Catalysts for heterogeneous catalysis

Aims:
Explain the role of catalysts in chemical processes.
Describe catalyst surface structures.
Determine possible rate-limiting processes.
Define active sites.
Explain why only certain surface atoms are catalytically active.
Relate catalyst structure to catalytic behavior.
Distinguish among common catalytic mechanisms.
Analyze experimental kinetic data.
Select appropriate characterization methods.
Interpret basic characterization data.
Identify common deactivation mechanisms.
Connect catalytic principles to industrial processes.

Required prerequisite knowledge from courses: Materials chemistry and Functional materials.

1. Introduction to Catalysis
   (Definition of catalysis and basic terminology)

2. Catalyst Solids and Surface Structure
   (Surface energy and surface reconstruction, Metal catalysts, Oxide catalysts, Zeolites and porous materials, Supported catalysts)

3. Elementary Steps in Heterogeneous Catalysis
   (External mass transfer, Internal diffusion, Adsorption, Surface reaction, Desorption, Product transport)

4. Active Sites and Structure–Activity Relationships
   (Definition of active sites, Surface defects
   Steps, edges, and kinks, Electronic effects, Metal-support interactions, Redox active sites)

5. Catalytic Reaction Mechanisms
   (Langmuir–Hinshelwood mechanism, Eley–Rideal mechanism, Mars–van Krevelen mechanism)

6. Kinetics of Heterogeneous Catalysis
   (Rate expressions, Surface coverage effects, Apparent activation energy, Reaction orders)

7. Catalyst Characterization Techniques
   (X-ray Diffraction, Electron Microscopy, Surface Characterization, Surface Area and Porosity, Spectroscopic Methods, Temperature Programmed Methods)

8. Catalyst Deactivation and Regeneration
   (Coking, Poisoning, Sintering, Fouling)

9. Industrial and Emerging Applications
   (Industrial Case Studies: Haber–Bosch ammonia synthesis, Fluid catalytic cracking (FCC), Methanol synthesis, Automotive catalytic converters)

Emerging Topics
(Photocatalysis, Inductively heated reactors, CO₂ utilization, Green hydrogen production)

Knowledge and understanding:
Understanding of heterogeneous catalysis.
Understanding of basic characteristics of heterogeneous catalysts.
Knowledge on design and development of industrial catalysts.

• G. Ertel, H. Knozinger, F. Schuth, J. Weitkamp, Handbook of Heterogeneous Catalysis, Wiley, Weinheim, 2008. E-gradivo
• E. Roduner, Understanding catalysts, TUTORIAL REVIEW ChemSocRev 2014. https://doi.org/10.1039/C4CS00210E
• Selected websites and review scientific articles on specific areas published

• Oral exam.
• Public presentation and defense of seminar

Dr. Petar Djinović is an Associate Professor in the field of Materials and a Senior Research Associate at the National Institute of Cemistry. His research focuses on heterogeneous catalysis, particularly the synthesis, characterization, and application of metallic and oxide nanomaterials as catalysts in efficient carbon dioxide conversion processes, such as the production of synthesis gas from methane and carbon dioxide, the hydrogenation of CO₂ to methane, and the conversion of hydrocarbons (including dehydrogenation and selective oxidation reactions). More recently, he has increasingly focused on the use of in situ and operando spectroscopic characterization techniques to monitor the dynamic behavior of catalysts during chemical reactions in real time.

1. OKORN, Miha, LORBER, Kristijan, MAZAJ, Matjaž, NOVAK TUŠAR, Nataša, DJINOVIĆ, Petar. Simultaneous photoactivation of copper and Ti-doped CeO2−x enables optimal acceleration of the RWGS reaction. Carbon energy. 2025. https://onlinelibrary.wiley.com/doi/epdf/10.1002/cey2.70102, DOI: 10.1002/cey2.70102.

2. LORBER, Kristijan, SHVALYA, Vasyl, ZAVAŠNIK, Janez, VENGUST, Damjan, ARČON, Iztok, HUŠ, Matej, PAVLIŠIČ, Andraž, TERŽAN, Janvit, CVELBAR, Uroš, LIKOZAR, Blaž, DJINOVIĆ, Petar. Non-oxidative calcination enhances the methane dry reforming performance of Ni/CeO2−x catalysts under thermal and photo-thermal conditions. Journal of materials chemistry. A. 2024. https://pubs.rsc.org/en/content/articlelanding/2024/ta/d4ta01823k, DOI: 10.1039/D4TA01823K.

3. LORBER, Kristijan, ZAVAŠNIK, Janez, SANCHO-PARRAMON, Jordi, BUBAŠ, Matej, MAZAJ, Matjaž, DJINOVIĆ, Petar. On the mechanism of visible-light accelerated methane dry reforming reaction over Ni/CeO2−x catalysts. Applied catalysis. B, Environmental. 2022. https://dirros.openscience.si/IzpisGradiva.php?id=14939, DOI: 10.1016/j.apcatb.2021.120745.

4. LORBER, Kristijan, DJINOVIĆ, Petar. Accelerating photo-thermal CO2 reduction to CO, CH4 or methanol over metal/oxide semiconductor catalysts. iScience. 2022. https://www.sciencedirect.com/science/article/pii/S2589004222003777, DOI: 10.1016/j.isci.2022.104107.

5. DJINOVIĆ, Petar, ZAVAŠNIK, Janez, TERŽAN, Janvit, JERMAN, Ivan. Role of CO2 during oxidative dehydrogenation of propane over bulk and activated-carbon supported cerium and vanadium based catalysts. Catalysis letters. 2021. https://link.springer.com/article/10.1007/s10562-020-03519-y, DOI: 10.1007/s10562-020-03519-y.