In the present study, four solid adsorbents were prepared via green synthesis sources, namely, nanohydroxyapatite (NHAP), nanocellulose (NC), nanocellulose/nanohydroxyapatite composite (NPC), and ferric@nanocellulose/nanohydroxyapatite composite (FNPC). Synthesis procedures were based on natural sources such as sea scallop shells and cotton stalks. All the prepared solid adsorbents were characterized by TGA, XRD, nitrogen adsorption/desorption isotherm, FTIR, pHPZC, SEM, and TEM. FNPC exhibited a higher surface area (358.32 m2/g), mesoporous surface (pore diameter, 12.29 nm), TEM particle size of 45 nm, and the availability of various surface functional groups. Static adsorption of Safranin-O (SO) dye was investigated for all the prepared solid adsorbents under different application conditions. Maximum adsorption capacity (239.23 mg/g) was achieved by FNPC after 24 h of equilibrium time, at pH 7, 2 g/L as adsorbent dosage, and 40 ℃. Adsorption of Safranin-O onto all the samples well-fitted Langmuir, Temkin, Freundlich, Dubinin–Radushkevich, pseudo-second-order, and Elovich models. Thermodynamic and kinetic parameters proved that Safranin-O adsorption is favorable, spontaneous, endothermic, and physisorption. Desorption studies confirmed that hydrochloric acid (0.03 mol/L) achieved the maximum desorption efficiency (92.8%). Reusability of FNPC showed a decrease in the adsorption capacity after five cycles of adsorption and desorption by only 7.8%.
The present study deals with the preparation of nanomagnetite (NM), potassium carrageenan (KC), and nanomagnetite/potassium carrageenan bio-composite beads (NC). Characterization of the prepared solid materials using different physicochemical techniques such as X-ray diffraction analysis (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscope (TEM), energy-disperse X-ray spectroscopy (EDX), diffuse reflectance spectrophotometer (DRS), swelling ratio (SR%), N2 adsorption, pH of point of zero charges (pHPZC), and Fourier transform infrared spectroscopy (FTIR). Comparing between adsorption and photo-Fenton degradation process for methylene blue (MB) on the surface of the prepared solid materials. Nanomagnetite/potassium carrageenan bio-composite (NC) exhibited high specific surface area (406 m2/g), mesoporosity (pore radius, 3.64 nm), point of zero charge around pH6.0, and the occurrence of abundant oxygen-containing functional groups. Comparison between adsorption and photo-Fenton oxidation process for methylene blue (MB) was carried out under different application conditions. NC exhibited the maximum adsorption capacity with 374.50 mg/g at 40 °C after 24 h of shaking time while 96.9% of MB was completely degraded after 20 min of photo-Fenton process. Langmuir's adsorption model for MB onto the investigated solid materials is the best-fitted adsorption model based on the higher correlation coefficient values (0.9771–0.9999). Kinetic and thermodynamic measurements prove that adsorption follows PSO, endothermic, and spontaneous process, while photo-Fenton degradation of MB achieves PFO, nonspontaneous, and endothermic process. Photo-Fenton degradation is a fast and simple technique at a lower concentration of dye (< 40 mg/L) while at higher dye concentration, the adsorption process is preferred in the removal of that dye.
In the current study, a novel nanomaterial called nanomagnetite/copper oxide/potassium carrageenan nanocomposite (MKCO) was fabricated to include Fenton (nanomagnetite, NM) and Fenton-like reagent (copper oxide nanoparticles, NCO) in a matrix of potassium carrageenan biopolymer. The prepared solid materials were characterized by different physicochemical techniques, such as TGA, N2 adsorption/desorption, SEM, TEM, XRD, DRS, pHPZC, and FTIR. The prepared MKCO showed unique properties like higher specific surface area of 652.50 m2/g, pore radius of 1.19 nm, pHPZC equals 7.80, and the presence of different surface chemical functional groups. Under various application conditions, comparative experiments between Safranin-O dye (SO) adsorption and Photo-Fenton catalytic degradation were conducted. After 24 h, MKCO had a maximum adsorption capacity of 384.61 mg/g at 42 °C, while the Photo-Fenton oxidation process took only 10 min to totally decompose 93% of SO at 21 °C. Based on the higher values of correlation coefficients, Langmuir’s adsorption model is the best-fitted adsorption model for SO onto all the prepared solid materials. Studies on SO adsorption’s kinetics and thermodynamics show that it is physisorption and that it operates according to endothermic, spontaneous, and PFO model processes. While, PFO, endothermic, and non-spontaneous processes are satisfied by the catalytic decomposition of SO. After five application cycles, MKCO demonstrated good catalyst reusability with a 3.4% decrease in degrading efficiency. For lower contaminant concentrations and shorter application times, Photo-Fenton catalytic degradation of organic pollutants is more effective than adsorption. Graphical abstract Fenton and Photo-Fenton degradation of Safranin-O
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