Non-linear and co-operative mechanisms of irreversible thermodynamics have not yet been adequately considered and explored for electrocatalysis even though it is probable that nature has exploited its advantages in biological structures. In the presence of positive feedback mechanisms (autocatalysis) a series of new electron-transfer phenomena, such as highly directional electron-transfer, co-operative multi-electron transfer, breakdown of resistivity and activation complexes generated as dissipative structures, become in principle possible. They may also enable the generation of order (local reduction of entropy) for the purpose of stabilizing a reactive interface and for molecular synthesis. In view of this approach the molecular function of the manganese centre of photosynthesis is re-evaluated and etectrochemically generated porous silicon interpreted as a product of a dissipative structure produced by autocatalytic reaction steps.