Defense of the dissertation of Parmanbek Nursanat for the degree of Doctor of Philosophy (PhD) in the specialty «8D05306 - Chemistry»
L.N. Gumilyov Eurasian National University, a dissertation defense for the degree of Doctor of Philosophy (PhD) by Parmanbek Nursanat on the topic «Development of modified composite track-etched membranes for removal of different types of pollutants from aqueous media» in the field of «8D05306 – Chemistry».
The dissertation was carried out at the «Chemistry» of L.N. Gumilyov Eurasian National University.
The language of defense is kazakh
Reviewers:
Онгарбаев Ердос Калимуллаулы - Doctor of Science, Professor
Кудайбергенов Саркыт Елекенович - Doctor of Science, Professor
Temporary members of the Dissertation Committee:
Мангазбаева Рауаш Амантаевна
Абдиев Калдибек Жамшаевич - Doctor of Science, Professor
Нуршат Нураджи
Мусабаева Бинур Хабасовна - Candidate of Science, Professor
Бакибаев Абдигали Абдиманапович - Doctor of Science, Professor
Тажбаев Еркеблан Муратович
Academic Advisors:
• Jakupova Zhanar Yerekeevna - Docent of the Department of Chemistry at the NP JSC “L.N. Gumilyov Eurasian National University”, Candidate of Chemical Sciences, Docent, Astana, Republic of Kazakhstan. • Mashentseva Anastassiya Alexandrovna - Head of the Technological laboratory of track-etched membranes of the Astana Branch of the RSE “Institute of Nuclear Physics” Ministry of Energy of the Republic of Kazakhstan, PhD, Associate Professor, Astana, Republic of Kazakhstan
Murat Barsbay – PhD, Professor of “Hacettepe University”, Faculty of Science, Department of Chemistry, Ankara, Turkey
The defense will take place on December 26, 2023, at 02:00 PM in the Dissertation Council for the training direction «8D053 – %!s(*string=0xc014a4fb80)» in the specialty «8D05306 – Chemistry» of L.N. Gumilyov Eurasian National University. The defense meeting is planned to be held online.
Link: https://rb.gy/xy1p98
Address: Online Microsoft Teams
Abstract (English): ANNOTATION on the dissertation of Parmanbek Nursanat on the topic “Development of modified composite track-etched membranes for removal of different types of pollutants from aqueous media”, submitted for the degree of Doctor of Philosophy (PhD) in the educational program “8D05306 – Chemistry” General description of the research. The thesis work is devoted to study of features of synthesis of hybrid track membranes based on polyethylene-terephthalate (PET) modified with functional monomers and metal nanoparticles, as well as to study of the possibility to use these hybrid composites during purification of aqueous media from various classes of organic and inorganic pollutants. The thesis work is presented in form of series of articles published by the doctoral candidate in accordance with the requirements of paragraph 5-1 of the Regulations on awarding degrees, approved by the order of the Minister of Education and Science of the Republic of Kazakhstan from 31 March 2011 № 127 (registered in the Register of state registration of normative legal acts under № 6951) as amended by the Order of the Minister of Education and Science of the Republic of Kazakhstan from 30.04.2020 № 170, amended by the Order of the Acting Minister of Education and Science of the Republic of Kazakhstan from 09.03.2021 № 98. 04.2020 № 170 and in accordance with the Order of the Minister of Education and Science of the RK from 09.03.2021 № 98 as amended by the Acting Minister of Science and Higher Education of the RK from 09.01.2023 №7. Relevance of the work. An effective purification of contaminated water sources from toxic pollutants is one of the most current problems of the world during the technogenic era of large-scale development of various extractive and processing industries. Industrial and textile dyes present one of the largest groups of toxic and carcinogenic organic compounds. According to an estimate of the World Bank, almost 20% of water pollution in the world is caused by dyes. The very high reactivity and extreme toxicity of dyes cause very serious environmental threat for environment. Pharmaceuticals and heavy metal ions as pollutants enter surface water and subsurface resources through municipal and industrial waste-water discharges, impairing traditional processes of wastewater treatment in filtration systems, as well as has toxic effect on living organisms. Existing industrial water treatment technologies such as filtration and coagulation do not destroy, but only concentrate contaminants. Traditional water treatment methods, such as sedimentation, chemical and membrane technologies, are associated with high operating costs and, in addition, can generate toxic secondary pollutants in the ecosystem. Therefore, the development of practical and inexpensive catalysts and sorbents with high efficiency in relation to various classes of pollutants is an urgent task that requires urgent solution. The purpose of the thesis research. Synthesis of hybrid track-etched membranes based on polyethylene terephthalate (PET) modified with functional monomers and metal nanoparticles, as well as study of the possibility of application of these hybrid composites during purification of aqueous media from various classes of organic and inorganic pollutants. Achievement of the assigned goal implies solution of the following tasks: - Study of features of HTM synthesis by RAFT-mediated modification of PET TeMs with 2-(Dimethylamino) ethyl methacrylate (PDMAEMA) and immobilization of silver nanoparticles. - Study of doping process with silver nanoparticles impact on the efficiency of HTM composition of Ag@PET-g-PDMAEMA in the processes of sorption removing As(III) ions in model systems. - Study of the nature effect of the reducing agents on immobilization efficiency of palladium nanoparticles in Pd@PET-g-PVP GTM and feasibility study of the use of such HTM during photocatalytic removal of the antibiotic metronidazole. - Comparative study of the source of ionizing radiation impact on the process of radiation-chemical synthesis of copper nanoclusters in the scope of PET TeMs modified with polyacrylic acid. - Study of kinetic and thermodynamic features of the reaction of photocatalytic decomposition of methylene blue dye in the presence of HTM based on copper and polyacrylic acid nanoclusters synthetized using gamma radiation and electron beam. The subject of the study. Hybrid composite materials based on microporous polymer templates made of PET TeMs modified with functional monomers and metal nanoparticles. Relation of the work to the plan of state scientific programs. This work was performed within the framework of grant funding projects of the Ministry of Science and Higher Education of the Republic of Kazakhstan “Development of modified composite track membranes for environmental protection” (URN AP08855527, implementation period 2020-2022), “Development and environmental application of biogenic catalysts and sorbents from endemic plants of Kazakhstan” (URN AP09057856, implementation period 2021-2023) and IAEA project “Radiation induced and template synthesis of the photocatalytically active ion-track membrane composites” performed within the framework program F22070 “Enhancing the Beneficial Effects of Radiation Processing in Nanotechnology” (Contract No. 23152, implementation period 2019-2023). Scientific novelty of the work. PET TeMs were modified for the first time by UV-induced and RAFT-mediated grafting PET TeMs of 2-(Dimethylamino) ethyl methacrylate (DMAEMA), vinyl-1-pyrrolidone-2 (VP) and acrylic acid (AA). The optimum conditions for modifying PET TM PDMAEMA, providing not only a high degree of PDMAEMA grafting, but also preserving the mechanical and technological characteristics of the membrane (conditions) were determined. It was demonstrated that the stage of quaternization of PET-g-PDMAEMA samples significantly increases the efficiency of immobilization of silver nanoclusters, however, the mechanical strength of the membrane becomes minimal. It was established that immobilization of silver nanoclusters on the surface and in the pores of PET-g-PDMAEMA increases the sorption capacity of arsenic(III) ions in HTM by 60% compared to the initial samples. It was demonstrated that the sorption process of As (III) ions can be described by the model of pseudo-second order Freundlich adsorption isotherm model. Systematic studies on modification of PET TeMs with PVP using the method of RAFT polymerization were conducted and optimal modification conditions were determined (grafting time - 360 min; solvent - water; monomer concentration - 20%). Four types of reducing agents were used for immobilization of palladium nanoclusters to meet the requirements of green chemistry - ascorbic acid (AA), plant extract of Betula Pendula Roth (BPR), sodium borehydrate (SBH) and thermal reduction (TR) procedure. AA provides 3 times more efficient immobilization of palladium NPs compared to BPR and TR method. Studying the catalytic activity of the obtained HTMs in the decomposition reaction of metronidazole (MTZ), it was established that Pd_Asc@PVP-g-PET HTMs were more efficient compared to HTMs of Pd_SBH@PVP-g-PET, Pd_PE@PVP-g-PET and Pd_TR@PVP-g-PET compositions and decompose 90% of MTZ within 180 min and maintain their properties during 10 consecutive cycles of tests. Studies on graft polymerization of PET TeM by (poly)acrylic acid (PAA) under the impact of accelerated electron beam have been conducted for the first time. The optimum grafting conditions, providing not only a high value of PAA grafting degree, but also preserving the mechanical strength of the membrane itself were determined. It was established that irradiation with accelerated electrons allows synthesizing homogeneous nanoparticles of copper hydroxide in the whole volume of the template with a small distribution of the nanoparticles size at a dose of 100 kGy, while irradiation with γ-rays can produce composites with nanoclusters of crystalline copper with a high degree of crystallinity. Studying kinetic and thermodynamic features of the photocatalytic decomposition reaction of MB dye in the presence of HTM based on copper and polyacrylic acid nanoclusters synthesized using gamma radiation and electron beam, it was demonstrated that the synthesized HTMs of Cu(OH)2@PET-g-PAA composition provide removal of about 91.9% of the dye, while Cu@PET-g-PAA samples - only 83.9%. It was demonstrated that both types of samples retain their efficiency for 12 consecutive cycles. Main provisions of the thesis offered for defense: - In case of optimal conditions of RAFT-mediated modification of polymer PET template, providing effective grafting of 2-(Dimethylamino) ethyl methacrylate (monomer concentration - 20%, reaction time - 60 min, solvent – acetone/water, DG - 20%), the degree of silver nanoclusters immobilization within 5 h is 9 mg/cm2. - Immobilization of silver nanoclusters in the pores and on the surface of PET-g-PDMAEMA TeM (Ag@PET-g-PDMAEMA) provides more efficient sorption of As(III) ions (85.6%) compared to samples of PET-g-PDMAEMA composition (56.0%). - The use of ascorbic acid as a reducing agent provides more efficient reduction of palladium nanoparticles in Pd@PVP-g-PET GTMs and ensures high catalytic activity of the specified HTMs in the photocatalytic removal reaction of the metronidazole antibiotic. - HTMs of Cu(OH)2@PET-g-PAA composition synthesized using electron beam catalyze the removal of about 91.9% of methylene blue dye, while samples synthesized using γ-rays only 83.9%. Practical relevance of the thesis research. The obtained results of the research on synthesis and investigation of properties of modified (hybrid) composite catalysts and sorbents have potential applications in further scientific and experimental developments of improved hybrid composite materials and expansion of the range of their application on for purification of pollutants from the aqueous media. In particular, they are promising for the treatment of wastewater from the pharmaceutical industry, the metallurgical industry and the sorption removal of heavy metal ions, the decomposition of antibiotics and organic dyes up to 90%. The personal contribution of the author to the thesis research consists in the analysis of literary sources, experimental and calculation works, interpretation, theoretical justification, generalization, and discussion of the obtained experimental results, preparation and design of graphs, and preparation of the manuscript of the article. Approbation of thesis research. The main provisions, conclusions and scientific results of the thesis work were reported and discussed at international conferences: Materials of the ХІ International Conference on Chemistry and Chemical Technology (Almaty, 2021); The 10th International Conference on Nanomaterials and Advanced Energy Storage Systems (Nur-Sultan, 2022); Ionizing radiation and polymers symposium - IRaP 2022 (Nara, Japan); International Scientific Conference “Science and Education 2023”, (Nur-Sultan, 2023). Publications. The basic results of the thesis research are specified in 8 published works, 3 articles of them are in the scientific publications, that are included into the first and/or second quartile according to impact-factor as reported by Journal Citation Reports of Clarivate Analytics company; 5 works in the materials of the republican and international conferences: The applicant is the original author in all the 3 articles in scientific publications included in the first and/or second quartile of impact factor according to Journal Citation Reports. Parmanbek N., Sütekin D. S., Barsbay M., Mashentseva A. A., Zheltov D.A., Aimanova N. A., Jakupova Zh. Ye., Zdorovets M. V. “Hybrid PET Track-Etched Membranes Grafted by Well-Defined Poly(2-(Dimethylamino)Ethyl Methacrylate) Brushes and Loaded with Silver Nanoparticles for the Removal of As(III)”. // Polymers. – 2022. – Vol. 14 (19). – P. 4026. (25 p.), (Q1 – by category Polymer Science, Q1 – Polymers and Plastics). Percentile by category of Materials Science (Polymers and Plastics) – 76 %, Chemistry (General Chemistry) – 76%. Parmanbek N., Sütekin D. S., Barsbay M., Aimanova N. A., Mashentseva A. A., Alimkhanova A. N., Zhumabayev A. M., Yanevich A., Almanov A. A., Zdorovets M. V. “Environmentally friendly loading of palladium nanoparticles on nanoporous PET track-etched membranes grafted by poly(1-vinyl-2-pyrrolidone) via RAFT polymerization for the photocatalytic degradation of metronidazole”. // RSC Advances – 2023. – Vol. 13(31). – P.18700. (15 p.). (Q2 – Chemical Engineering (miscellaneous), Q2 – Chemistry (miscellaneous). Percentile by category of Chemical Engineering (General Chemical Engineering) – 78 %, Chemistry (General Chemistry) - 77%. Parmanbek N., Aimanova N. A., Mashentseva A. A., Barsbay M., Abuova F. U., Nurpeisova D. T., Jakupova Zh. Ye., Zdorovets M. V. “e-Beam and γ-rays Induced Synthesis and Catalytic Properties of Copper Nanoclusters-Deposited Composite Track-Etched Membranes”. // Membranes. – 2023. – Vol.13(7). – P.659. (21 p.). (Q2 – Polymer science, Q2 – Chemical Engineering (miscellaneous). Percentile by category of Chemical Engineering (miscellaneous) – 61 %, Chemical Engineering (Filtration and Separation) – 52%, Chemical Engineering (Process Chemistry and Technology) – 47%.
Conclusion of the Research Ethics Committee
Defense of the dissertation: https://youtu.be/clet26yrJ5Q?si=uGwC_oDdZbhXFafv
