Defense of the dissertation of Алтынбаева Лилия Шарифулловна 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 Алтынбаева Лилия Шарифулловна on the topic «Investigation of catalytic and sorption properties of composite materials based on polymer track membranes and copper microstructures» in the field of «8D05306 – Chemistry».
The dissertation was carried out at the «» of L.N. Gumilyov Eurasian National University.
The language of defense is russian
Reviewers:
Нечаев Александр Николаевич
Зазыбин Алексей Георгиевич
Temporary members of the Dissertation Committee:
Копишев Эльдар Ертаевич - Candidate of Science, Head of the cafedra
Гавриленко Михаил Алексеевич - Doctor of Science, Professor, professor
Байкенов Мурзабек Исполович - Doctor of Science, Professor, professor
Аубакиров Ермек Айтказынович - Doctor of Science, Assistant Professor, Head of the cafedra
Ефремов Сергей Анатольевич - Doctor of Science, Professor, professor
Токпаев Рустам Ришатович - Doctor of Science, Professor, Head of Laboratory
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, 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 April 17, 2024, at 03:00 PM in the Dissertation Council for the training direction «8D053 – %!s(*string=0xc003ec5e20)» 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/0ym9rp
Address: Microsoft Teams платформасында
Abstract (English): General description of the thesis The thesis is devoted to the study of the features of electroless template synthesis of composite track-etched membranes (СTMs) based on copper microtubes (MTs) using various types of reducing agents, synthesis of multicomponent composites on their basis with the aim of obtaining highly efficient catalysts and sorbents suitable for purification of aqueous media from various classes of pollutants. The thesis is submitted in the form of a series of articles published by the doctoral student as required by paragraph 5-1 of the Degree Awarding Regulations approved by the Order of the Minister of Education and Science of the Republic of Kazakhstan No. 127 dated March 31, 2011 (recorded in the Register of State Registration of Laws and Regulations under No. 6951) as amended by the Order of the Minister of Education and Science of the Republic of Kazakhstan No. 170 dated 30.04.2020 and in accordance with the Order No. 7 of the Acting Minister of Science and Higher Education of the Republic of Kazakhstan dated 09.01.2023. Relevance of the topic. The unique properties of nanoscale materials, their reactivity and efficiency are characterized by high potential in comparison with traditional approaches in surface phenomena. NMs modified with active functional groups impart additional specific properties and affect the functional characteristics of the material. In particular, the potential for using CТМs based on copper micro- and nanostructures as effective catalysts has been noted in the dehydrogenation reactions of aromatic compounds. In light of the increasing demands for the development of low-cost, high-performance environmentally friendly methods for the production of new generation functional materials, this is an urgent task that requires urgent solutions. Purpose of the thesis. Study of the features of templated synthesis of composite track membranes based on copper microtubes using different types of reducing agents, as well as study of the influence of the composition of the deposition solution on the catalytic and sorption properties of the synthesised composites in the reactions of removal of organic and inorganic pollutants in aqueous media. Achieving the set goal involves solving the following tasks: - Comparative study of chemical templated synthesis of copper microtubes using deposition solutions based on ascorbic and glyoxylic acids, as well as formaldehyde and dimethylaminborane. - Study of the potential application of copper MT-based composite TMs for catalytic removal of Fe (III) and Cr(VI). - Study of the features of the synthesis of multicomponent CTMs by galvanic substitution and their application for photocatalytic removal of carbendazim pesticide. - Study of the influence of oxidative modification of polymeric polyethylene terephthalate (PET) template as part of CTMs on the efficiency ofsorption removal of arsenic (III) ions in steady-state mode. - Study of the kinetics and mechanism of sorption removal of lead (II) ions in the presence of CTMs obtained using different compositions of copper deposition solution. Study object: Composite materials based on microporous polymer templates made of polyethylene terephthalate (PET) and electroless deposited mono- and polycomponent copper microtubular structures of 410±25 nm in size and pore density of 4×107 cm-2 . Relation of the thesis to the plan of state scientific programmes. Thisthesis was carried out as part of the Ministry of Science and Higher Education grant projects: 1. "Development of composite arsenic sorbents based on track-etched membranes and metallic nanostructures" (IRN AP05130797, implementation period 2018-2020). 2. "Development of modified composite track-ethced membranes for environmental protection" (IRN AP08855527, implementation period 2020-2022). Scientific novelty of the thesis: A comprehensive study of the process of chemical synthesis of copper MTs in porous PET-based templates using deposition solutions based on non-toxic reducing agents (ascorbic and glyoxylic acids, dimethylamineborane) was carried out for the first time. The optimal synthesis conditions ensuring the formation of copper MTs with a high degree of crystallinity were determined. The kinetic and thermodynamic properties of the decomposition reaction of potassium hexacyanoferrate (III) inorganic pollutant of wastewater were studied in the presence of CTМs synthesized using ascorbic acids (AA). When studying the influence of copper MT structural parameters on the removal efficiency of potassium hexacyanoferrate, it was found that the degree of conversion increases linearly and reaches the value of 94.4% for samples with the wall thickness of copper MTs equal to 88.4±13.0 nm. The removal efficiency of Cr (VI) ions was studied for CTMs samples produced using different types of reducing agents. It was found that the composites produced using DMAB as a reducing agent have the lowest activity in the decomposition reaction of Cr(VI) ions, which is caused by the presence of copper(I) oxide phase in the composite composition. The thermodynamic properties of the catalysts were determined; the lowest value of activation energy was calculated for the catalysts of the composition Cu_CHOH@PET. Studies on the synthesis of multicomponent CTМs by galvanic substitution approach where CTМs of Cu2O@PET composition were used as a substrate and zinc (II) ions as a doping agent were carried out for the first time. The higher catalytic activity of the mixed Cu2O/ZnO@PET composite was demonstrated on the example of the decomposition reaction of the pesticide carbendazim. Kinetic and thermodynamic properties of mono- and polycomponent CTM-based catalysts have been studied. When studying the features of using copper MT-based CTMs for sorption removal of arsenic(III) ions, it was found that the sorption process can be described most reliably in terms of the pseudo-second-order model, and the samples of composites produced by copper deposition in a modified templat (Cu@PET_Ox) have a higher sorption capacity compared to the samples of CTMs synthesised in unmodified PET template. The sorption activity of synthesized composite sorbents in steady-state mode against lead(II) ions has been studied; the influence of various factors on sorption efficiency, such as pH and concentration of sorbate solution, duration of sorption, number of repeated tests, has been studied. Through the comparison of regression coefficients R2 it is shown that, the Freundlich model describes the experimental data on arsenic adsorption by synthesized composites better than other considered ones. The highest sorption capacity with respect to lead and arsenic ions was found to be possessed by copper microtube-based CTMs produced using ascorbic acid as a reducing agent. The main provisions of the thesis, submitted for defence: - During the chemical synthesis of copper MTs using ascorbic acid as a reducing agent, a monolayer of copper nanoparticles with the size of 10-15 nm is formed in the template volume. In this case, it is recommended to activate the PET template at least three times, the pH of the deposition solution is to be within the value of 4.0, and the deposition time is 90 min. During copper deposition using glyoxylic acid, by increasing the pH level of the solution from 12.65 to 13.49, the specific copper deposition rate increases 15 times and after 45 sec of deposition, copper tubular structures with wall thicknesses of 31.6 and 103.9 nm are formed, respectively. The use of DMAB as a copper reducing agent in the temperature range of 26-55°C provides the formation of two phases - crystalline copper and Cu2O cuprite phase. - Cu_Asc@PET composites produced at different deposition times (90-480 min) effectively remove from 82 to 95% of iron(III) ions depending on the synthesis conditions, while the efficiency of potassium hexacyanoferrate decomposition is directly proportional to the wall thickness of copper microtubes in the CTM composition and remains practically unchanged during 6 consecutive test cycles. - Composites produced using DMAB as a reducing agent show the lowest activity in the decomposition reaction of Cr(VI) ions, which is caused by the presence of copper(I) oxide phase in the composite. More efficient removal of Cr(VI) ions occurs in the presence of samples of Cu_CHOH@PET composition, which is confirmed by the data of kinetic and thermodynamic parameters of the reaction. - The mixed composite (Cu2O/ZnO@PET) catalysed the decomposition more efficiently compared to Cu2O@PET and ZnO@PET and decomposed more than 93% of Czm after 140 min of irradiation. The highest reaction rate constant (1.76 × 10-2 min-1) and the lowest activation energy (11.9 kJ/mol) were calculated for the mixed Cu2O/ZnO@PET composite, which is attributed to the synergistic catalytic effect due to the presence of both active phases (ZnO and Cu2O) and intermetallide (CuZn) in its composition. - Oxidative modification of polymeric PET template, preceding the stage of chemical deposition of copper MTs, provides 35% higher value of the sorption capacity parameter for the removal of arsenic(III) ions compared to samples produced on the basis of unmodified PET templates (pH -5.0, concentration of As(III) - 50 ppm). - The CTMs of Cu_Asc@PET composition have the highest sorption capacity of 560 µg/g for removal of lead(II) ions in the model systems and the process of lead(II) ion sorption in the presence of CTMs can be described most reliably in terms of the pseudo-second-order model. The analysis of experimental adsorption isotherms used to describe the distribution of arsenic molecules between the adsorbent using the Langmuir, Freundlich and DubininRadushkevich models and the liquid and the comparison of standard deviations (R2 ) indicate that the Freundlich model describes the adsorption of arsenic and lead on the surface and in the pores of copper MT-based CTMs better than others. Practical significance of the thesis. The results of the studies on synthesis and investigation of properties of composite catalysts and sorbents may be used in further scientific and experimental development of advanced composite materials and expansion of the range of their application on the real objects. The results of using composite TM in the reactions of catalytic decomposition of inorganic pollutants, pesticides, sorption removal of heavy metal ions also open wide prospects for the introduction ofsuch composites in the process flow diagrams for wastewater treatment of industrial enterprises. High practical significance of the studies carried out is confirmed by the patent for invention No. 108984 "National Institute of Intellectual Property" RSE, Ministry of Justice of the Republic of Kazakhstan. The author's personal contribution to the thesis research is in the analysis of literature and patent sources, carrying out experimental and calculation works, interpretation, generalisation and discussion of the obtained experimental results. Thesis approbation. The main provisions, conclusions and scientific results of the thesis were reported and discussed at international conferences: The 7th International Congress on Energy Fluxes and Radiation Effects(EFRE-2020 online), Tomsk, Russia, 2020, The 8th International Conference on Nanomaterials and Advanced Energy Storage Systems (INESS-2020), 6 August, 2020 - Nur-Sultan, Kazakhstan, The 1st International SchoolConference "Atom. Science. Technologies", RSE "Institute of Nuclear Physics", Almaty, Advanced materials manufacturing and research: new technologies and techniques (AMM&R-2021 online), Ust-Kamenogorsk: Publishing House of D. Serikbayev EKTU, 2021, International Scientific Conference "Science and Education 2021", Nur-Sultan: L.N.Gumilev ENU, 2021, III International Scientific Forum Nuclear Science and Technologies, RSE "Institute of Nuclear Physics", Almaty, The 10th Republican Scientific Conference on topical issues of chemical science and chemical education. - Nur-Sultan: L.N. Gumilyov, 2022. Publications. The major results of the thesis research are reflected in 13 published papers, including 3 articles in scientific editions included in the first and/or second quartile of the impact factor according to Journal Citation Reports of Clarivate Analytics; 2 articles in editions from the list approved by the Committee for Quality Assurance in Science and Higher Education; 8 papers in the materials of national and international conferences. The contribution of the doctoral student consists in planning, direct implementation of the experimental part of the work, processing and interpretation of the obtained data, theoretical justification, preparation and design of graphs. In addition, L.Sh. Altynbayeva participated in the preparation of articles according to the requirements of the journal. In the article “Kinetic and Isotherm Study of As(III) Removal from Aqueous Solution by PET Track-Etched Membranes Loaded with Copper Microtubes”. Russakova A.V., Altynbaeva L.Sh., Barsbay M., Zheltov D.A., Zdorovets M.V., Mashentseva A.A. Membranes. – 2021. – Vol.11 (2). – P. 116. (19 p.). The impact factor of the journal is 4,562, Q2 - in the category Polymer Science, Q2 – Physical chemistry, chemistry. The percentile in the category of Chemical Engineering (miscellaneous) is 58 %. The doctoral student is the first author in the article "Novel Cu2O/ZnO@PET Composite Membrane for the Photocatalytic Degradation of Carbendazim” and Altynbaeva L.Sh., Barsbay M., Aimanova N.A., Jakupova Zh.Ye., Nurpeisova D.T., Zdorovets M.V., Mashentseva A.A. Nanomaterials – 2022. – Vol. 12(10). – P.1724. (19 p.). The impact factor of the journal is – 5,719. Q1 – Physics, Applied, Q2 – Chemistry, multidisciplinary. The percentile in the category of General Chemical Engineering – 81 %, Materials Science (General Materials Science) - 78%. In the article "Eco-Friendly Electroless Template Synthesis of Cu-Based Composite Track-Etched Membranes for Sorption Removal of Lead(II) Ions”. Altynbaeva L.Sh., Aimanova N.A., Zheltov D.A., Shlimas D.I., Nurpeisova D.T., Barsbay M., Abuova F.U., Zdorovets M.V. Mashentseva A.A. Membranes. – 2023. – Vol.13(5). – P.495. (19 p.). The impact factor of the journal is – 4,2. Q2 – Polymer science, Q2 – Physical chemistry, chemistry. The percentile in the category of Chemical Engineering (miscellaneous) – 47 %.
Conclusion of the Research Ethics Committee
Defense of the dissertation: https://youtu.be/OrjEA1RTbe4?si=Uovus9TtQBEFo6Ac
