Experimental and theoretical study for removal of trimethoprim from wastewater using organically modified silica with pyrazole-3-carbaldehyde bridged to copper ions

Abstract

Background Human and veterinary antibiotics are typically discharged as parent chemicals in urine or feces and are known to be released into the environment via wastewater treatment plants (WWTPs). Several research investigations have recently been conducted on the removal and bioremediation of pharmaceutical and personal care products (PPCPs) disposed of in wastewater. Results SiNP-Cu, a chelating matrix, was produced by delaying and slowing 1.5-dimethyl-1H-pyrazole-3-carbaldehyde on silica gel from functionalized with 3-aminopropyltrimethoxysilane. The prepared sorbent material was characterized using several techniques including BET surface area, FT-IR spectroscopy, Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and nitrogen adsorption–desorption isotherm. The pseudo-second-order model provided the best correlation due to the big match between the experimental and theoretical of different adsorption coefficients. The Langmuir and Freundlich adsorption models were used and the study showed a better match with the Freundlich model with a capacity of removal reached up to 420 mg g−1. The removal capacity was dependent on pH and increased by increasing pH. The removal percentage reached 91;5% at pH = 8. The adsorbent demonstrated a high percentage removal of TMP, reaching more than 94% when increased pH. The sample was simply regenerated by soaking it for a few minutes in 1 N HCl and drying it. The sorbent was repeated five times with no discernible decrease in removal capacity. The thermodynamic study also showed endothermic, increasing randomness and not spontaneous. The free energy was 2.71 kJ/mol at 320 K. The findings of the DFT B3LYP/6–31 + g (d, p) local reactivity descriptors revealed that nitrogen atoms and π-electrons of the benzene and pyrimidine rings in the TMP are responsible for the adsorption process with the SiNP surface. The negative values of the adsorption energies obtained by molecular dynamic simulation indicated the spontaneity of the adsorption process. Conclusion The global reactivity indices prove that TMP is stable and it can be removed from wastewater using SiNP surface. The results of the local reactivity indices concluded that the active centers for the adsorption process are the nitrogen atoms and the π-electrons of the pyrimidine and benzene rings. Furthermore, the positive value of the maximum charge transfer number (ΔN) proves that TMP has a great tendency to donate electrons to SiNP surface during the process of adsorption.

Adsorption of Methylene Blue Dye and Analysis of Two Clays: A Study of Kinetics, Thermodynamics, and Modeling with DFT, MD, and MC Simulations

“…These results, which are substantiated in references, add substantially to our understanding of the behavior and attributes of the system under the conditions we simulated. 66 , 68 , 77 , 78 Moreover, computation of the relative concentration of MB (methylene blue) on the respective surfaces, as illustrated in Figure 16 b, lends additional support to our findings. This analysis reveals a notable affinity of MB molecules for the surfaces, demonstrating their effective adhesion.…”

“…Our confidence in the accuracy of the data we’ve collected and in the validity of the observations we’ve made, thanks to the small temperature swings we’ve seen, is further bolstered by the fact that they’re consistent with the simulation’s predictions, as shown in the supporting refs ,, . These results, which are substantiated in references, add substantially to our understanding of the behavior and attributes of the system under the conditions we simulated. ,,, Moreover, computation of the relative concentration of MB (methylene blue) on the respective surfaces, as illustrated in Figure b, lends additional support to our findings. This analysis reveals a notable affinity of MB molecules for the surfaces, demonstrating their effective adhesion.…”

Methods to prepare biosorbents and magnetic sorbents for water treatment: a review

“…Both studies reported that the main adsorption driving force was the electrostatic interaction between the anionic surface charge of the respective drugs and the protonated adsorbent surface. Besides, Jodeh et al (2022) recorded high adsorptive capacity while adsorbing trimethoprim onto a chelating matrix synthesized via a reaction between 1.5-dimethyl-1H-pyrazole-3-carbaldehyde, 3-aminopropyltrimethoxysilane and silica gel. According to the study, efficient drug binding occurred via complexation between the nitrogen atoms of the adsorbent and π-electrons originating from the benzene and pyrimidine rings in the drug.…”

“…According to the study, efficient drug binding occurred via complexation between the nitrogen atoms of the adsorbent and π-electrons originating from the benzene and pyrimidine rings in the drug. Also, low adsorption enthalpy values were recorded throughout the entire sorption process due to the hydrogen bond formation and the formation of a water bridge between the nitrogen/oxygen-containing groups of the trimethoprim and the amine groups of the adsorbent (Jodeh et al 2022). Dipyridyl-based organo-silica nanosheets were successfully synthesized and utilized for adsorbing clofibric acid, ketoprofen, and naproxen sodium from wastewater (Guo et al 2020).…”

Green synthesis of Ag2O nanoparticles using Punica granatum leaf extract for sulfamethoxazole antibiotic adsorption: characterization, experimental study, modeling, and DFT calculation

“…Jodeh et al 2022). The energies of the HOMO and LUMO frontier orbitals and the gap energy of the molecules calculated by the DFT/B3LYP 6-31 + G (d,p) method under different pH conditions from the optimized structures are given in Table6, a unprotonated and protonated state.…”