Electrochemical Promotion of Catalysis

Electrochemical Promotion of Catalysis (EPOC), also called Non-Faradaic Electrochemical Modification of Catalytic Activity (NEMCA), is a promising concept for boosting catalytic processes and advancing the frontiers of catalysis [1]. This innovative field aims to modify in-operando both the activity and the selectivity of catalysts, in a reversible and controlled manner. EPOC utilizes solid electrolyte materials (ionically conducting ceramics) as catalytic carriers. Ions contained in these electrolytes are electrochemically supplied to the catalyst surface and act as promoting agents to modify the catalyst electronic properties in order to achieve optimal catalytic performance. It thus provides a unique means of varying promoter levels at the metal surface under reaction conditions by simply changing the potential of the catalyst film. The main advantage of EPOC is that the electrochemical activation magnitude is much higher than that predicted by Faraday’s law. Therefore, EPOC requires low currents or potentials. Moreover, promoting species such as O2- cannot be formed via gaseous adsorption and cannot be easily dosed by chemical ways. The EPOC technology consists in the implementation of catalysis in an electrochemical cell by using electrochemical catalysts which consist of a catalytic layer interfaced on an ionically conducting ceramic support. The latter serves as an electrically controlled source or sink of ionic promoter species that activate and modulate the behavior of the catalytic surface. Figure 1a displays a typical EPOC reactor. The catalytic layer, typically 40 nm to 10 mm thick, is deposited on a dense solid electrolyte membrane (Figure 1a). This catalytic layer must be electronic conductor to allow the polarization. Therefore, the catalyst is also an electrode and is then named catalyst-electrode. A counter-electrode and a reference electrode, both catalytically inert, are deposited on the other side of the membrane (Figure 1a). An electrical current density (1-500 µA/cm2) or potential (±2 V) is applied between the catalyst and the counter electrode. The reactants are co-fed over the porous electrochemical catalytic layer. Figure 1b displays a typical example of an EPOC experiment for the propane deep oxidation. The electrochemical catalyst was composed of a Pt thin film deposited by Physical Vapor Deposition (PVD) on a dense membrane of Yttria-Stabilized Zirconia (YSZ), an O2- ionic conductor. A positive current (from +10 up to +500µA) can strongly increase the propane conversion with a non-Faradaic manner, since the activation is up to 300 times higher than that predicted by the Faraday’s law through the electrochemical oxidation of propane. This latter reaction will be used to highlight recent advances of the EPOC technology both for the understanding (18O2 isotopic exchange) of the process and its applications via the proof of concept of electropromoted nanoparticles. [1] P. Vernoux, L. Lizarraga, M.N. Tsampas, F.M. Sapountzi, A. De Lucas-Consuegra,  J.L. Valverde, S. Souentie, C.G. Vayenas, D. Tsiplakides, S. Balomenou, E.A. Baranova, Chem. Rev. 113 (2013) 8192. Figure 1