Adsorption of phosphate on iron oxide doped halloysite nanotubes.
ABSTRACT: Excess phosphate in water is known to cause eutrophication, and its removal is imperative. Nanoclay minerals are widely used in environmental remediation due to their low-cost, adequate availability, environmental compatibility, and adsorption efficiency. However, the removal of anions with nanoclays is not very effective because of electrostatic repulsion from clay surfaces with a net negative charge. Among clay minerals, halloysite nanotubes (HNTs) possess a negatively charged exterior and a positively charged inner lumen. This provides an increased affinity for anion removal. In this study, HNTs are modified with nano-scale iron oxide (Fe2O3) to enhance the adsorption capacity of the nanosorbent. This modification allowed for effective distribution of these oxide surfaces, which are known to sorb phosphate via ligand exchange and by forming inner-sphere complexes. A detailed characterization of the raw and (Fe2O3) modified HNTs (Fe-HNT) is conducted. Influences of Fe2O3 loading, adsorbent dosage, contact time, pH, initial phosphate concentration, and coexisting ions on the phosphate adsorption capacity are studied. Results demonstrate that adsorption on Fe-HNT is pH-dependent with fast initial adsorption kinetics. The underlying mechanism is identified as a combination of electrostatic attraction, ligand exchange, and Lewis acid-base interactions. The nanomaterial provides promising results for its application in water/wastewater treatment.
Project description:The exponential growth in technologies incorporating engineered nanomaterials (ENMs) requires plans to handle waste ENM disposal and accidental environmental release throughout the material life cycle. These scenarios motivate efforts to quantify and model ENM interactions with diverse background particles and solubilized chemical species in a variety of environmental systems. In this study, quantum dot (QD) nanoparticles and clay minerals were mixed in a range of water chemistries in order to develop simple assays to predict aggregation trends. CdSe QDs were used as a model ENM functionalized with either negatively charged or zwitterionic small molecule ligand coatings, while clays were chosen as an environmentally relevant sorbent given their potential as an economical water treatment technology and ubiquitous presence in nature. In our unbuffered experimental systems, clay type impacted pH, which resulted in a change in zwitterionic ligand speciation that favored aggregation with kaolinite more than with montmorillonite. With kaolinite, the zwitterionic ligand-coated QD exhibited greater than ten times the relative attachment efficiency for QD-clay heteroaggregation compared to the negatively charged ligand coated QD. Under some conditions, particle oxidative dissolution and dynamic sorption of ions and QDs to surfaces complicated the interpretation of the removal kinetics. This work demonstrates that QDs stabilized by small molecule ligands and electrostatic surface charges are highly sensitive to changes in water chemistry in complex media. Natural environments enable rapid dynamic physicochemical changes that will influence the fate and mobility of ENMs, as seen by the differential adsorption of water-soluble QDs to our clay media.
Project description:This paper investigates merits of using a wood-based biocrude (WB) from aspen wood to improve the compatibility of halloysite nanotubes (HNTs) with high-impact polystyrene to develop nanocomposites with desirable thermomechanical properties. Morphological, thermal, and rheological properties of the resulting nanocomposite are used as indicators of the compatibility and dispersion of the modified HNT within the polymer matrix. Computational modeling using density functional theory is used along with laboratory experiments to provide a multiscale characterization of the above biocrude and nanocomposites. Studies performed through dispersion-corrected density functional theory calculations show that the active functional groups of WB molecules including carbonyl, hydroxyl, and carboxylic interact with the HNT surface, while their aromatic tails interact with the phenyl groups of the polystyrene. Furthermore, the studies reveal how WB molecules act as bridges between the hydrophobic polymer and the hydrophilic clay improving the compatibility. The latter was confirmed by Hansen solubility parameters and was evidenced in improved dispersion of clay within the polystyrene matrix observed by microscopy. Rheological and thermal analyses of the modified HNT and nanocomposites showed physical interactions of WB with HNT surface as well as interactions between the WB-modified HNT and the high-impact polystyrene. The WB was found to be a strong candidate as a green compatibilizing agent for HNT in high-impact polystyrene. The study results can provide insights for formulators and manufacturers looking for green compatibilizing agents in conventional nanocomposites for construction and manufacturing applications.
Project description:As antibiotic contamination increases in wastewater and aqueous environments, the reduction of antibiotics has become a pertinent topic of research regarding water treatment. Clay minerals, such as smectite or kaolinite, are important adsorbents used in water treatment, and sufficient removal of antibiotics by clay minerals is expected. In this study, the adsorption of oxytetracycline (OTC) on kaolinite was investigated. The experimental data of OTC adsorption on kaolinite fit the pseudo-second-order kinetics model well (R2>0.98). After 24 h, adsorption equilibrium of OTC on kaolinite was reached. The Langmuir model was better fitting with the adsorption isotherms generated from experimental data and OTC adsorption occurred on the external surface of kaolinite. The analysis of several thermodynamic parameters indicated that the adsorption of OTC on kaolinite was spontaneous and thermodynamically favorable. With the increase of the pH of a solution, the adsorption capacity increased and then decreased. The adsorption coefficient (Kd) of 102-103 were obtained for adsorption process of OTC on kaolinite.
Project description:The quality of interphase in carbon fibers (CFs) composites makes a key contribution to overall performance of composites. Here, we achieved for the first time the chemical grafting of halloysite nanotubes (HNTs) with amino or carboxyl groups onto the CFs surface aiming to increase composites interfacial strength. HNTs were grafted using 3-aminopropyltriethoxysilane (APS) followed by succinic anhydride treatment, and HNTs with amino groups (HNT⁻NH₂) or carboxyl groups (HNT⁻COOH) were separately introduced into the interphase of composites. Functional groups of HNTs and fiber surface structures were characterized, which confirmed the modification success. The wettability between the modified CFs and resin have been enhanced obviously based on the improved fiber polarity and enhanced surface roughness by the introduced two functionalized HNTs with the uniform distributions onto fiber surface. Moreover, interfacial properties and anti-hydrothermal aging behaviors of modified methylphenylsilicone resin (MPSR) composites were improved significantly, especially for HNT⁻COOH grafting. In addition, the interfacial reinforcement mechanisms for untreated and modified CF composites are discussed and compared.
Project description:Chemical dyes are used in a wide range of anthropogenic activities and are generally not biodegradable. Hence, sustainable recycling processes are needed to avoid their accumulation in the environment. A one-step synthesis of Fecore-maghemiteshell (Fe-MM) for facile, instantaneous, cost-effective, sustainable, and efficient removal of brilliant green (BG) dye from water has been reported here. The homogenous and monolayer type of adsorption is, to our knowledge, the most efficient, with a maximum uptake capacity of 1000 mg·g-1, for BG on Fe-MM. This adsorbent was shown to be efficient in occurring in time-scales of seconds and to be readily recyclable (ca. 91%). As iron/iron oxide possesses magnetic behavior, a strong magnet could be used to separate Fe-MM coated with BG. Thus, the recycling process required a minimum amount of energy. Capping Fe-MM by hydrophilic clay minerals further enhanced the BG uptake capacity, by reducing unwanted aggregation. Interestingly, capping the adsorbent by hydrophobic plastic (low-density polyethylene) had a completely inverse effect on clay minerals. BG removal using this method is found to be quite selective among the five common industrial dyes tested in this study. To shed light on the life cycle analysis of the composite in the environment, the influence of selected physicochemical factors (T, pH, h?, O3, and NO2) was examined, along with four types of water samples (melted snow, rain, river, and tap water). To evaluate the potential limitations of this technique, because of likely competitive reactions with metal ion contaminants in aquatic systems, additional experiments with 13 metal ions were performed. To decipher the adsorption mechanism, we deployed four reducing agents (NaBH4, hydrazine, LiAlH4, and polyphenols in green tea) and NaBH4, exclusively, favored the generation of an efficient adsorbent via aerial oxidation. The drift of electron density from electron-rich Fecore to maghemite shells was attributed to be responsible for the electrostatic adsorption of N+ in BG toward Fe-MM. This technology is deemed to be environmentally sustainable in environmental remediation, namely, in waste management protocol.
Project description:Halloysite (HNT) is treated with sulfuric acid and the physico-chemical properties of its morphology, surface activity, physical and chemical properties have been investigated when HNT is exposed to sulfuric acid with treatment periods of 1 h (H1), 3 h (H3), 8 h (H8), and 21 h (H21). The significance of this and similar work lies in the importance of using HNT as a functional material in nanocomposites. The chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR). The spectrum demonstrates that the hydroxyl groups were active for grafting modification using sulfuric acid, promoting a promising potential use for halloysite in ceramic applications as filler for novel clay-polymer nanocomposites. From the X-ray diffraction (XRD) spectrum, it can be seen that the sulfuric acid breaks down the HNT crystal structure and alters it into amorphous silica. In addition, the FESEM images reveal that the sulfuric acid treatment dissolves the AlO₆ octahedral layers and induces the disintegration of SiO₄ tetrahedral layers, resulting in porous nanorods. The Bruncher-Emmett-Teller (BET) surface area and total pore volume of HNTs showed an increase. The reaction of the acid with both the outer and inner surfaces of the nanotubes causes the AlO₆ octahedral layers to dissolve, which leads to the breakdown and collapse of the tetrahedral layers of SiO₄. The multi-fold results presented in this paper serve as a guide for further HNT functional treatment for producing new and advanced nanocomposites.
Project description:Eco-friendly betanin/clay minerals hybrid materials with good stability were synthesized by combining with adsorption, grinding, and heating treatment using natural betanin extracted from beetroot and natural 2:1 type palygorskite or 1:1 type halloysite. After incorporation of clay minerals, the thermal stability and solvent resistance of natural betanin were obviously enhanced. Due to the difference in the structure of palygorskite and halloysite, betanin was mainly adsorbed on the outer surface of palygorskite or halloysite through hydrogen-bond interaction, but also part of them also entered into the lumen of Hal via electrostatic interaction. Compared with palygorskite, hybrid materials prepared with halloysite exhibited the better color performance, heating stability and solvent resistance due to the high loading content of betanin and shielding effect of lumen of halloysite.
Project description:A novel approach was employed to load ?-Fe2O3 and ?-FeOOH onto sewage sludge biochar (SBC) with the purpose of efficient nickel (Ni) removal. A high Ni(II) adsorption capacity of 35.50 mg·g-1 in 100 ppm Ni(II) solution with 10 mg modified sewage sludge biochar (MSBC) was achieved. The adsorption kinetic and isotherm were fitted well by the pseudo-second-order model and the Langmuir model, respectively. The optimal pH was found around a neutral pH of 7. The adsorption mechanisms of Ni(II) onto MSBC were described as the synergistic effects of electrostatic attraction, ion exchange, inner-sphere complexation and co-precipitation. The initial rapid adsorption phenomenon could be attributed to electrostatic attraction and ion exchange, and then inner-sphere complexation and co-precipitation acted as a crucial role in the following step. The remarkable performance of MSBC provides an effective waste utilization approach to simultaneous sewage sludge recycle and Ni removal from aqueous solution.
Project description:The stability of organomineral aggregates in soils has a key influence on nutrient cycling, erosion, and soil productivity. Both clay minerals with distinct basal and edge surfaces and organic molecules with reactive functional groups offer rich bonding environments. While clay edges often promote strong inner-sphere bonding of -COOH-laden organics, we explore typically weaker, outer-sphere bonding of such molecules onto basal planes and its significance in organomineral interactions. In this surface force apparatus study, we probed face-specific interactions of negatively charged mica basal surfaces in solutions containing carboxyl-bearing, low-molecular-weight dicarboxylic acids (DAs). Our experiments provide distance-resolved, nanometer-range measurements of forces acting between two (001) mica surfaces and simultaneously probe DA adsorption. We show that background inorganic ions display crucial importance in nanoscale forces acting between basal mica surfaces and in DA adsorption: Na<sup>+</sup> contributes to strong repulsion and little binding of dicarboxylic anions, while small amounts of Ca<sup>2+</sup> are sufficient to screen the basal surface charge of mica, facilitate strong adhesion, and enhance dicarboxylic anion adsorption by acting as cationic bridges. Despite reversible and weak adsorption of DAs, we resolve their multilayer binding via assembly of hydrophobic chains in the presence of Ca<sup>2+</sup>, pointing the importance of abundant, less reactive basal clay surfaces in organomineral interactions.
Project description:Both Fe(III)-bearing clay minerals and humic acids (HAs) are abundant in the soils and sediments. Previous studies have shown that bioreduction of structural Fe(III) in clay minerals could be accelerated by adding anthraquinone compound as a redox-active surrogate of HAs. However, a quinoid analogue could not reflect the adsorption and complexation properties of HA, and little is known about the effects of real HAs at environmental concentration on bioreduction of clay minerals. Here, it was shown that 10-200?mg l<sup>-1</sup> of natural or artificially synthesized HAs could effectively stimulate the bioreduction rate and extent of Fe(III) in both iron-rich nontronite NAu-2 and iron-deficient montmorillonite SWy-2. After adsorption to NAu-2, electron-transfer activities of different HA fractions were compared. Additionally, Fe(II) complexation by HAs also contributed to improvement of clay-Fe(III) bioreduction. Spectrosopic and morphological analyses suggested that HA addition accelerated the transformation of NAu-2 to illite, silica and siderite after reductive dissolution.