Comprehensive study of adsorbents based on nanoparticles of hexagonal boron nitride for wastewater treatment from drugs
At present, the development of new drugs and their production have become the most important branch of domestic science and industry. The creation of local pharmaceutical production in the Russian Federation is one of the priorities of the country's development. In Russia, the Strategy for the Development of the Pharmaceutical Industry (“PHARMA-2020”) was approved, which was extended for the period until 2024 [1]. Among the important objectives of the strategy is to increase the share of domestically produced products in the domestic market up to 50%. With the growth of the pharmaceutical industry and the widespread use of drugs, their release into the environment is inevitable. In this regard, the search for effective methods and new ways to remove antibiotics from water bodies is currently an important scientific and practical task. The rapid development of nanotechnologies, in particular the field of low-dimensional nanomaterials, can make a significant contribution to the development of this area and the improvement of the described situation. The adsorption of drug molecules on a safe carrier is the most preferred purification methods, since they offer the possibility of using simple chemical-physical processes in the purification of water, air, and surfaces from organic pollutants, which makes this process environmentally friendly and economical. Nanomaterials with a high specific surface area are ideal platforms for the development and production of low-cost and high-performance biosensors, biofilters, and carriers of antibacterial agents. These materials include hexagonal boron nitride (h-BN). This material has a unique set of properties: low specific gravity, high thermal and chemical stability, heat resistance, biocompatibility, good adsorption capacity and a wide band gap. Thus, nanostructured h-BN is an ideal candidate for an absorbent material. However, the efficiency of adsorption on an ideal surface of hexagonal boron nitride is hampered by a small number of activated centers, which requires its modification. The novelty of the project lies in conducting a systematic experimental and theoretical study and building a general model for the sorption / desorption of various antibacterial drugs on the surface of modified boron nitride nanoparticles. The main objective of this project is to study the processes of sorption and desorption of various types of antibiotics in relation to h-BN nanostructures by both theoretical and experimental methods. Such a systematic approach will make it possible to deeply study the process of sorption/desorption of antibiotics of various classes, to describe the type of analyte binding to the adsorbent, to determine the nature of sorption, and to study its dependence on external conditions. Nanoparticles based on h-BN with various surface modifications will be studied - introducing defects, decorating with atoms and/or metal nanoparticles, introducing foreign atoms into the structure, etc. Antibiotics of various groups will be selected as analytes, including macrolides (erythromycin), sulfonamides (sulfamethoxazole ), diaminopyrimidines (trimethoprim), aminoglycosides (ciprofloxacin), tetracyclines (tetracycline), and β-lactams (penicillin). Such a comprehensive study will ultimately make it possible to produce effective adsorbents and membranes based on them for wastewater treatment from pharmaceutical pollution.
Main performers
Target
The aim of this project is to systematically study the processes of sorption and desorption of various types of antibiotics in relation to h-BN nanostructures using theoretical modeling of various systems and further verification in practice of the results obtained in order to develop biological sensors, filters and adsorbates. The relationship between the structure and physicochemical properties of BN particles (BNNP) will be established depending on the type of surface functionalization in relation to antibiotics of various types. The study of these nanohybrid materials will be carried out using both theoretical and experimental approaches. A theoretical model will be built to determine the relationship between the morphology and sorption activity of BNNP. The result of the work will be the production of a stable high-performance adsorbent based on h-BN with selectivity to various classes of antibiotics. The most important part of the project is a detailed study of BNNP surface modification by various methods. h-BN can be synthesized in the form of various morphological types: graphene-like nanosheets, nanotubes, nanoneedles, hollow and hard spherical nanoparticles with a smooth or developed surface [1]. Modification of its surface (introduction of defects, decoration of the surface with metals) will strongly affect the sorption of analytes. To solve this problem, the project will use theoretical methods to determine how one or another modification of BNNP affects the physico-chemical and, consequently, the sorption properties of the surface. Experimental studies will provide direct verification of the data obtained from theoretical modeling and will make it possible to create an effective selective adsorbent for cleaning wastewater from various therapeutic drugs.
Specific task
The main objective of this project is to study the processes of sorption and desorption of various types of drugs in relation to h-BN nanostructures using theoretical modeling of various systems and further verification in practice of the results obtained in order to develop effective adsorbents and filters based on them for wastewater treatment from pharmaceutical contaminants. drugs. The project will study the process of sorption and desorption of antibiotics on the surface of modified nanostructured boron nitride with the possibility of controlling its structure to solve problems of water purification from therapeutic drugs. To achieve this goal, various problems will be solved, both in the field of computer simulation of the obtained materials and structures, and in terms of experimental production and study of nanostructures. So, in theory, various substrates based on boron nitride as sorbents of antibiotics of various groups (macrolides (erythromycin), sulfonamides (sulfamethoxazole), diaminopyrimidines (trimethoprim), aminoglycosides (ciprofloxacin), tetracyclines (tetracycline) and β-lactams (penicillin) will be studied in detail. )). Theoretically, nitride-boron structures with various surface modifications will be simulated - the introduction of defects, decoration with metal atoms and/or nanoparticles, the introduction of foreign atoms into the structure, etc. The sorption of each type of antibiotic on the modified surface will be evaluated and the binding energy and type of attachment to various types of substrates. Conclusions will be drawn on the type of substrate modification for the best sorption of one or another type of antibiotics. Based on the results of theoretical modeling, nanoparticles based on boron nitride with a given surface will be obtained by experimental methods. Studies will be carried out to study the process of sorption on the surface of a certain class of antibiotics. The resulting nanohybrid materials will be investigated by various methods: Fourier transform IR spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, spectrophotometry, scanning electron microscopy. The sorption process itself will be studied by spectrophotometry, detecting changes in the antibiotic concentration after the addition of nanoparticles. This approach will make it possible to determine the sorption capacity of nanoparticles with respect to each type of antibiotics under study. In addition, a protocol for the purification of particles from analytes for their reuse will be developed. Thus, the theoretical data on the sorption process will be verified in the experiment, while the presence of theoretical predictions will allow a more directed experimental search to study the sorption of antibiotics from aqueous solutions.
Main results of the project
It has been shown that nanoparticles from hexagonal BN, obtained in a horizontal tubular CVD reactor by chemical interaction of amorphous boron particles with ammonia, are promising sorbents for reusable wastewater treatment from various types of antibiotics. The maximum sorption capacity of tetracycline, ciprofloxacin, amoxicillin and amphotericin B was 502.78, 315.75, 400.17 and 269.7 μg/g, respectively. BNNPs exhibit significantly higher adsorption capacity for CIP, TET, and AMOX compared to other adsorbents. The possibility of effective water purification from amphotericin B was demonstrated for the first time. The rate of removal of antibiotics on the first day was high in all cases of the experiment, then a gradual decrease in the rate of adsorption was observed. Antibiotic removal efficiency can be expressed as follows: TET > CIP> AMOX> AMP. It has been shown theoretically and experimentally that the acidity of the medium significantly affects the kinetics of adsorption: with increasing acidity of the medium from pH 4, the efficiency increased; after pH 7, a gradual decrease in efficiency was observed, but in an alkaline environment it was higher than in an acidic environment. The possibility of repeated use of nanostructured hexagonal BNNPs has been demonstrated, which will have a positive effect on their economic and environmental efficiency. The loss of efficiency during repeated coating is no more than 5%, which confirms the prospects for reusable use. Based on theoretical modeling data, we can conclude that adsorption is the main process of water purification from antibiotics. In the presence of a conjugated system in a drug molecule, the interaction of antibiotics with the BN surface occurs through π-π interaction. Electrostatic interaction between the functional groups of the antibiotic and the surface of boron nitride also plays an important role. In an acidic environment, the redistribution of electron density is concentrated mainly on the antibiotic molecule and almost does not affect BN, which explains the weaker binding compared to an alkaline or neutral environment. Using the example of riboflavin adsorption, it is shown that the defectiveness of boron nitride can significantly affect the binding of the drug molecule and boron nitride.
It has been shown that modification of boron nitride with a pHEMA polymer containing multiple –OH groups promotes the formation of hydrogen bonds and increased electrostatic interaction with antibiotics.
Project Publications
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L. Yu. Antipina, K. Yu. Kotyakova, MV Tregubenko, DV Shtansky Experimental and Theoretical Study of Sorption Capacity of Hexagonal Boron Nitride Nanoparticles: Implication for Wastewater Purification from Antibiotics // Nanomaterials 2022, V. 12, No. 18, P. 3157
Press about us
NUST MISIS researchers have created a reusable and environmentally friendly sorbent for cleaning wastewater from antibiotics. It has a number of advantages compared to already known counterparts - low production costs, simple design and ease of operation in treatment facilities. The results of the study are published in the journal Nanomaterials.
NUST MISIS researchers have created a reusable and environmentally friendly sorbent for cleaning wastewater from antibiotics. It has a number of advantages compared to already known counterparts - low production costs, simple design and ease of operation in treatment facilities. The results of the study are published in the journal Nanomaterials.
NUST MISIS researchers have created a reusable and environmentally friendly sorbent for cleaning wastewater from antibiotics. It has a number of advantages compared to already known counterparts - low production costs, simple design and ease of operation in treatment facilities. The results of the study are published in the journal Nanomaterials.