Electrochemical activation of catalysis: promotion, by Costas G. Vayenas, Symeon Bebelis, Costas Pliangos, Susanne

By Costas G. Vayenas, Symeon Bebelis, Costas Pliangos, Susanne Brosda, Demetrios Tsiplakides

I knew not anything of the paintings of C. G. Vayenas on NEMCA until eventually the early nineties. Then I realized from a paper of his notion (gas interface reactions might be catalyzed electrochemically), which appeared rather great; yet i didn't know how it labored. therefore, i made a decision to correspond with Professor Vayenas in Patras, Greece, to arrive a greater figuring out of this idea. i feel that my early papers (1946, 1947, and 1957), at the dating among the paintings functionality of steel surfaces and electron move reactions thereat to debris in resolution, held me in solid stead to be receptive to what Vayenas informed me. because the electrode power alterations, so after all, does the paintings functionality on the interface, and fuel steel reactions there contain adsorbed debris that have bonding to the outside. no matter if electron move is whole in this kind of case, or even if the impression is at the desorption of radicals, the paintings functionality determines the power in their bonding, and if one varies the paintings functionality by way of various the electrode strength, you'll range the response price on the interface. I bought the belief. After that, it's been soft crusing. Dr. Vayenas wrote a seminal article in sleek features of Electrochemistry, quantity 29, and taken the sphere into the general public eye. It has due to the fact grown and its usefulness in chemical catalytic reactions has been proven and confirmed around the globe.

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Upon plotting the data vs work function (Fig. 6c) a linear variation is observed with a positive slope. As we shall see below and throughout this book this type of behaviour is quite common and reflects strong lateral repulsive interactions between the adsorbed atoms. The strong lateral repulsive interactions between the adatoms favours uniform distribution of alkali promoters on catalyst surfaces and formation of ordered structures. 30,31 Only the Na adatoms are to be seen in this STM (Scanning tunneling microscopy) image, not the underlying Pt(111)-(2×2)-O adlattice which we shall see in more detail in Chapter 5.

But the fact is that positive potentials (+1V) can further significantly enhance the performance of an already promoted catalyst. So one can electrochemically promote an already classically promoted catalyst. Why do negative potentials fail to further enhance to any significant extent catalyst performance of the promoted catalyst whereas the unpromoted Rh catalyst is electrochemically promoted with both positive and negative potentials? (Fig. 3). The answer will become apparent in subsequent chapters: In a broad sense negative potential application is equivalent to alkali supply on the catalyst surface.

Bockris, Electrochimica Acta, 19947 Despite the surprise caused by the first literature reports of such large nonFaradaic rate enhancements, often accompanied by large variations in product selectivity, in retrospect the existence of the NEMCA effect can be easily rationalized by combination of simple electrochemical and catalytic principles. g. g. direct reaction of with CO). In case (c), however, the new species introduced electrochemically onto the catalyst surface will interact with coadsorbed reactants and will change the catalytic properties of the catalyst surface in an a priori unpredictable manner, which is nevertheless not subject to Faraday’s law.

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