The modification of the biobased polymer chitosan is a broad and widely studied field. Herein, an insight into the hydrophobization of low-molecular-weight chitosan by substitution of amino functionalities with hexanoyl chloride is reported. Thereby, the influence of the pH of the reaction media was investigated. Further, methods for the determination of the degree of substitution based on 1H-NMR, FTIR, and potentiometric titration were compared and discussed regarding their accuracy and precision. 1H-NMR was the most accurate method, while FTIR and the potentiometric titration, though precise and reproducible, underlie the influence of complete protonation and solubility issues. Additionally, the impact of the pH variation during the synthesis on the properties of the samples was investigated by Cd2+ sorption experiments. The adjusted pH values during the synthesis and, therefore, the obtained degrees of substitution possessed a strong impact on the adsorption properties of the final material.
23 September 2022 in Journal of Environmental Management
Due to the existence-threatening risk to aquatic life and entire ecosystems, the removal of oxyanions such as sulfate and phosphate from anthropogenic wastewaters, such as municipal effluents and acid mine drainage, is inevitable. Furthermore, phosphorus is an indispensable resource for worldwide plant fertilization, which cannot be replaced by any other substance. This raises phosphate to one of the most important mineral resources worldwide. Thus, efficient recovery of phosphate is essential for ecosystems and the economy. To face the harsh acidic conditions, such as for acid mine drainage, an adsorber material with a high chemical resistivity is beneficial. Poly(melamine-co-formaldehyde) (PMF) sustains these conditions whilst its very high amount of nitrogen functionalities (up to 53.7 wt.%) act as efficient adsorption sides. To increase adsorption capacities, PMF was synthesized in the form of mesoporous particles using a hard-templating approach yielding specific surface areas up to 409 m2/g. Different amounts of silica nanospheres were utilized as template and evaluated for the adsorption of sulfate and phosphate ions. The adsorption isotherms were validated by the Langmuir model. Due to their properties, the PMF particles possessed outperforming maximum adsorption capacities of 341 and 251 mg/g for phosphate and sulfate, respectively. Furthermore, selective adsorption of sulfate from mixed solutions of phosphate and sulfate was found for silica/PMF hybrid particles.
Providing safe drinking water free of heavy metal ions like iron and oxyanions like sulfate has become a worldwide issue. Starch, as one of the widely cheapest and available biomaterials, has demonstrated its capability to adsorb heavy metal ions from water in various scientific research, but in low adsorption rates. Therefore, this paper aims to prepare a biopolymer based on a starch–chitosan blend to raise the adsorption efficiency of starch. Two types of chitosan were used to modify potato starch (ps): low molecular chitosan (ch60) and high molecular chitosan (ch4000). Nano potato starch (n.ps) was prepared from potato starch and was also modified with both chitosans. The surface property, the morphology, the particle size, and the structure of the samples were analyzed. Moreover, the investigation of the samples by the zeta potential and charge density were evaluated to determine the charge of the adsorbents’ surface. Furthermore, the pseudo first order (PFO) and pseudo second order (PSO) were employed to examine the adsorption kinetic. The adsorption isotherms of Fe2+/3+ and SO42− were fitted employing Langmuir, Sips, and Dubinin-Radushkevich adsorption models. The maximum achieved sorption capacities from the FeSO4 solution for Fe2+/3+ were as follows: 115 mg/g for n.ps & ch4000, 90 mg/g for ps & ch4000, 80 mg/g for n.ps & ch60, and 61 mg/g for ps & ch60. Similarly, for SO42−, it was 192 mg/g for n.ps & ch4000, 155 mg/g for n.ps & ch60, 137 mg/g for ps & ch4000, and 97 mg/g for ps & ch60.
The purity and safety of water as a finite resource is highly important in order to meet current and future human needs. To address this issue, the usage of environmentally friendly and biodegradable adsorbers and flocculants is essential. Chitosan, as a biopolymer, features tremendous properties as an adsorber and flocculant for water treatment. For the application of chitosan as an adsorber under acidic aqueous conditions, such as acid mine drainage, chitosan has been modified with hydrophobic hexanoyl chloride (H-chitosan) to reduce the solubility at a lower pH. In order to investigate the influence of the substitution of the hexanoyl chloride on the adsorption properties of chitosan, two chitosans of different molecular weights and of three different functionalization degrees were analyzed for the adsorption of CdSO4(aq) and Al2(SO4)3(aq). Among biobased adsorbents, H-chitosan derived from the shorter Chitosan exhibited extraordinarily high maximum adsorption capacities of 1.74 mmol/g and 2.06 mmol/g for Cd2+ and sulfate, and 1.76 mmol/g and 2.60 mmol/g for Al3+ and sulfate, respectively.