Chemical sciences

1. Memory phenomena in thin layers of coordination compounds

Supervisor: prof. dr hab. Konrad Szaciłowski

Auxiliary supervisor: dr Tomasz Mazur

Academic Centre for Materials and Nanotechnology

Summary of research problem: Memristors are unique electronic elements: they are classified as passive elements (they can dissipate energy and are not sources of current) and have memory features. These features make the memristors the prospective building blocks for the computers of the future. Until now, memristors are mainly made of ceramic materials (TiO2, HfO2, IGZO). Their durability is low, and the production requires advanced and expensive technologies. The alternative may be simple complexes containing main group metals (as well as some transition metals, e.g. iron, nickel and copper). In this research, design (supplemented with quantum-chemical modeling) of new coordination compounds with potential application in memory systems, synthesis of these complexes, as well as production and testing of thin-film memristors will be carried out.

Research facilities: The laboratory at Academic Centre of Materials and Nanotechnology is fully equipped with research instruments required for each step of the project except of some elements for construction of memristor/memfractor system for signal processing.

For the first 2 years of the PhD course one of the candidates will be working in NCN grant 2018/31/D/ST5/02813 "Flexible optoelectronic and information processing devices", with additional funding.

Number of places: 2

 

2. Electrochemical synthezis of Cu-Cu2O composite and its photoelectrochemical properties towards reduction of CO2 to hydrocarbons.

Supervisor: prof. dr hab. Konrad Szaciłowski

Auxiliary supervisor: dr inż. Krzysztof Mech

Academic Centre for Materials and Nanotechnology

Summary of research problem: Recently a number of articles concerning subjects related to limitation of greenhouse gasses emission or neutralization of greenhouse gasses present in atmosphere significantly increased. Global warming negatively influences on non-failure operation of ecosystem and due to glaciers melting resulting in water volume increase causing raising of water level in seas and oceans. Large number of negative factors resulting from global warming effect creating necessity of performance of intensified investigations going to development of technologies enabling limitation of emission or neutralization of greenhouses gasses through its conversion to chemical compounds which can be applied in synthesis of other useful chemical compounds or functional materials. Other important problem beyond limitation of CO2 amount in atmosphere is related to possibilities of its conversion to chemical compounds which can be used as energy carriers. It creates possibilities for its applications in renewable energy storage oriented systems.

The proposed investigations are focused on photoelectrochemical conversion of one of main greenhouse gas, CO2 to hydrocarbons. The main aim of proposed investigations is electrochemical synthesis of composite materials consist of Cu matrix – the only metal enabling selective reduction of CO2 to ethylene [1] and Cu2O.

Obtained materials will be characterized and optimized in the frame of its application in photoelectroreduction of carbon dioxide to hydrocarbons.

[1] Y. Kwon, Y. Lum, E.L. Clark, J.W. Ager, A.T. Bell, ChemElectroChem, 3 (2016) 1012-1019.

Research facilities: ACMiN laboratories are fully equipped with apparatus necessary to correct performance of all proposed measurements including gas chromatograph Shimadzu QP-2020 equipped with mass spectrometer and TCD. In laboratories are located devices enabling analysis of spectroscopic properties of synthesized materials such as: spectrometer UV-Vis-NIR Perkin Elmer Lambda 850 with integrating sphere, spectrometer UV-Vis diode-array type Agilent 8453 and spectrometer FTIR Bruker Equinox 55 (FIR, IR, NIR). For electrochemical investigations following apparatus will be used: Autolab PGSTAT 302N potentiostat/galvanostat, BioLogic SP-300 bipotentiostat with EIS module, Biologic SP-150, Zahner (with optic bench, EIS and low current modules), photoelectric spectrometer (Instytut Fotonowy), measuring system Keithley 4200-SCS with ac and pulse modules, microprobes and microscope, diode illuminator with high power LED matrix, Kelvin probe with system for photovoltage measurement (Kelvin Probes, UK and Besocke Delta Phi/Instytut Fotonowy) will be applied. Additionally in ACMiN’s laboratories are located electron microscopes (FEI TECNAI TF20 X-TWIN and FEI QUANTA 3D 200i), XPS spectrometer (Versa Probe II, PHI Electronics), and also X-Ray diffractometers spectrofluorimeters. ACMiN possess also well-equipped laboratories of samples preparation (metallographic microscopes, polishing machines, cutting-off machines, plasma etching system and machine-shop.

Number of places: 1

 

3. The influence of chemical composition, local disorder and the nature of chemical bonding on mobility of copper ions and transport properties of thermoelectric materials with tetrahedrite structure.

Supervisor: dr hab. inż. Andrzej Koleżyński, prof. AGH

Faculty of Materials Science and Ceramics

Abstract: The aim of this research topic is a comprehensive theoretical study employing advanced computational methods of solid state physics and chemistry on the influence of chemical composition and structural properties (local disorder and chemical bonding) on copper ion mobility and thermoelectric efficiency of copper compounds with tetrahedrite structure. High copper ion mobility in these materials results in deterioration of thermoelectric properties due to electromigration (leading to material’s decomposition) and increase of thermal conductivity. Understanding the relationship between chemical composition, crystal structure and bonding properties and copper mobility and thermoelectric efficiency of tetrahedrite based materials would enable improvement of their chemical stability and thermoelectric performance. The use of advanced theoretical research methods will provide a deeper insight into relations between copper ions mobility and chemical composition and structure of tetrahedrites, impossible by experimental methods and will allow better understanding of the complex impact of local disorder and chemical bond properties on the ionic conductivity of copper ions and transport properties of tetrahedrites and, as a consequence, also shaping structural and transport properties for known materials and the design of new high-performance thermoelectric materials.

Research facilities: This research topic will be realized within the scientific project financed by Polish National Science Centre. All theoretical, time-consuming calculations, requiring significant computer recourses will be carried out using Prometheus supercomputer available within PL-GRID infrastructure, while remaining simpler calculations will be performed on computer servers available at Department of Silicate Chemistry and Macromolecular Compounds, Faculty of Materials Science and Ceramics, AGH University of Science and Technology in Krakow.

Number of places: 1

 

4. Modifications of fibrous carbon scaffolds for activation of regeneration processes of cartilage and bone defects.

Supervisor: dr hab. Marek Smoluch

Auxiliary supervisor: dr Anna Drabik

Faculty of Materials Science and Ceramics

Abstract: Abuse of psychoactive substances become a real problem, because of the serious health and social risks generated by their usage. They are developed and introduced as a legal replacement for the banned psychoactive substances, such as opiates,amphetamines,cocaine, cannabinoids or LSD. Although new designer drugs are subsequently identified, characterized,and introduced on the lists of controlled and illegal substances, next generations of these compounds constantly appear on the market. One of the most troublesome aspects of the explosion in designer drugs'popularity and availability, is a need for continuous development of new analytical techniques and procedures used byanti-drug agencies and toxicological laboratories. In the last years, many papers describing identification and characterization of selected classes of designer drugs have been published, often together with complete analytical procedures for their isolation and determination. However, many of the available psychoactive substances are still not characterized by the common analytical techniques and only selected data are available in literature or databases. The requirement for development of a fast, universal method, capable of identification and determination of a wide range of compounds, is one of the most blazing problems of modern analytical chemistry.

Research facilities: Bruker SL mass spectrometer equipped with ESI source or alternatively FAPA source, liquid chromatography system. The possibility of carrying out research confirmed by numerous publications from the Philadelphia List on a selected topic.

Number of places: 1

 

5. Hybrid systems of transition metal compounds for photocatalytic applications.

Supervisor: prof. dr hab. inż. Marta Radecka

Auxiliary supervisor: dr inż. Anna Kusior

Faculty of Materials Science and Ceramics

Abstract: The aim of the research will be to obtain a new class of hybrid semiconductor materials with a developed specific surface area and increased adsorption capacity for environmental protection. The key will be to examine the interface/interface of two semiconductor materials and determine its effect on the transfer of electron bearers. The influence of synthesis conditions on the basic relations between the obtained hybrid system and the surface and photocatalytic properties of materials will also be analyzed.

Research facilities: The apparatus necessary for the implementation of the project is provided by the Faculty of Materials Science and Ceramics at AGH, including X-ray diffractogram, scanning electron microscope or high-pressure reactor. It will be possible to use the following research techniques: optical spectroscopy, Raman spectroscopy, TG / DTA analysis, and measurement of zeta potential. In order to determine the photocatalytic properties, a specially constructed photoreactor will be used.

Number of places: 1

 

6. Miniaturized electrochemical sensor systems for medical and environmental applications.

Supervisor: dr hab. inż. Beata Paczosa-Bator

Faculty of Materials Science and Ceramics

Abstract: Electrochemical sensors as one of the simplest devices providing analytical information are gaining more and more popularity. Their unquestionable advantage is the ability to perform determinations directly in the sample taken, while the disadvantage is the need to perform the calibration based on which the result of the analysis is determined. The subject matter of the work is directly related to the development of multi-electrode systems of miniaturized sensors with limited need for calibration and ultimately its lacking. Metallic, carbon and ceramic nanomaterials will be used for this purpose. The developed multisensors will be designed for the determination of basic ionic components in medical and environmental samples.

Research facilities: The basic equipment and apparatus necessary to carry out the work is at the Faculty of Materials Science and Ceramics. Electrochemical analyzer Autolab PGSTAT 302N with FRA impedance spectroscopy module and EQCM electrochemical quartz microbalance system, automatic calibration system for Dosino electrodes (Metrohm, Swiss), multi-meter for measurement of sensor potential (Lawson, USA) will be used for electrochemical measurements. In addition, it is planned to use the SEM, TEM and AFM surface imaging methods and to examine the composition of EDS, IR and AAS. The work will be partially implemented as part of cooperation with the 3D-nano company specializing in in the development of new nanomaterials.

Number of places: 2

 

7. High sensitivity voltammetric determinations of selected analytes used in the treatment and prevention of selected diseases.

Supervisor: dr hab. inż. Robert Piech

Faculty of Materials Science and Ceramics

Abstract: Many analytical methods used in the determination of different analytes are often characterized by insufficient sensitivity, susceptibility to multiple interferences, high costs of a single determination and long analysis time. In the proposed subject, it is planned to use low-cost instrumental techniques - voltammetric, amperometric, and flow injection analysis for high-sensitivity determinations of specific substances. The studies will include: use of film electrodes with minimized mercury consumption, development of new electroactive layers as receptors for the construction of new voltammetric and amperometric sensors based on carbon nanoparticles and polymers with proton and mixed conductivity, development of the necessary operational methodology, development of calibration and validation principles, practical applications for the necessities of industrial control, pharmaceutical, clinical and environmental analysis.

Research facilities: The future promoter has the necessary equipment to perform voltammetric and amperometric measurements (two multifunctional electrochemical analyzers M161 with M163 electrode stands both mtm, Anko), a modular kit for flow injection analysis, a sufficient number of substrate electrodes (Mineral) and film electrodes.

Number of places: 1

 

8. A study of the effect of ZrO2 stabilization with calcium and magnesium on the catalytic activity of ZrO2/M-SrTi1-xMxO3 system (where M = Co, Ni, Cu) in hydrocarbon reforming reaction.

Supervisor: dr hab. Ewa Drożdż

Faculty of Materials Science and Ceramics

Abstract: The studies will concern the possibility of using ZrO2/M-SrTiO3 system based composite with mixed ionic-electronic conductivity in electrochemical systems fed with CH4 or higher hydrocarbons. The main aim of the work will be to obtain composite material composition optimal from the point of view of both, electrical (high mixed conductivity) and catalytic (high catalytic activity in the reaction of dry reforming and high selectivity to H2) properties. It is expected that the introduction of small amounts of element having catalytic activity in the above-mentioned reactions into strontium titanate structure, while simultaneously doping ZrO2 with calcium or magnesium, will result in a significant increase in the efficiency of the reforming reaction due to synergistic effect, while maintaining high values of electronic-ionic conductivity. As part of the work, it is planned a synthesize respective materials in ZrO2/M-SrTiO3 system and then their detailed characteristics in terms of structural (XRD, XPS), microstructural (SEM, mercury porosimetry, BET specific surface area measurements), and electrical (EIS) properties as well as the ability to participate in redox reactions (TPR / TPOx) and finally - performing catalytic tests. The research will be carried out at the Faculty of Materials Science and Ceramics, AGH University of Science and Technology. The cooperation with the Faculty of Chemistry at Jagiellonian University and the Faculty of Technical Physics and Applied Mathematics at Gdańsk University of Technology is also planned.

Research facilities: The vast majority of the equipment necessary to carry out the described studies is available at the Faculty of Materials Science and Ceramics AGH University of Science and Technology. Part of the research will be carried out in cooperation with other research centers:

- XPS measurements - Faculty of Technical Physics and Applied Mathematics, Gdańsk University of Technology,

- catalytic tests - in cooperation with the Faculty of Chemistry, Jagiellonian University in Krakow.

Number of places: 1

 

9. Alumina layers as catalyst carriers.

Supervisor: prof. dr hab. inż. Maciej Sitarz

Second supervisor: prof. dr hab. Joanna Łojewska

Faculty of Materials Science and Ceramics

Abstract: One of the main problems associated with the development of a structural reactor based on metal foams for methane post-combustion is the achievement of tight and stable at high temperatures layers that support catalysts and methods of applying the catalyst to the internal surfaces of foams. Therefore, as part of the PhD thesis, firstly, aluminum oxide-based layers obtained by various methods: sol-gel and/or electrophoretic deposition (EPD) will be developed. Subsequently, methods for applying catalysts will be developed. In both cases, different parameters of obtaining planned materials will be tested and optimized to obtain the most active material. The preparation will be correlated with the microstructure and structure analysis of the surface and the catalyst active centers and its activity based on the results of in situ and operando spectroscopic analyzes using surface probe molecules. This will allow optimizing the catalyst composition for the process being tested. Both the classic palladium catalyst and non-classical solutions based on cobalt spinel subsidized with a small amount of palladium will be used for optimization. For selected catalysts, based on DRIFT in situ analysis of reaction intermediates, a mechanism for methane post-combustion and developed methane post-combustion kinetics will be proposed. All this will enable the development of catalyst supports for structural reactors based on metal foams.

Research facilities: At the Faculty of Materials Science and Ceramics, there is a Laboratory of Thin Films and Coatings equipped with all necessary devices such as: mechanical stirrers with adjustable mixing and heating speed, dryers, etc. The equipment of this laboratory also includes devices specially designed for our needs, i.e. dip-coating and for application by the EPD method. All this equipment is necessary to obtain the planned layers on metallic substrates. The Faculty also has equipment for testing: a) the structure of the materials obtained - MIR and Raman spectrometers and XRD diffractometers that allow to conduct in-situ tests in a wide range of temperatures and in a controlled atmosphere. b) analysis of grain size and porosity, c) analysis of surface and chemical composition - SEM, TEM, AFM microscopy. At the Faculty of Chemistry of the Jagiellonian University (cooperation) in the Laboratory of Catalysis Research, whose head is Prof. J. Łojewska there are available apartus for catalytic tests - Catlab (Hiden). For the first two years, the doctorate will be financed by the grant „What if not ceramic monolith? Development of foam based catalytic converter for methane combustion” (Head – prof. M. Sitarz). Next, the Preludium grant is planned.

Number of places: 1

 

10. Geopolymer materials as a matrix for immobilization of dangerous ions.

Supervisor: prof. dr hab. inż. Włodzimierz Mozgawa

Second Supervisor: dr hab. inż. Magdalena Król

Faculty of Materials Science and Ceramics

Abstract: The project aims at elaboration a method of the synthesis of novel type of geopolymer composites as a matrix for disposal of bottom ash from waste incineration containing heavy metal ions. Particular emphasis will be placed on determining the effect of heavy metal ions on the structure of the obtained composites. Both aluminosilicate and boroaluminosilicate geopolymers will be analyzed, which will constitute an innovative approach to the analyzed problem. The implementation of the assumed objective will include the use of vibrational spectroscopy (both FT-IR and Raman) to describe the structure of the obtained materials. The interpretation of spectra will correlate with the results of theoretical research on structural models for which calculations using quantum mechanical methods will be carried out. The main goal of the project will be implemented in two threads. The first one will be focused on conducting structural studies of model systems corresponding to the hydration products of alkali-activated aluminosilicates, both in the absence and in the presence of heavy metal ions. The second part of the work will be the so-called application thread in which the actual bottom ash from waste incineration plants will be used as the raw material (in a mixture with coal fly ash) for alkali-activated pastes.

Research facilities: The proposed project will be implemented within of the NCN Opus 17 project No. 2018/31 / B / ST8 / 03109 "Structure of geopolymer material as a matrix for the immobilization of dangerous ions".

Number of places: 1