Ionic Cross-Linking Fabrication of Chitosan-Based Beads Modified with FeO and TiO₂ Nanoparticles: Adsorption Mechanism toward Naphthalene Removal in Seawater from Cartagena Bay Area

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are complex molecules produced by the thermal decomposition of organic matter in anthropogenic activities. Novel composites with enhanced physicochemical properties aim to overcome limitations such as adsorption capacity, affinity, and stability for PAHs adsorption. Composites based on chitosan are promising due to the good biocompatibility and adsorption properties. This study focuses on the facile preparation of chitosan beads modified with iron oxide (FeO) and titanium dioxide (TiO 2 ) nanoparticles via ionic cross-linking (Ch-FeO/TiO 2 ). FeO and TiO 2 were synthesized performing co-precipitation and green chemistry methods, respectively. The characterization evidenced the formation of Ch-FeO/TiO 2 with good crystallinity, excellent thermal stability, and superparamagnetic response, attributed to the presence of FeO and TiO 2 nanoparticles. High thermal stability up to 270 °C was related to the cross-linked chitosan network. The enhanced adsorption mechanism of Ch-FeO/TiO 2 was determined by removing naphthalene from water and seawater samples. The Ch-FeO/TiO 2 showed a higher adsorption capacity of 33.1 mg/g compared to 29.8 mg/g of the unmodified chitosan (un-Ch) beads. This is due to the higher functional surface area of 27.13 m 2 /g, compared to that of 0.708 m 2 /g for un-Ch. We found a rapid adsorption rate of 240 min and the maximum adsorption capacity of 149.3 mg/g for Ch-FeO/TiO 2 . A large number of actives sites allows for increasing the naphthalene molecules interaction. Adsorption in seawater samples from Cartagena Bay (Colombia) exhibits an outstanding efficiency of up to 90%. These results suggest a promising, cheap, and environmentally friendly composite for remediation of water sources contaminated with complex compounds.

Advances in Polymer Nanocomposite Materials for Photocatalytic Degradation of Polynuclear Aromatic Hydrocarbons in Environmental Matrices: A Review

“…The determination of derivatives or fragments obtained after any degradation is normally performed using methods that are also used to determine the concentrations of PAHs, parent phenols and other hydroxylated-or alkylated-PAHs (Morueco, 2018). Like other POPs, emerging contaminants of concerns, PAHs and their derivatives are normally analyzed using a gas chromatography-mass spectrometry (GC-MS) (Munyengabe, 2016;Diao et al, 2019;Rani, & Shanker, 2019c;Patiño-Ruiz et al, 2020), high-performance liquid chromatography (HPLC) (Das, Mukherjee, & Sen, 2008), liquid chromatography-quadrupole time-of-flight mass spectrometry (Ye et al, 2019), HPLC with a fluorescence detector (Vela et al, 2012), GC-MS/tandem mass spectrometry (GC-MS/MS) (Sun et al, 2020), solid-phase luminescence (SPL) (Tatarinov et al, 2021), and liquid chromatography-tandem mass spectrometry (Shang et al, 2019).…”

“…Characterization plays a big role in chemistry where the structure and properties of the material have to be identified and compared with the literature. However, like other solid materials, the surface morphology, density and core-shell structure of the prepared nanocomposites can be determined using field-emission scanning electron microscope coupled to an electron dispersive spectroscopy detector and a high-resolution transmission electron microscopy (TEM) (Di Mauro et al, 2017;Alizadeh, Delnavaz, & Shakeri, 2018;Rebekah et al, 2020;Patiño-Ruiz et al, 2020;Solano et al, 2021). The physical and chemical characteristics, thermal stability and crystallinity of the PNMs can be explored using thermogravimetric analyzer and an X-ray powder diffraction (XRD) (Bhaumik, Setshedi, Maity, & Onyango, 2013;Alizadeh, Delnavaz, & Shakeri, 2018).…”

“…The physical and chemical characteristics, thermal stability and crystallinity of the PNMs can be explored using thermogravimetric analyzer and an X-ray powder diffraction (XRD) (Bhaumik, Setshedi, Maity, & Onyango, 2013;Alizadeh, Delnavaz, & Shakeri, 2018). Their pore volume, pore diameter and surface area can also be identified using Brunauer-Emmett-Teller (BET) (Patiño-Ruiz et al, 2020) while functional groups are normally identified by Fourier-transform infrared spectroscopy (FTIR) (Rebekah et al, 2020;Patiño-Ruiz et al, 2020;Solano et al, 2021). They can also be characterized using atomic force microscope and small-angle X-ray scattering (Gestranius et al, 2020), Rheometric technique, Raman spectroscopy (Solano et al, 2021), thermomechanical, dynamic modulus analysis (DMA), differential scanning calorimeter (DSC) (Ray, & Okamoto, 2003), and X-ray photoelectron spectroscopy (Abinaya et al, 2019).…”

Comparative Studies of RSM, RSM–GA and ANFILS for Modeling and Optimization of Naphthalene Adsorption on Chitosan–CTAB–Sodium Bentonite Clay Matrix

“…Liu et al [11] investigated the adsorption of naphthalene on coal-based activated carbons. However, recently one of the reputable low-cost adsorbents found in the literature for the effective adsorption of PAHs from aqueous solution are the chitosan and clay minerals [12][13].…”

A Hybrid Methodology to Minimize Freshwater Consumption during Shrimp Shell Waste Valorization Combining Multi-Contaminant Pinch Analysis and Superstructure Optimization

“…One of them is obtaining polymer chitosan composed of β- (1–4) D-glucosamine units with physicochemical properties such as biodegradability, biocompatibility, bioactivity, and low toxicity. For that reason, this compound has been investigated in different fields, for example, antimicrobial activity, wastewater treatment, food industries, nanoparticles, and biopolymers, among others [ 4 , 5 ]. Chitosan is produced by enzymatic or chemical deacetylation of chitin; this last route is characterized by high freshwater consumption and availability of intermediate streams.…”