Synthesis of low-density polyethylene derived carbon nanotubes for activation of persulfate and degradation of water organic micropollutants in continuous mode.

Plastic derived carbon nanotubes (CNTs) were tested as catalysts in persulfate activation for the first time. Four catalysts were prepared by wetness impregnation and co-precipitation (using Al2O3, Ni, Fe and/or Al) and implemented to grow CNTs by chemical vapour deposition (CVD) using low-density polyethylene (LDPE) as carbon feedstock. A catalyst screening was performed in batch mode and the best performing CNTs (CNT@Ni+Fe/Al2O3-cp) led to a high venlafaxine mass removal rate (3.17 mg g-1 h-1) in ultrapure water after 90 min (even with a mixture of micropollutants). Its degradation increased when the matrix was replaced by drinking water and negligibly affected in surface water. A composite polymeric membrane was then fabricated with CNT@Ni+Fe/Al2O3-cp and polyvinylidene fluoride (PVDF), a high venlafaxine mass removal rate in surface water being also observed in 24 h of continuous operation. Therefore, the results herein reported open a window of opportunity for the valorisation of plastic wastes in this catalytic application performed in continuous mode.

Adsorption of Sudan-IV contained in oily wastewater on lipophilic activated carbons: kinetic and isotherm modelling.

Up to nine kinetic and fourteen isotherm adsorption models are employed to model the adsorption of Sudan IV, a lipophilic model pollutant present in a biphasic mixture of cyclohexane-water system to simulate oily wastewater. Six different modified activated carbons were used as adsorbents. The highest amount adsorbed of Sudan IV was found in the material prepared by successive treatments of the parent commercial activated carbon Norit ROX 0.8 with nitric acid and urea, followed by thermal treatment at 800 °C under continuous flow of nitrogen. Kinetic and isotherm adsorption models can be employed to simulate the process, since the effect of the presence of water in the adsorption of Sudan IV from the cyclohexane phase was found to be negligible, owing to the high lipophilic character of both adsorbent and adsorbate. All kinetic and isotherm coefficients, coupling with statistical parameters (r2, adjusted r2 and sum of squared errors), are determined by non-linear regression fitting and compared to literature data. The model of Avrami is found to be the most appropriate model to represent the adsorption of the pollutant in any of the six modified carbons tested, the highest value of the kinetic constant being 0.055 min-1. The isotherm adsorption is well-modelled by using the general isotherm equation of Tóth and the multilayer Jovanovic expression for the adsorption of Sudan-IV on that material, resulting in a high monolayer uptake capacity (qm = 193.6 mg g-1).

Degradation of methylparaben by sonocatalysis using a Co-Fe magnetic carbon xerogel.

The degradation of methylparaben (MP) through 20 kHz ultrasound coupled with a bimetallic Co-Fe carbon xerogel (CX/CoFe) was investigated in this work. Experiments were performed at actual power densities of 25 and 52 W/L, catalyst loadings of 12.5 and 25 mg/L, MP concentrations between 1 and 4.2 mg/L and initial pH values between 3 and 10 in ultrapure water (UPW). Matrix effects were studied in bottled water (BW) and secondary treated wastewater (WW), as well as in UPW spiked with bicarbonate, chloride or humic acid. The pseudo-first order kinetics of MP degradation increase with power and catalyst loading and decrease with MP concentration and matrix complexity; moreover, the reaction is also favored at near-neutral conditions and in the presence of dissolved oxygen. The contribution of the catalyst is synergistic to the sonochemical degradation of MP and the extent of synergy is quantified to be >45%. This effect was ascribed to the ability of CX/CoFe to catalyze the dissociation of hydrogen peroxide, formed through water sonolysis, to hydroxyl radicals. Experiments in UPW spiked with an excess of tert-butanol (radical scavenger), sodium dodecyl sulfate or sodium acetate (surfactants) led to substantially decreased rates (i.e. by about 8 times), thus implying that the liquid bulk and the gas-liquid interface are major reaction sites. The stability of CX/CoFe was shown by performing reusability cycles employing magnetic separation of the catalyst after the treatment stage. It was found that the CX/CoFe catalyst can be reused in up to four successive cycles without noteworthy variation of the overall performance of the sonocatalytic process.

Multifunctional graphene-based magnetic nanocarriers for combined hyperthermia and dual stimuli-responsive drug delivery.

The synthesis of hydrophilic graphene-based yolk-shell magnetic nanoparticles functionalized with copolymer pluronic F-127 (GYSMNP@PF127) is herein reported to achieve an efficient multifunctional biomedical system for mild hyperthermia and stimuli-responsive drug delivery. In vitro tests revealed the extraordinary ability of GYSMNP@PF127 to act as smart stimuli-responsive multifunctional nanomedicine platform for cancer therapy, exhibiting (i) an outstanding loading capacity of 91% (w/w, representing 910 µg mg-1) of the chemotherapeutic drug doxorubicin, (ii) a high heating efficiency under an alternating (AC) magnetic field (intrinsic power loss ranging from 2.1-2.7 nHm2 kg-1), and (iii) a dual pH and thermal stimuli-responsive drug controlled release (46% at acidic tumour pH vs 7% at physiological pH) under AC magnetic field, in just 30 min. Additionally, GYSMNP@PF127 presents optimal hydrodynamic diameter (DH = 180 nm) with negative surface charge, high haemocompatibility for blood stream applications and tumour cellular uptake of drug nanocarriers. Due to its physicochemical, magnetic and biocompatibility properties, the developed graphene-based magnetic nanocarrier shows high promise as dual exogenous (AC field)/endogenous (pH) stimuli-responsive actuators for targeted thermo-chemotherapy, combining magnetic hyperthermia and controlled drug release triggered by the abnormal tumour environment. The presented strategy and findings can represent a new way to design and develop highly stable added-value graphene-based nanostructures for the combined treatment of cancer.

Degradation of propyl paraben by activated persulfate using iron-containing magnetic carbon xerogels: investigation of water matrix and process synergy effects.

An advanced oxidation process comprising an iron-containing magnetic carbon xerogel (CX/Fe) and persulfate was tested for the degradation of propyl paraben (PP), a contaminant of emerging concern, in various water matrices. Moreover, the effect of 20 kHz ultrasound or light irradiation on process performance was evaluated. The pseudo-first order degradation rate of PP was found to increase with increasing SPS concentration (25-500 mg/L) and decreasing PP concentration (1690-420 µg/L) and solution pH (9-3). Furthermore, the effect of water matrix on kinetics was detrimental depending on the complexity (i.e., wastewater, river water, bottled water) and the concentration of matrix constituents (i.e., humic acid, chloride, bicarbonate). The simultaneous use of CX/Fe and ultrasound as persulfate activators resulted in a synergistic effect, with the level of synergy (between 35 and 50%) depending on the water matrix. Conversely, coupling CX/Fe with simulated solar or UVA irradiation resulted in a cumulative effect in experiments performed in ultrapure water.

Activation of sodium persulfate by magnetic carbon xerogels (CX/CoFe) for the oxidation of bisphenol A: Process variables effects, matrix effects and reaction pathways.

An advanced oxidation process comprising sodium persulfate (SPS) and a novel magnetic carbon xerogel was tested for the degradation of bisphenol A (BPA), a model endocrine-disrupting compound. The catalyst, consisting of interconnected carbon microspheres with embedded iron and cobalt microparticles, was capable of activating persulfate to form sulfate and hydroxyl radicals at ambient conditions. The pseudo-first order degradation rate of BPA in ultrapure water (UPW) was found to increase with (i) increasing catalyst (25-75 mg/L) and SPS (31-250 mg/L) concentrations, (ii) decreasing BPA concentration (285-14,200 µg/L), and (iii) changing pH from alkaline to acidic values (9-3). Besides UPW, tests were conducted in drinking water, treated wastewater, groundwater and surface water; interestingly, the rate in UPW was always lower than in any other matrix containing several organic and inorganic constituents. The effect of natural organic matter (in the form of humic acids) and alcohols was detrimental to BPA degradation owing to the scavenging of radicals. Conversely, chlorides at concentrations greater than 50 mg/L had a positive effect due to the formation and subsequent participation of chlorine-containing radicals. Liquid chromatography time-of-flight mass spectrometry was employed to identify major transformation by-products (TBPs) of BPA degradation in the absence and presence of chlorides; in the latter case, several chlorinated TBPs were detected confirming the role of Cl-related radicals. Based on TBPs, main reaction pathways are proposed.

Catalytic properties of carbon materials for wet oxidation of aniline.

A mesoporous carbon xerogel with a significant amount of oxygen functional groups and a commercial activated carbon, were tested in the catalytic wet air oxidation of aniline at 200 degrees C and 6.9 bar of oxygen partial pressure. Both carbon materials showed high activity in aniline and total organic carbon removal, a clear increase in the removal efficiency relatively to non-catalytic wet air oxidation being observed. The best results in terms of aniline removal were obtained with carbon xerogel, an almost complete aniline conversion after 1h oxidation with high selectivity to non-organic compounds being achieved. The materials were characterized by thermogravimetric analysis, temperature programmed desorption, N(2) adsorption and scanning electron microscopy, in order to relate their performances to the chemical and textural characteristics. It was concluded that the removal efficiency, attributed to both adsorption and catalytic activity, is related to the mesoporous character of the materials and to the presence of specific oxygen containing functional groups at their surface. The effect of catalytic activity was found to be more important in the removal of aniline than the effect of adsorption at the materials surface. The results obtained indicate that mesoporous carbon xerogels are promising catalysts for CWAO processes.