Syllabus
1) Introduction to catalysis General introduction and description of catalysis: Aims and scope of the course. Brief history of catalysis – Noble Prize winners in catalysis. Definition of a catalysed reaction Basic phenomena in catalytic reactions (physical and chemical steps); genegal mechanism of a catalysed reaction;7 steps in heterogeneously catalysed reaction. Thermodynamic aspect of catalysis – a catalyst will never influence a chemical equilibrium and why. Temperature effects in catalysis. Basic terms in catalysis: activation energy, Arrhenius equation, reaction coordinate, kvazi-stationary state assumtion, conversion, selectivity, TOF, TON, initial reaction rate, stability, environmental factor; and where these terms will apply. Definition and examples of homogeneous, heterogeneous, enzymatic, photocatalysis and electrocatalysis. Current challenges in catalysis; sustainable and green energy and technology transition
2) Kinetics and thermodynamics of catalysed reactions Rate determining step, kinetic vs. diffusion regime of a reaction, general conditions needed to achieve a kinetic regime. Diffusion in a catalyst; pore definition and classification. Role of adsorption in a catalytic reaction; physisorption, chemisorption, strenght of adsoprtion and its meassurement, isosteric heat of adsorption; adsorption site and active site, adsorption isotherms (Henry, Langmuir, Freudlich, BET). Basic mechamisms of heterogeneously catalysed reactions (Langmuir-Hinshelwood, Rideal-Eley, Mars-van Krevelen). Langmuir-Hinshelwood – examples of kinetic equations derivation; time dependence of the product composition for different types of reactions. Thiele modulus and catalyst usage efficiency (effectiveness factor).
3) Heterogeneous catalysis Types of heterogeneous catalysts; catalyst, support, binder, activator Nano – micro – macro – scale of a real catalyst Active sites in heterogeneous catalysts Zeolites: structure (primary and secondary building units, channel system, atlas of zeolites), synthesis (hydrothermal synthesis, template, mineralization agents), active sites (chemical composition of zeolites, acid sites (Bronsted vs. Lewis), ion-exchanging properties, redox centres), application examples. Oxidic and sulphidic catalysts Raney metals Supported metal catalysts – why do we need a support? Bifunctional catalysts – metal support synergy; metals in zeolites, metal nanoparticles encapsulation, acidic+redox catalysts.
4) Homogenous catalysis (organocatalysis) General approach; TON and catalyst lifetime Selected types of homogeneous catalysts – acids, organometallic complexes, chiral complexes Application examples and discussing particular catalyst structure Asymmetric hydrogenation, BINAP and role of ligands in OM complexes Hydroformylation Ziegler-Natta catalysts, propylene polymeration Heterogenization of homogeneous catalysts: functionalization of support; modification of aluminosilicate support (e.g. metallocenes for polymeration); biphase catalysis
5) Enzymatic catalysis, photocatalysis, electrocatalysis General approaches, TON and lifetime in enzymatic catalysis; general mechanism of enzymatic reaction; Michaelis-Menton kinetics Practical use of enzymes: enzyme catalysed sugar isometrization; enzyme encapsulation Inhibition of enzymatic reactions
6) Catalyst preparation and characterization Lab scale – pilot plant – industrial synthesis Resources: lab vs. industry Catalyst characterisation: Powder X-ray diffraction Electron microscopy techniques MAS NMR EXAFS/XANES Infrared spectroscopy Chemical analysis Adsorption techniques
7) Catalytic experiment and related analytical techniques Aim of a catalytic test Research vs. industrial catalyst Lab scale catalytic experiment: apparatus and methodology; reactors, saturators, linear pumps and other dosing systems Basic types of catalytic reactors, size of a catalyst bed, particle size Test on kinetic vs. diffusion regime Catalyst dezactivation Analytical techniques for catalytic reactions Chromatography Infrared spectroscopy Mass spektrometry In-situ a Operando techniques
8) Invited talk on selected topic given by an expert in the field
Annotation
Catalysis represents is essential in production of intemediates as well as final products of chemical industry. 85-90% of industrial processes are designed with involvement of some catalyst. The aim of this course is to introduce fundamental principles of catalysis. The course will focus on understanding the role of catalysts and their behavior in catalytic reactions, reaction mechanisms, and application of the most important experimental techniques in catalyst characterization and evaluation in catalytic reactions. The lectures (2 hours per week in average) will be accompanied by exercises or experimental practices (1 hour per week in average).
General knowledge of inorganic, organic and physical chemistry is expected. The course if followed by Catalysis is Practice course.
During the COVID restrictions, the lectures will be held online via Zoom application and seminars will use google classroom/google meet environment.