Promoters, adsorption theory, catalyst criteria

Promoters

Promoters (activators) are substances that, though not themselves catalysts, increase the activity of a catalyst when added in a small quantity. They may increase the active surface or change the crystal structure (creating more defects/active sites), or they may improve the adsorption of the reactants.

• In Haber's process, Mo (or Al₂O₃ + K₂O) is a promoter for the iron catalyst.
• In the water-gas shift reaction, Cr₂O₃ promotes Fe₂O₃.
• Cu promotes Ni in some hydrogenation reactions.

Adsorption theory of catalysis

According to the adsorption theory (for heterogeneous catalysis), the catalyst works by adsorbing the reactant molecules on its surface. The steps are:

1. Diffusion and adsorption: reactant molecules diffuse to the catalyst surface and are adsorbed on the active sites, so their concentration at the surface becomes high.
2. Activation: adsorption weakens the bonds of the reactants (e.g. H–H breaks), forming activated, reactive species. Adsorption is exothermic, and the heat released helps to supply activation energy.
3. Surface reaction: the activated adsorbed molecules, now close together, react to form the product.
4. Desorption: the product molecules have little affinity for the surface; they leave the surface, which frees the active sites.
5. The freed sites adsorb new reactant molecules and the cycle repeats.

 H₂    C₂H₄          H–H  C=C         H H
  ↓     ↓             ↓    ↓           | |
 ▒▒▒▒▒▒▒▒▒▒▒  →  ▒▒▒▒▒▒▒▒▒▒▒  →   H–C–C–H   (leaves)
 Ni surface      adsorbed, H–H      | |
 (adsorption)    bond broken        H H

Example: hydrogenation of ethene on nickel: C₂H₄ + H₂ → C₂H₆ (Ni). H₂ is adsorbed on Ni and splits into H atoms, ethene is also adsorbed, the H atoms add to the double bond, and ethane is desorbed.

The theory explains why a finely divided catalyst is more active (larger surface), why poisons stop catalysis (they occupy the active sites) and why promoters help (they increase the active surface).

Criteria of an industrial catalyst

• High activity: gives a high rate at moderate temperature and pressure.
• High selectivity: favours the desired product and avoids side reactions.
• Stability / long life: keeps its activity for long periods at working temperature and pressure; good mechanical strength.
• Resistance to poisons, and easy regeneration if poisoned.
• Large surface area (finely divided or porous, or on a support).
• Low cost and ready availability; easily separated from the products.