Surface Science: Foundations of Catalysis and Nanoscience

Chapter 6. Complex Surface Reactions: Catalysis & Etching: Supplemental Material

Wilhelm Ostwald won his 1909 Nobel Prize in Chemistry in recognition of his work on catalysis and for his investigations into the fundamental principles governing chemical equilibria and rates of reaction.

Heterogeneous catalysis was greatly advanced by the work of Paul Sabatier, who shared the 1912 Nobel Prize in Chemistry for, as stated by the Committee, "his method of hydrogenating organic compounds in the presence of finely disintegrated metals whereby the progress of organic chemistry has been greatly advanced in recent years." His work laid the basis of what would be developed into Fischer-Tropsch chemistry.

Fritz Haber won his Nobel Prize in Chemistry in 1918 for the synthesis of ammonia from its elemnets.

Carl Bosch, who commercialized the catalyst shared the 1931 Nobel Prize in Chemistry in recognition of his contributions to the invention and development of chemical high pressure methods. Haber is an interesting character, perhaps very much so in the sense of the Chinese proverb that it is a curse to be born in interesting times. Perhaps no scientific achievement has had more impact than the discovery of the nanostructured material that is the iron-based ammonia catalyst. It is estimated by Smil in his fascinating book Enriching the Earth: Fritz Haber, Carl Bosch, and the Transformation of World Food Production that 2.5 billion more people survive on the planet than would be possible without the iron catalyst. Yet in 1918 World War I was still being fought and Haber, who was an ardent nationalist, sought to help his country's war effort by introducing chemical weapons to the battlefield. This was a less admirable gift (pardon the pun in German) from Haber to mankind. Later, disgusted by Nazi Germany he would leave the country that he had long tried to serve, recognizing that this was not a regime that he could follow and that they were the ruin of his ideal of the German state. He died in exile. The Fritz-Haber-Institut in Berlin would later be named for him. Fritz's story has had an impact on me. Two tangible ways are that my grandfather was gassed in WWI. He survived but suffered lingering effects. Later, I took up a post doc at the FHI and worked in the very lab that Fritz had once used.

One of the most profound influences of the field of surface science was Irving Langmuir, who essentially established surface chemistry from a molecular perspective and was awarded the 1932 Nobel Prize in Chemistry. His research at the General Electric research labs were wide ranging. He sought literally to make a better ligh bulb and the pursuit (and achievement) of that goal lead him to fundemental studies of the interactions of gases with solid surfaces.

What is a catalytic converter? Engelhard has a site dedicated to their industrial engine emission control catalysts. Here's a link to catalysis at Haldor Topsoe. And a link to catalysis at Johnson Matthey.

BASF has a site dedicated to Milestones In Catalyst Development of BASF.

Franz Fischer and Hans Tropsch reported using Co, Fe & Ni catalysts to make liquid hydrocarbons from syngas (CO+H2) in 1926. There is a tremendous wealth of information on FT synthesis at the Fischer-Tropsch Archive. The site is a bit difficult to navigate but if you're interested, it's worth the effort. For instance, you can find a shed load of presentations.

Questions and Exercises

  1. What is the dispersion of a catalyst?
  2. What is the difference between a desorption limited TPD peak and a reaction limited TPD peak?
  3. State three advantages of using isotopic labelling in the study of surface reactions.
  4. What are active sites?
  5. Under normal conditions, dissociation of N2 to form 2N* is the rate determining step for ammonia synthesis. Under these conditions, how does the rate of every step that follows in series after the RDS compare to the rate of N* production?
  6. What are Fischer-Tropsch synthesis, steam reforming of methane, and the water-gas shift reaction?
  7. What is coking of a catalyst?
  8. Why does sintering reduce the activity of a dispersed transition metal catalyst?
  9. Why is methanol synthesis from syngas favoured by high pressure? Why is the favorability of high-pressure synthesis anticorrelated with the entropy change?
  10. What is spillover?
  11. What is the ligand effect?
  12. What is a bifunctional catalyst?
  13. What is asymmetric inhibition?
  14. What is the Sabatier principle?
  15. Does the presence of a poison or promoter affect the kinetics or thermodynamics of a reaction?

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