Where to go in electrochemistry? A personal view
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FEATURE ARTICLE
Where to go in electrochemistry? A personal view Ernesto J. Calvo 1 Received: 7 July 2020 / Revised: 7 July 2020 / Accepted: 8 July 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
In this report, we present a personal view on the present scientific challenges of electrochemistry in terms of fundamental understanding of electrochemical reactions and processes. In particular, we will illustrate a few examples with the oxygen electrode kinetics. To this end, we start by revising the fundamental contributions of electrochemistry as a branch of physical chemistry: Alessandro Volta developed the “Electrical Pile” in 1800 with the availability of electricity from chemical conversion. Michael Faraday formulated the law of electrolysis in 1834 relating the amount of matter to the electrical charge circulated. The development of the theory of electrolytes was advanced among others by Arrhenius, Vant’t Hoff, Debye, Hückel, Ostwald, Onsager, etc. Walter Nernst was able to measure entropy from the temperature dependence of electrochemical cells, which led to the formulation of the Third Principle of Thermodynamics and the Nobel Prize in 1921. A thermal theory of electrochemical reactions by Butler, Volmer, and Erdey-Gruz advanced understanding on the peculiar potential-current dependence described earlier by Julius Tafel in 1905 for the electrocatalytic hydrogen reduction reaction on different metals. Eyring, Laidler and Glasstone in 1939 applied for the first time the Theory of Absolute Reaction Rates to the overvoltage of the hydrogen electrode. The invention of polarography was the first automatic chemical analysis method which resulted in the Nobel Prize in Chemistry 1959 to Jaroslav Heyrovský. Following to the successful mercury drop electrode, with a renewable electrode surface, the more complex study of solid electrodes was approached among others by Bocrkris, Conway, Parsons, Gerischer, Vielstich, etc. More recently, electrodes were modified with molecules to achieve selectivity and biomolecules gave rise to electrochemical biosensors and biofuel cells [1]. The theory of the electron transfer reactions in chemistry by Marcus, Hush, Levich, Dogonadze, etc. was recognized in the
* Ernesto J. Calvo [email protected] 1
INQUIMAE, CONICET, University of Buenos Aires, Pabellón 2, Ciudad Universitria, AR-1428 Buenos Aires, Argentina
Nobel Prize in Chemistry to Rudolph Marcus in 1982 [2]. Finally, the predictions of Marcus on electrode kinetics were demonstrated in 1991 by Chris Chidsey in a very elegant experiment using self-assembled monolayers functionalized with ferrocene redox end groups [3]. Electrochemical industrial processes cover a wide range of society needs from chlorine-alkali industry to metal electrowinning and electrodeposition, from metal corrosion to chemical sensors and biosensors, and from systems for electrochemical energy conversion such as fuel cells to energy storage with batteries that evolved with the telegraph and the conquest of the far west in the USA to the
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