CHEM 710/7100 - Homogeneous and Heterogeneous Catalysis

Semester: Fall 2021

Professor: M. Schlaf | Discipline: Inorganic | Campus: Guelph

Description

This course will provide an introduction and overview of the field of catalysis using (supported) heterogeneous metal/metal oxide and transition metal complexes focusing on

  • general principles and reaction patterns of catalytically active transition metal centres,  metal/metal oxide surfaces and supported metals.
  • mechanisms: kinetic and thermodynamic parameters and how to determine them.
  • activation of small molecules such as hydrogen, carbon monoxide, carbon dioxide, methane, ethylene, propylene, ethylene oxide, etc.
  • large scale industrially relevant processes and their socio-economic importance.

The ultimate objective of the course is to provide you with the know-how to understand (or at least make some educated guesses on) the mechanisms of any catalyzed reactions and have some insight into the principles of catalyst, reaction and process design. The course will be – as much as possible – conceptual in nature and thus should be suitable for students in any field of chemistry (inorganic, organic, physical and analytical) with 3rd year level undergraduate courses in inorganic and organic chemistry.

Tentative topics to be covered in lectures:

  1. What is catalysis ? Some simple truth and definitions: TOF, TON, catalyst life-times and space-time yields.
  2. Homogeneous vs heterogeneous catalysts.
  3. Heterogeneous catalysts: types of catalysts, active sites and defects.
  4. Synthesis and characterization of metal and metal oxide catalysts.
  5. Types of reactors and some important heterogeneously catalyzed processes.
  6. Homogeneous catalysts: Overview of types of ligands and their electronic and steric properties. Reaction patterns of transition metal centres and their coordinated ligands.
  7. The tools of the trade: mechanistic investigations through thermodynamic, kinetic and isotope labelling studies.
  8. Two historical perspectives on homogeneous catalysts: The Wacker process and Wilkinson’s Catalyst.
  9. Hydrogenation and hydrogenolysis reactions beyond Wilkinson: The Shvo and Noyori systems: ionic and enantioselective hydrogenations.
  10. Oxidation and epoxidation beyond Wacker: The search for efficient and “green” aerobic oxidation catalysts. The Sharpless catalyst.
  11. Adding carbons I:  Hydroformylation, hydrocyanation, carbonylation, Fischer-Tropsch chemistry and related reactions – the Monsanto process.
  12. Adding carbons II: Oligomerization and dimerization reactions. The Shell Higher Olefin Process (SHOP). Metallocenes and other single-site polymerization catalysts. Metathesis reactions and ROMP using Grubb’s catalyst.
  13. The Holy Grail I: Catalytic C-H bond activation in simple hydrocarbons: The Catalytica process (Periana Catalyst) and related fundamental processes.
  14. The Holy Grail II: Catalytic Hydrodeoxygenation of biomass to fuel and chemicals.
  15. Cross-coupling and other miscellaneous reactions: Heck, Stille, Sonogashira, Hartwig, Buchwald, etc.
  16. Doing things differently: Ionic liquids, supercritical solvents and homogeneous catalysts on solid supports: Biphasic reactions and catalyst recovery and reuse.
  17. … we will see !

Materials

No textbook – instead extensive lecture notes and reading material in form of primary (i.e., research articles) and secondary (i.e., review articles) will be made available online for download.

Evaluation

Midterm (take-home with online submission):   40 %

Presentation                                                     30 %

Research proposal (as take-home final)         30 %

Lab/Project

No laboratory component.

Each student in the course will be required to give a ~30 min. presentation (PowerPoint or OpenOffice – max. 30 slides) on a topic of his/her choice within the field of catalysis. In order to coordinate this effort and avoid overlap, I will suggest and discuss potential topics in the first class.

The final exam will be take-home in the form of a research proposal in NSERC format (5 pages  + 1 page literature) on a specific topic of your choice within the field of homogeneous catalysis. The proposal and presentation cannot be on the same topic. Proposals can also not be on a topic covered by someone else in class. Guidelines on the preparation of NSERC proposals can be found on the NSERC website at www.nserc.ca.  The proposal should give a brief 2-2 1/2 pages mini-review of the (patent) literature relevant to your chosen topic and include mechanistic and/or synthetic discussion and a 2 -2 1/2 page description of the actual research proposed outlining the conceptual and experimental approach.

Due date for take-home exam (research proposal): 2021-12-03

Required mode of submission of your research proposal is as a word processor or pdf file by e-mail to [email protected] or by upload to the Course Cloud (login & password to be announced).

Schedule
Time: Monday evenings, 19:00 – 21:00 h

Location: Mini-Link room, (C2-278/MACN-203)

Simulcasted and recorded on TEAMS or ZOOM (tbd).

Start: 2021-09-13

No class on Monday 2021-10-11 – Thanksgiving.
Midterm: As a take-home exam – dates to be determined by in class discussion and dependent on the number of students in the course.

Student Lectures: TBA – depends on the number of students in the course.

End: 2021-12-03 (Friday – rescheduled from Thanksgiving as per UofG calendar).

Schedule

  • Mon: 7:00 pm - 9:20 pm in MacN 203/C2 278

Office Hours

Anytime as needed by appointment in person or online remote by TEAMS, ZOOM or SKYPE.