Cellulose substrate waste has demonstrated great potential as a biosorbent of pollutants from contaminated water. In this study, Neriumoleander fruit, an agricultural waste biomaterial, was used for the biosorption of methylene blue from synthetic solution. Fourier-transform infrared (FTIR) spectroscopy indicated the presence of the main absorption peak characteristics of cellulose, hemicellulose, and lignin compositions. X-ray diffraction (XRD) pattern exhibited peaks at 2θ = 14.9° and 2θ = 22°, which are characteristics of cellulose I. Scanning electron microscopy (SEM) showed a rough and heterogeneous surface intercepted by some cavities. Thermogravimetric analysis (TGA) showed more than a thermal decomposition point, suggesting that Nerium fruit is composed of cellulose and noncellulosic matters. The pH_pzc value of Nerium surface was experimentally determined to be 6.2. Nerium dosage, pH, contact time, dye concentration, and temperature significantly affected the adsorption capacity. The adsorption capacity reached 259 mg/g at 19 °C. The mean free energy ranged from 74.53 to 84.52 KJ mol⁻¹, suggesting a chemisorption process. Thermodynamic parameters define a chemical, exothermic, and nonspontaneous mechanism. The above data suggest that Nerium fruit can be used as an excellent biomaterial for practical purification of water without the need to impart chemical functionalization on its surface.

Ligno-cellulosic biomasses had been recognized for their potential use to produce chemicals and biomaterials. The current study focused on the use of a new cellulosic Robinia Pseudoacacia fiber and extracted lignin as adsorbents for methylene blue (a cationic dye). The biomaterials were analyzed using FT-IR spectroscopy, SEM, XRD, and TGA-DTA techniques. The surface of Robinia fibers was rough and porous. The crystallinity index (CrI) value for Robinia fibers was found to be 32%. The ability of the studied samples to remove methylene blue from water was assessed under the variation of time, pH, dye concentration, temperature, and NaCl concentration. The maximum adsorption capacity of methylene blue reached 191 mg/g for Robinia fibers and it achieved 22 mg/g for the extracted lignin (T = 20 °C, pH = 6, and time = 90 min). The adsorption data complied with the pseudo second-order kinetic model and both Langmuir and Freundlich isotherms. Based on these findings, the process suggested the occurrence of many physicochemical interactions between methylene blue molecules and the studied biomaterials. The adsorption mechanism was exothermic, non-spontaneous, and it was described by the decrease of the disorder. Adsorption results proved that Robinia fiber was an attractive candidate for the removal of cationic dyes from water. A low-cost and abundant Robinia Pseudoacacia fiber and its extracted lignin are characterized and further studied as adsorbents for cationic dyes under the change of the experimental conditions.

In this work, pectin biopolymers were functionalized with dichloride (5,10,15,20-tetraphenylporphyrinato) antimony [Sb(TPP)Cl₂] at various compositions (0.5%, 1%, and 2%). The prepared compounds were characterized with several analytical methods, including X-ray fluorescence (XRF) spectrometry, Fourier-transform infrared spectroscopy (FT-IR), electrospray ionization mass spectrometry (EIS), scanning electron microscope (SEM), X-ray diffraction (XRD), and thermogravimetric-differential thermal (TGA/DTG) analysis. The XRF technique evidenced the presence of Sb metal in the composite beads. FT-IR suggested that the interaction between pectin and the [Sb(TPP)Cl₂] complex was assured by inter- and intramolecular C-H⋯O, C-H⋯Cl hydrogen bonds and weak C–H⋯Cg π interactions (Cg is the centroid of the pyrrole and phenyl rings). The morphological features of the prepared polymeric beads were affected by the addition of [Sb(TPP)Cl₂] particles, and the surface became rough. The thermal residual mass for the composite beads (29%) was more important than that of plain beads (23%), which confirmed the presence of inorganic matter in the modified polymeric beads. At 20 °C, the highest adsorption amounts of methylene blue were 39 mg/g and 68 mg/g for unmodified pectin and pectin-[Sb(TPP)Cl₂] beads, respectively. The adsorption mechanism correlated well with the kinetic equation of the second order and the isotherm of Freundlich. The prepared polymeric beads were characterized as moderate-to-good adsorbents. The calculated thermodynamic parameters demonstrated an exothermic and thermodynamically nonspontaneous mechanism.

In the current work, chloro(meso-tetrakis(phenyl)porphyrin) manganese(III) [Mn(TPP)Cl] was synthesized following two steps: the preparation of meso-tetraphenylporphyrin (H_⁠2TPP) and the insertion of manganese into the free porphyrin H₂TPP. The compounds were characterized using SEM, FT-IR, UV, TGA/DTA, and XRD analyses. Manganese(III) meso-porphyrins exhibited hyper-type electronic spectra with a half-vacant metal orbital with symmetry, such as [dπ:dxz and dyz]. The thermal behavior of [Mn(TPP)(Cl)] changed (three-step degradation process) compared to the initial H₂TPP (one-step degradation process), confirming the insertion of manganese into the core of the free porphyrin H₂TPP. Furthermore, [Mn(TPP)Cl] was used to degrade calmagite (an azo dye) using H₂O₂ as an oxidant. The effects of dye concentration, reaction time, H₂O₂ dose, and temperature were investigated. The azo dye solution was completely degraded in the presence of [Mn(TPP)(Cl)]/H₂O₂ at pH = 6, temperature = 20 °C, C₀ = 30 mg/L, and H₂O₂ = 40 mL/L. The computed low activation energy (Ea = 10.55 Kj/mol) demonstrated the efficiency of the proposed catalytic system for the azo dye degradation. Overall, based on the synthesis process and the excellent catalytic results, the prepared [Mn(TPP)Cl] could be used as an effective catalyst for the treatment of calmagite-contaminated effluents.