Electrochemical Activation of Catalysis

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I knew nothing of the work of C.

Electrochemical Activation of Cp* Iridium Complexes for Electrode-Driven Water-Oxidation Catalysis

Then I learned from a paper of his idea gas interface reactions could be catalyzed electrochemically , which seemed quite marvelous; but I did not understand how it worked. Consequently, I decided to correspond with Professor Vayenas in Patras, Greece, to reach a better understanding of this concept.

Energy Diagrams, Catalysts, and Reaction Mechanisms

I think that my early papers , , and , on the relationship between the work function of metal surfaces and electron transfer reactions thereat to particles in solution, held me in good stead to be receptive to what Vayenas told me. As the electrode potential changes, so of course, does the work function at the interface, and gas metal reactions there involve adsorbed particles which have bonding to the surface.

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Whether electron transfer is complete in such a case, or whether the effect is on the desorption of radicals, the work function determines the strength of their bonding, and if one varies the work function by varying the electrode potential, one can vary the reaction rate at the interface. I got the idea. After that, it has been smooth sailing.

Vayenas wrote a seminal article in Modern Aspects of Electrochemistry, Number 29, and brought the field into the public eye.


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It has since grown and its usefulness in chemical catalytic reactions has been demonstrated and verified worldwide. No matching affiliation detected.


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Find all citations in this journal default. Or filter your current search. Journal of the American Chemical Society [22 Sep , 39 ].

Electrochemical activation of molecular catalysts : from basics to applications

Abstract Organometallic iridium complexes bearing oxidatively stable chelate ligands are precursors for efficient homogeneous water-oxidation catalysts WOCs , but their activity in oxygen evolution has so far been studied almost exclusively with sacrificial chemical oxidants. We have ruled out the formation of heterogeneous iridium oxides, either as colloids in solution or as deposits on the surface of the electrode, and found indication that the conversion of the precursor to the active molecular species occurs by a similar process whether carried out by chemical or electrochemical methods.

This work makes these WOCs more practical for application in photoelectrochemical dyads for light-driven water splitting. Read Article at publisher's site.

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