Electrochemical promotion effect

D.I. Kondarides, G.N. Papatheodorou, C.G. Vayenas, and X.E. Verykios, In situ High Temperature SERS study of Oxygen adsorbed on Ag Support and Electrochemical Promotion Effects, Ber. Buns. Phys. Chem. 97, 709-720 (1993). 

The observed pronounced electrochemical promotion effect is due to the weakening of the Rh = O bond and the strengthening of the bond... 

In this region of classical Ir02 promotion by Ti02 (0[Pg.375]

Interestingly the electrochemical promotional effect was found only in the case of perchloric acid supporting electrolyte. No promotion effect was found in presence of strongly adsorbed anions (HS04 Cl ). 

The significance of Equation (11.31), in conjunction with Figure 11.13 and the definitions of 11, P and J (Table 11.1) is worth emphasizing. In order to obtain a pronounced electrochemical promotion effect, i.e. in order to maximize p (=r/ro), one needs large II and r p values. The latter requires large J and small 0P values (Fig. 11.13). Small k and L values satisfy both requirements (Table 11.1). This implies that the promoting species must not be too reactive and the catalyst film must be thin. 

Catalyst films used in electrochemical promotion (NEMCA) studies are usually prepared by using commercial metal pastes. Unfluxed pastes should be used, as fluxes may introduce unwanted side reactions or block electrocatalytic and catalytic sites. This action may obscure or even totally inhibit the electrochemical promotion effect. 

Before starting an electrochemical promotion experiment, one should check carefully that the catalytic reaction under study is not subject to external or internal mass transfer limitations within the desired operating temperature range, which can obscure or even completely hide the electrochemical promotion effect. 

The electrochemical promotion effect, or nonfaradaic electrochemical modification of catalytic activity (NEMCA), is due to the controlled migration (backspillover) of ions from the solid electrolyte to the gas-exposed catalyst-electrode surface under the influence of the applied current or potential." ... 

Thus, as will be shown in this book, the effect of electrochemical promotion (EP), or NEMCA, or in situ controlled promotion (ICP), is due to an electrochemically induced and controlled migration (backspillover) of ions from the solid electrolyte onto the gas-exposed, that is, catalytically active, surface of metal electrodes. It is these ions which, accompanied by their compensating (screening) charge in the metal, form an effective electrochemical double layer on the gas-exposed catalyst surface (Fig. 1.5), change its work function and affect the catalytic phenomena taking place there in a very pronounced, reversible, and controlled manner. 

Can one further enhance the performance of this classically promoted Rh catalyst by using electrochemical promotion The promoted Rh catalyst, is, after all, already deposited on YSZ and one can directly examine what additional effect may have the application of an external voltage UWR ( 1 V) and the concomitant supply (+1 V) or removal (-1 V) of O2 to or from the promoted Rh surface. The result is shown in Fig. 2.3 with the curves labeled electrochemical promotion of a promoted catalyst . It is clear that positive potentials, i.e. supply of O2 to the catalyst surface, further enhances its performance. The light-off temperature is further decreased and the selectivity is further enhanced. Why This we will see in subsequent chapters when we examine the effect of catalyst potential UWR on the chemisorptive bond strength of various adsorbates, such as NO, N, CO and O. 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. 

In fact, the key to understand electrochemical promotion is to understand the mechanism by which the effect of polarization at the catalyst/electrolyte interface propagates to the catalyst/gas interface ... 

Normally in heterogeneous catalysis compensation effect behaviour is obtained either for the same reaction upon using differently prepared catalysts of the same type, or with the same catalyst upon using a homologous set of reactants. In the case of electrochemical promotion (Figs. 4.38 and 4.39) one has the same catalyst and the same reaction but various potentials, i.e. various amounts of promoter on the catalyst surface. 

As already noted the strength of chemisorptive bonds can be varied in situ via electrochemical promotion. This is the essence of the NEMCA effect. Following initial studies of oxygen chemisorption on Ag at atmospheric pressure, using isothermal titration, which showed that negative potentials causes up to a six-fold decrease in the rate of 02 desorption,11 temperature programmed desorption (TPD) was first used to investigate NEMCA.29... 

One of the most interesting and potentially important from a practical viewpoint aspect of electrochemical promotion is the permanent NEMCA effect first discovered and studied by Comninellis and coworkers at Lausanne. 

Figure 4.53. Effect of temperature on the faradaic efficiency, A, values measured in electrochemical promotion (NEMCA) studies of C2H4 oxidation on various metals.30 Reprinted with permission from Academic Press.

The unique characteristic of the effective double layer is that it is directly accessible to gaseous reactants. Thus electrochemical promotion is catalysis in the presence of a controllable (via current and potential) electrochemical double layer. The theoretical implications and practical opportunities are obvious and numerous. 

Figure 6.3. Examples for the four types of global electrochemical promotion behaviour (a) electrophobic, (b) electrophilic, (c) volcano-type, (d) inverted volcano-type, (a) Effect of catalyst potential and work function change (vs I = 0) for high (20 1) and (40 1) CH4 to 02 feed ratios, Pt/YSZH (b) Effect of catalyst potential on the rate enhancement ratio for the rate of NO reduction by C2H4 consumption on Pt/YSZ15 (c) NEMCA generated volcano plots during CO oxidation on Pt/YSZ16 (d) Effect of dimensionless catalyst potential on the rate constant of H2CO formation, Pt/YSZ.17 n=FUWR/RT (=A(D/kbT).

Electrochemical promotion studies have used from the beginning5 7 two very simple qualitative rules in order to explain all the observed effects of varying potential Uwr or work function d> on the reaction kinetics ... 

Such a model should be as simple as possible, without however missing any of the underlying thermodynamic and physicochemical factors which cause electrochemical promotion. In particular it will be shown that even the use of Langmuir-type adsorption isotherms, appropriately modified due to the application of potential (or equivalently by the presense of promoters) suffice to describe all the experimentally observed rules G1 to G7 as well as practically all other observations regarding electrochemical promotion including the effect of potential on heats of adsorption as well as on kinetics and reaction orders. 

In the case of electrochemically promoted (NEMCA) catalysts we concentrate on the adsorption on the gas-exposed electrode surface and not at the three-phase-boundaries (tpb). The surface area, Ntpb, of the three-phase-boundaries is usually at least a factor of 100 smaller than the gas-exposed catalyst-electrode surface area Nq. Adsorption at the tpb plays an important role in the electrocatalysis at the tpb, which can affect indirectly the NEMCA behaviour of the electrode. But it contributes little directly to the measured catalytic rate and thus can be neglected. Its effect is built in UWr and [Pg.306]

It will also be shown that the absolute electrode potential is not a property of the electrode but is a property of the electrolyte, aqueous or solid, and of the gaseous composition. It expresses the energy of solvation of an electron at the Fermi level of the electrolyte. As such it is a very important property of the electrolyte or mixed conductor. Since several solid electrolytes or mixed conductors based on ZrC>2, CeC>2 or TiC>2 are used as conventional catalyst supports in commercial dispersed catalysts, it follows that the concept of absolute potential is a very important one not only for further enhancing and quantifying our understanding of electrochemical promotion (NEMCA) but also for understanding the effect of metal-support interaction on commercial supported catalysts. 

The presence of this backspillover formed effective double layer is important not only for interpreting the effect of electrochemical promotion, but also for understanding the similarity of solid state electrochemistry depicted in Fig. 7.3 with the case of emersed electrodes in aqueous electrochemistry (Fig. 7.2) and with the gedanken experiment of Trasatti (Fig. 7.1) where one may consider that H2O spillovers on the metal surface. This conceptual similarity also becomes apparent from the experimental results. 

Equations (7.11) and (7.12) provide a firm basis for understanding the effect of Electrochemical Promotion but also provide an additional, surface chemistry, meaning to the emf of solid electrolyte cells in addition to its usual Nerstian one. 

Figure 8.12. Effect of Ir02 mol fraction in the Ir02-Ti02 catalyst on the open-circuit catalytic rate, r0 of C2H4 oxidation (O), on the electrochemically promoted (1=200 pA) catalytic rate, r, ( ) and on the corresponding rate enhancement ratio p (A).19 (T=380°C, pO2=20 kPa, Pc2h4=0.15 kPa).

Figure 8.62 shows the effect of temperature and of positive potential application on the reaction rates and on the nitrogen selectivity for the C3H6/N0/02 reaction.67,68 Electrochemical promotion significantly enhances both activity and N2 selectivity (e.g. from 58% to 92% at 350°C) and causes a pronounced (60°C) decrease in the light-off temperature of NO reduction in presence of 02. Positive potentials weaken the Rh=0 bond, decrease the O coverage and thus liberate surface sites for NO adsorption and dissociation. 

The effect shown in Figs. 4.30, 9.4 and 9.5 is quite reversible and the catalyst restores its Na-free activity upon pumping away the Na from the catalyst surface by increasing the catalyst potential. NASICON could be used as an alternative to (3"-Al203 for potential practical applications of electrochemical promotion due to its better thermal stability and resistance to water vapour. 

As shown in Fig. 9.25, upon current interruption rH2, ro and Urj,e return to their open circuit values, showing the reversibility of the effect. It is worth noting that the rate transient parallels, to a large extent, the catalyst potential. This shows the important role of catalyst potential in describing electrochemical promotion. 

Figure 11.4. Effect of the mole fraction, XIro2, of Ir02 in the Ir02-Ti02 catalyst film on the rate of C2H4 oxidation under open-circuit conditions (open circles) and under electrochemical promotion conditions (filled circles) via application of 1=200 pA T=380°C, Pc2h4=015 kPa, Po2=20 kPa. Triangles indicate the corresponding electrochemical promotion rate enhancement ratio p values.22,29...

Figure 11.8. Effect of po2 on the rate (TOF) of C2H4 oxidation on Rh supported on five supports of increasing d>. Catalyst loading 0.5wt%.22,27 Inset Electrochemical promotion of a Rh catalyst film deposited on YSZ Effect of potentiostatically imposed catalyst potential Uwr on the rate and TOF dependence on po2 at fixed Pc2H4-22,33 Reprinted with permission from Elsevier Science (ref. 27) and Academic Press (ref. 33).

An important question frequently raised in electrochemical promotion studies is the following How thick can a porous metal-electrode deposited on a solid electrolyte be in order to maintain the electrochemical promotion (NEMCA) effect The same type of analysis is applicable regarding the size of nanoparticle catalysts supported on commercial supports such as Zr02, Ti02, YSZ, Ce02 and doped Zr02 or Ti02. What is the maximum allowable size of supported metal catalyst nanoparticles in order for the above NEMCA-type metal-support interaction mechanism to be fully operative ... 

---