest Oxytetracycline (OTC) degradation rate of 0.0902 min-1 at 50 mg/L of Co3O4-CuO@CN-2 dosage, 2.0 mM of PMS and 20 mg/L of OTC, which was 4.25 and 4.96 times that of CuO@CN and Co3O4@CN, respectively. Furthermore, Co3O4-CuO@CN-2 was efficient over a wide pH range (pH 1.9-8.4), and possessed good stability and reusability without OTC degradation decrease after five consecutive uses at pH 7.0. In a comprehensive analysis, the rapid regeneration of Cu(II) and Co(II) is responsible for their excellent catalytic performance, and the p-p heterojunction structure formed between Co3O4 and CuO acts as an intermediary of electron transfer to accelerate PMS decomposition. Moreover, it was interesting to find that Cu rather than Co species played a vital role in the PMS activation. The quenching experiments and electron paramagnetic resonance demonstrated that .OH, SO4•-, and 1O2 were the reactive species responsible for oxidation of OTC and the non-radical pathway triggered by 1O2 was dominant.

The Research Status, Potential Hazards and Toxicological Mechanisms of Fluoroquinolone Antibiotics in the Environment.

Fluoroquinolone antibiotics are widely used in human and veterinary medicine and are ubiquitous in the environment worldwide. This paper recapitulates the occurrence, fate, and ecotoxicity of fluoroquinolone antibiotics in various environmental media. The toxicity effect is reviewed based on in vitro and in vivo experiments referring to many organisms, such as microorganisms, cells, higher plants, and land and aquatic animals. Furthermore, a comparison of the various toxicology mechanisms of fluoroquinolone antibiotic residues on environmental organisms is made. This study identifies gaps in the investigation of the toxic effects of fluoroquinolone antibiotics and mixtures of multiple fluoroquinolone antibiotics on target and nontarget organisms. The study of the process of natural transformation toward drug-resistant bacteria is also recognized as a knowledge gap. This review also details the combined toxicity effect of fluoroquinolone antibiotics and other chemicals on organisms and the adsorption capacity in various environmental matrices, and the scarcity of data on the ecological toxicology evaluation system of fluoroquinolone antibiotics is identified. The present study entails a critical review of the literature providing guidelines for the government to control the discharge of pollutants into the environment and formulate policy coordination. Future study work should focus on developing a standardized research methodology for fluoroquinolone antibiotics to guide enterprises in the design and production of drugs with high environmental biocompatibility.

Superparamagnetic iron oxide nanoparticles target BxPC-3 cells and silence MUC4 for the treatment of pancreatic cancer.

PURPOSE: Superparamagnetic iron oxide nanoparticles (SPION) are excellent magnetic resonance imaging (MRI) contrast agents. Mucin 4 (MUC4) acts as pancreatic cancer (PC) tumor antigen and influences PC progression. Small interfering RNAs (siRNAs) are used as a gene-silencing tool to treat a variety of diseases. METHODS: We designed a therapeutic probe based on polyetherimide-superparamagnetic iron oxide nanoparticles (PEI-SPION) combined with siRNA nanoprobes (PEI-SPION-siRNA) to assess the contrast in MRI. The biocompatibility of the nanocomposite, and silencing of MUC4 were characterized and evaluated. RESULTS: The prepared molecular probe had a particle size of 61.7 ± 18.5 nm and a surface of 46.7 ± 0.8mV and showed good biocompatibility in vitro and T2 relaxation efficiency. It can also load and protect siRNA. PEI-SPION-siRNA showed a good silencing effect on MUC4. CONCLUSION: PEI-SPION-siRNA may be beneficial as a novel theranostic tool for PC.

Synthesis of Bimetallic FeCu-MOF and Its Performance as Catalyst of Peroxymonosulfate for Degradation of Methylene Blue.

Bimetallic MOFs have recently emerged as promising materials for wastewater treatment based on advanced oxidation processes. Herein, a new bimetallic MOF (FeCu-MOF) was fabricated by hydrothermal process. The structural, morphological, compositional and physicochemical properties of the as-synthesized bimetallic FeCu-MOF were characterized by XRD, FT-IR, SEM, TEM, BET, and XPS. TEM and XPS confirmed the homogeneous distribution of CuO2 nanoparticles in the as-synthesized materials. The result of wastewater treatment indicated that 100% of MB was removed by 6.0 mM PMS activated with 0.6 g/L of FeCu-MOF in 30 min. The high catalytic performance of FeCu-MOF was probably due to the accelerated electron and mass transfer resulting from the existence of a homogeneous distribution of unsaturated metal sites and an abundant mesoporous structure. The obtained results from the competitive quenching tests demonstrated that sulfate radicals (SO4•-) were the major species responsible for MB oxidation. In addition, hydroxyl (·OH) and singlet oxygen (1O2) also had a nonnegligible role in the MB removal. Interestingly, the addition of acetate ion (CHCOO-) promoted the removal of MB while other anions (including NO2-, H2PO4-, SO42-, HPO42-, and HCO3-) inhibited the MB removal. Furthermore, a possible mechanism based on both heterogeneous and homogeneous activation of PMS was proposed, along with the MB degradation mechanism.

Coking-Resistant Polyethylene Upcycling Modulated by Zeolite Micropore Diffusion.

Although the mass production of synthetic plastics has transformed human lives, it has resulted in waste accumulation on the earth. Here, we report a low-temperature conversion of polyethylene into olefins. By mixing the polyethylene feed with rationally designed ZSM-5 zeolite nanosheets at 280 °C in flowing hydrogen as a carrier gas, light hydrocarbons (C1-C7) were produced with a yield of up to 74.6%, where 83.9% of these products were C3-C6 olefins with almost undetectable coke formation. The reaction proceeds in multiple steps, including polyethylene melting, flowing to access the zeolite surface, cracking on the zeolite surface, formation of intermediates to diffuse into the zeolite micropores, and cracking into small molecules in the zeolite micropores. The ZSM-5 zeolite nanosheets kinetically matched the cascade cracking steps on the zeolite external surface and within micropores by boosting the intermediate diffusion. This feature efficiently suppressed the intermediate accumulation on the zeolite surface to minimize coke formation. In addition, we found that hydrogen participation in the cracking process could hinder the formation of polycyclic species within zeolite micropores, which also contributes to the rapid molecule diffusion. The coking-resistant polyethylene upcycling process at a low temperature not only overturns the general viewpoint for facile coke formation in the catalytic cracking over the zeolites but also demonstrates how the polyethylene-based plastics can be upcycled to valuable chemicals. In addition to the model polyethylene, the reaction system worked efficiently for the depolymerization of multiple practically used polyethylene-rich plastics, enabling an industrially and economically viable path for dealing with plastic wastes.

Physical mixing of a catalyst and a hydrophobic polymer promotes CO hydrogenation through dehydration.

In many reactions restricted by water, selective removal of water from the reaction system is critical and usually requires a membrane reactor. We found that a simple physical mixture of hydrophobic poly(divinylbenzene) with cobalt-manganese carbide could modulate a local environment of catalysts for rapidly shipping water product in syngas conversion. We were able to shift the water-sorption equilibrium on the catalyst surface, leading to a greater proportion of free surface that in turn raised the rate of syngas conversion by nearly a factor of 2. The carbon monoxide conversion reached 63.5%, and 71.4% of the hydrocarbon products were light olefins at 250°C, outperforming poly(divinylbenzene)-free catalyst under equivalent reaction conditions. The physically mixed CoMn carbide/poly(divinylbenzene) catalyst was durable in the continuous test for 120 hours.

Fischer-Tropsch synthesis to olefins boosted by MFI zeolite nanosheets.

Catalytic reactions are severely restricted by the strong adsorption of product molecules on the catalyst surface, where promoting desorption of the product and hindering its re-adsorption benefit the formation of free sites on the catalyst surface for continuous substrate conversion1,2. A solution to this issue is constructing a robust nanochannel for the rapid escape of products. We demonstrate here that MFI zeolite crystals with a short b-axis of 90-110 nm and a finely controllable microporous environment can effectively boost the Fischer-Tropsch synthesis to olefins by shipping the olefin molecules. The ferric carbide catalyst (Na-FeCx) physically mixed with a zeolite promoter exhibited a CO conversion of 82.5% with an olefin selectivity of 72.0% at the low temperature of 260 °C. By contrast, Na-FeCx alone without the zeolite promoter is poorly active under equivalent conditions, and shows the significantly improved olefin productivity achieved through the zeolite promoter. These results show that the well-designed zeolite, as a promising promoter, significantly boosts Fischer-Tropsch synthesis to olefins by accelerating escape of the product from the catalyst surface.

Selective and leaching-resistant palladium catalyst on a porous polymer support for phenol hydrogenation.

Selective hydrogenation of phenol is promising for the utilization of renewable lignocellulose and production of cyclohexanone that usually relies on petroleum, but it is challenging to simultaneously achieve high activity and selectivity. Herein, we report an amino-functionalized nanoporous polymer stabilized palladium nanoparticle catalyst, which is prepared via a one-pot co-polymerization method, as highly active and selective catalysts for the phenol hydrogenation, giving cyclohexanone selectivity over 99.5% with full conversion of phenol under mild reaction conditions without any soluble additives. Importantly, the palladium leaching was efficiently hindered, maintaining the catalytic performances in continuously recycle tests. In contrast, the commercial palladium catalysts exhibit much lower selectivity and obvious deactivation because of the palladium leaching.

A comprehensive study on the combustion kinetic modeling of typical electronic plastic waste-television set (TV) plastic shell.

Electronic waste is the fastest growing waste stream and one of the most significant constituents is electronic plastics. In this study, the combustion kinetic of typical electronic plastic waste-television set (TV) plastic shell-was investigated using two basic kinetic methods. The reaction mechanism and kinetic compensation effect were probed as well. The thermogravimetric analysis (TGA) revealed that its degradation process can be divided into four stages, namely, reaction initiation stage (20-300 °C), major reaction stage (300-450 °C), minor reaction stage (450-600 °C), and reaction cessation stage (600-1,000 °C). The activation energy (E) were calculated and indicated that, the kinetic parameters from six model-free methods gradually decreased with α increasing from 0.1 to 0.35, and then slightly increased. The Flynn--Wall--Ozawa (FWO) method was more reliable and E values decreased from 155.0 to 147.51 kJ/mol with α range of 0.1-0.35, then gradually increased to 165.21 kJ/mol. Within the Coats--Redfern method, the first-order (F1) model had higher coefficient of determination (R2) and comparable E values with that from FWO method. The result of kinetic compensation effect confirmed that the compensation effect existed between E and A during the plastic waste combustion. A linear relationship lnA = 0.183E-3.11 (R2 = 0.991) was obtained. The pre-exponential factors (A) were also determined as 7.67 × 1010 min-1 based on the F1 reaction model and FWO method.Implications: Municipal solid waste (MSW) is a complex mixture of different components and the plastic takes up a significant portion in total MSW. Understanding the combustion process of typical electronic plastic waste and further probing its combustion kinetic are significant. Through this study, it will be significant for the reactor designing and optimizing in practice.

Pyrolysis kinetic study of cathode material derived from spent lithium ion batteries (LIBs): Comparison of different models.

Separating cathode material and Al foil from spent lithium-ion batteries (LIBs) is a critical step for LIBs recycling. As compared to chemical dissolving and decomposition, the pyrolysis pretreatment is an alternative and simple method. In this work, the pyrolysis kinetics of cathode material were comparatively studied using various isoconversional methods, including Flynn-Wall-Ozawa (FWO), Friedman, Kissinger-Akahira-Sunose, Starink, Tang, and Boswell. The thermal degradation mechanism was investigated by the Coats-Redfern (CR) and master-plot methods as well. The thermogravimetric analysis revealed that cathode material decomposition could be divided into three stages with mass losses of 1.51%, 0.787%, and 0.449%, respectively. Activation energy (Eα) calculated using the six model-free methods showed a similar trend, gradually increasing as the degree of conversion (α) increased from 0.001 to 0.009, and then significantly elevating. The FWO method gave the best fitting and Eα values first increased from 12.032 to 24.433 kJ·mol-1 with α elevating from 0.001 to 0.009, then increased further to 43.187 kJ·mol-1. Both CR and Criado methods indicated that the degradation of cathode material can be explained by the diffusion models.Implications: The rapid growth in the production and consumption of lithium-ion batteries (LIBs) for portable electronic devices and electric vehicles has resulted in an increasing number of spent LIBs. Thermal treatment offers advantages of high-efficiency and simple operation. Understanding the thermal process of spent LIBs and probing its kinetic are significant for the large-scale treatment. Through this study, it will be significant for the reactor designing and optimizing in practice.

Environmental distribution, transport and ecotoxicity of microplastics: A review.

Microplastics (MPs) have become a global environmental pollutant because of their unique properties. The extensive MP toxicity reports have focused on the aquatic environment, while the pervasive MP contamination in the soil and air has largely been overlooked. This review summarizes the abundance, sources and transport of MPs in different environments. It analyzes the toxicity of MPs based on various environmentally relevant bacterial, cellular, plant, aquatic animal and mammalian test groups, using both in vitro and in vivo experiments. The combined toxicity effects of MPs and various other environmental pollutants on ecosystems are also discussed. Currently, data on the adverse effects on combined MP toxicity are very limited. Thus, a systematic assessment of the environmental risk in different environments and in various species from MPs is challenging. Thus, this review proposes the possible risks and identifies the knowledge gaps posed by MPs to food safety and human health.

Pyrolysis characteristics of cathode from spent lithium-ion batteries using advanced TG-FTIR-GC/MS analysis.

Thermal treatment offers an alternative method for the separation of Al foil and cathode materials during spent lithium-ion batteries (LIBs) recycling. In this work, the pyrolysis behavior of cathode from spent LIBs was investigated using advanced thermogravimetric Fourier transformed infrared spectroscopy coupled with gas chromatography-mass spectrometer (TG-FTIR-GC/MS) method. The fate of fluorine present in spent batteries was probed as well. TG analysis showed that the cathode decomposition displayed a three-stage process. The temperatures of maximum mass loss rate were located at 470 °C and 599 °C, respectively. FTIR analysis revealed that the release of CO2 increased as the temperature rose from 195 to 928 °C. However, the evolution of H2O showed a decreasing trend when the temperature increased to above 599 °C. The release of fluoride derivatives also exhibited a decreasing trend, and they were not detected after temperatures increasing to above 470 °C. GC-MS analysis indicated that the release of H2O and CO displayed a similar trend, with larger releasing intensity at the first two stages. The evolution of 1,4-difluorobenzene and 1,3,5-trifluorobenzene also displayed a similar trend-larger releasing intensity at the first two stages. However, the release of CO2 showed a different trend, with the largest release intensity at the third stage, as did the release of 1,2,4-trifluorobenzene, with the release mainly focused at the temperature of 300-400 °C. The release intensities of 1,2,4-trifluorobenzene and 1,3,5-trifluorobenzene were comparable, although smaller than that of 1,4-difluorobenzene. This study will offer practical support for the large-scale recycling of spent LIBs.

A review of microplastics in the aquatic environmental: distribution, transport, ecotoxicology, and toxicological mechanisms.

The interactions between microplastics (MPs) and aquatic organisms are becoming increasingly frequent due to the extensive distribution of MPs in aquatic environments. MPs from the aquatic environment tend to accumulate and move through living organisms. Therefore, MPs can affect human health though the food chain and human consumption. In this brief review, the environmental distribution, sources, and transport of MPs are reviewed, and the potential consequences of the presence of MPs in the aquatic environment to human food are discussed. This review also summarized the toxicity effects and toxicity mechanisms of MPs based on various environmentally relevant test species and discussed the combined toxicity effects of MPs and various pollutants in aquatic ecosystems. The knowledge of the adverse effects on combined toxicity and the mechanism of MPs toxicity are very limited. Thus, a systematic assessment of the aquatic environmental risk in various species from MPs is challenging. In the end, we identify the knowledge gaps that need to be filled and provide suggestions for future research.

ZnO nanoparticles: recent advances in ecotoxicity and risk assessment.

The widespread application of zinc oxide nanoparticles (nano-ZnO) has received increasing attention because of their potential risks to human health and the environment. This review summarizes the relationship between the toxic effects and physicochemical properties of nano-ZnO and the underlying toxicity mechanisms of nano-ZnO. This study presents the possible human health hazards posed by nano-ZnO exposure and the biotoxicity to bacteria, algae, higher plants, aquatic animals, terrestrial invertebrates and vertebrates in vitro and in vivo. The advances in research on the ecotoxicity of nano-ZnO and the potential risks to human health are discussed. Finally, the current research deficiencies in this area are identified, and recommendations for future research are proposed.

A review of organophosphorus flame retardants (OPFRs): occurrence, bioaccumulation, toxicity, and organism exposure.

Organophosphorus flame retardants (OPFRs) are increasingly being applied as flame retardants due to their unique properties. OPFRs are commonly detected in various environmental matrices, and organisms are extensively exposed to them. Considering the adverse effects of OPFRs, many researchers have devoted their attention to environmental risk assessments. This review outlines the current knowledge regarding the toxicity of OPFRs based on both in vitro and in vivo experiments in various environmentally relevant test species. The production, absorption, bioaccumulation, and biomagnification of OPFRs in animals and humans are also described. The joint effects of OPFRs and their coexisting characteristics are also discussed based on the limited available data and results. Finally, knowledge gaps and perspectives for future exposure studies of OPFRs in animals and humans are identified.

Cu@Co-MOFs as a novel catalyst of peroxymonosulfate for the efficient removal of methylene blue.

In this study, for the first time, we describe the single step synthesis of a Cu particle-doped cobalt-based metal-organic framework (Cu@Co-MOF) using a hydrothermal method. The as-prepared materials were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy-energy disperse spectroscopy, thermogravimetry, and X-ray photoelectron spectroscopy, which confirmed the incorporation of zero-valent copper on the surface of the Co-MOFs. The heterogeneous catalytic activity of Cu@Co-MOFs was tested to activate peroxymonosulfate (PMS) for the removal of methylene blue (MB). The ratio of n(Cu)/n(Co) in the Cu@Co-MOFs showed a strong impact on the catalytic activity of the Cu@Co-MOFs, whereas a n(Cu)/n(Co) of 1 : 1 exhibited the best catalytic performance and obtained 100% MB removal within 30 min. The effects of initial pH, reaction temperature, PMS concentration, and catalyst dosages were investigated in this study. The stability and reusability of the Cu@Co-MOFs were also investigated. The results showed a low decline in the MB removal with the increase in cycle numbers, whereas 100% MB was removed by prolonging the reaction time. Heterogeneous reactions taking place in the pores and surface of the Cu@Co-MOFs played an important role in the generation of the sulfate radicals (SO4˙-) and hydroxyl radicals (·OH) that were the primary reactive species responsible for MB degradation.

A review on silver nanoparticles-induced ecotoxicity and the underlying toxicity mechanisms.

Silver nanoparticles (Ag-NPs) are increasingly being applied in many consumer products due to their unique properties. Widespread use of Ag-NPs leads to an increasing human exposure to Ag-NPs in many different pathways. This review summarized the toxicity mechanisms of Ag-NPs based on various environmentally relevant test species, such as bacteria, cells, plants, aquatic animals and mammals, in both in vitro and in vivo experiments. Nanoparticles were usually exposed to combination chemicals but to single chemicals in the environment and thereby exert combined toxicities to the organisms. Therefore, the joint effects of nanomaterials and their co-existing characteristics were also discussed. The current knowledge gaps and safe product designs of Ag-NPs have been discussed in detail. The limited and existing data implied that understanding the toxicity mechanisms is crucial to the future research development of nanomaterials.