Issue 24, 2014

Understanding catalysis

Abstract

The large majority of chemical compounds underwent at least one catalytic step during synthesis. While it is common knowledge that catalysts enhance reaction rates by lowering the activation energy it is often obscure how catalysts achieve this. This tutorial review explains some fundamental principles of catalysis and how the mechanisms are studied. The dissociation of formic acid into H2 and CO2 serves to demonstrate how a water molecule can open a new reaction path at lower energy, how immersion in liquid water can influence the charge distribution and energetics, and how catalysis at metal surfaces differs from that in the gas phase. The reversibility of catalytic reactions, the influence of an adsorption pre-equilibrium and the compensating effects of adsorption entropy and enthalpy on the Arrhenius parameters are discussed. It is shown that flexibility around the catalytic centre and residual substrate dynamics on the surface affect these parameters. Sabatier's principle of optimum substrate adsorption, shape selectivity in the pores of molecular sieves and the polarisation effect at the metal–support interface are explained. Finally, it is shown that the application of a bias voltage in electrochemistry offers an additional parameter to promote or inhibit a reaction.

Graphical abstract: Understanding catalysis

  • This article is part of the themed collection: Primer

Supplementary files

Article information

Article type
Tutorial Review
Submitted
20 6 2014
First published
14 10 2014

Chem. Soc. Rev., 2014,43, 8226-8239

Author version available

Understanding catalysis

E. Roduner, Chem. Soc. Rev., 2014, 43, 8226 DOI: 10.1039/C4CS00210E

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