Volcano effect

The combined use of the modem tools of surface science should allow one to understand many fundamental questions in catalysis, at least for metals. These tools afford the experimentalist with an abundance of information on surface structure, surface composition, surface electronic structure, reaction mechanism, and reaction rate parameters for elementary steps. In combination they yield direct information on the effects of surface structure and composition on heterogeneous reactivity or, more accurately, surface reactivity. Consequently, the origin of well-known effects in catalysis such as structure sensitivity, selective poisoning, ligand and ensemble effects in alloy catalysis, catalytic promotion, chemical specificity, volcano effects, to name just a few, should be subject to study via surface science. In addition, mechanistic and kinetic studies can yield information helpful in unraveling results obtained in flow reactors under greatly different operating conditions. 

Despite the fact that hydrogen is an important product of reforming, it is nevertheless added in the process primarily to combat deactivation by coking, and is a key process variable. Rohrer,20 and Franck,24 have demonstrated the volcano effect of a reduction in hydrogen pressure on the rate of dehydrocyclisation. The progressive reduction in rate at pressures less than 87 psig (0.7 mPa) is a result of the increased rate of deactivation by carbon-laydown as hydrogen pressure is reduced. 

Studies of atmospheric particles show that their distribution is often birno-dal i.e., the particles are made up of rwo separate fractions, one with fine and one with coarse particles (Fig. 9.1). The coarse particles, from about 2.5 pm upward, are made up of natural dust from the effect of wind, erosion, plants, volcanoes, etc. The finer fraction is made up of particles smaller than 2.5 pm and consists primarily of particles from human activity, combustion, traffic, and processes. 

Figure 4.30. Volcano-type behaviour Effect of catalyst potential on the rate of ethylene oxidation on a Pt film deposited on NASICON (Na3Zr2Si2PO 2), a Na+ conductor T=430°C, P02 =7.2 kPa, Pc2H4= kPa.102 Reproduced by permission of The Electrochemical Society.

Figure 4.31. Transition from volcano-type behaviour at low Po2 to electrophobic behaviour at high po2 during CO oxidation on Pt/j3"-A]203.51 Effect of UWr and linearized51 Na coverage 0Na on the rate of CO oxidation on Pt/p"-Al203 at varying po2- Other conditions pco=2 kPa, T=350°C. The top part of the figure shows the corresponding variation of the actual51 Na coverage, 0Na, with UWr- Reprinted with permission from Academic Press.

Figure 4.32. Volcano type behaviour. Effect of Uwr on the rates of C02, N2> N20 formation and on the selectivity to N2 during NO reduction by propene on Pt/p"-Al20j.98,99 Reprinted from ref. 98 with permission from Elsevier Science.

Figure 4.33. Inverted volcano behaviour. Effect of catalyst potential and work function on the rate of C2H6 oxidation on Pt/YSZ. po2=107 kPa, pc2H6 65 kPa T=500°C , T=460°C , T=420°C.24 Reprinted with permission from Academic Press.

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).

Figure 6.8. Example of rule G3 (volcano-type behaviour) Effect of Ph2(=Pd) (a), Po2 (=Pa) (b) and of potential UWR and AO (c) on the rate of H2 oxidation on Pt /graphite (a and b) and Pt/black (c) in aqueous 0.1 M KOH solutions.72,73 Note that under the pH2, Po2 conditions of Fig. 6.7c the open-circuit rate is positive order in H2 (Fig. 6.8a) and negative order in 02 (Fig. 6,8b) and that the orders are reversed with the applied positive potential (Uwr=1 -2 V). At this potential the rate passes through its maximum (volcano) value (Fig. 6.8c). Reprinted with permission from McMillan Magazines Ltd (ref. 72) and from the American Chemical Society (ref. 73).

Figure 6.12. Example of rules Gl, G2 and G3 Effect of pCo (=Pd) and of Na coverage and corresponding UWr and AO values on the rate of CO oxidation on Pt films deposited on P"-A1203 at fixed Po2=6 kPa71 Note that dr/dO(= dr/edUWR) always traces dr/dpco for negative, positive and zero (volcano peak) values. In the right figure the raw data (left) have been fitted to a polynomial expression.71 Reprinted with permission from Academic Press.

Effect of partial electron transfer parameter Figure 6.23 depicts the effect of the value of the partial charge transfer parameter A,d for fixed XA(= 0.15) on the rate enhancement ratio p(=r/r0) for the four main types of promotional behaviour, i.e., electrophobic, electrophilic, volcano and inverted volcano. The main feature of the Figure is that it confirms in general the global mle... 

Figure 6.23. Effect of partial charge transfer coefficient XD on catalyst performance for fixed X.A depending on dimensionless potential n, (a) electrophobic, (b) electrophilic, (c) volcano-type, (d) inverted volcano-type.

The effect of catalyst overpotential and potential on the rates of these two reactions is shown in Figs. 8.45 and 8.46. They both exhibit electrophobic behaviour for Uwr>U r and electrophilic behaviour for UWR< U, i.e. the reaction exhibits pronounced inverted volcano behaviour. 

The parameter a in Equation (11.6) is positive for electrophobic reactions (5r/5O>0, A>1) and negative for electrophilic ones (3r/0Oelectrochemical promotion behaviour is frequently encountered, leading to volcano-type or inverted volcano-type behaviour. However, even then equation (11.6) is satisfied over relatively wide (0.2-0.3 eV) AO regions, so we limit the present analysis to this type of promotional kinetics. It should be remembered thatEq. (11.6), originally found as an experimental observation, can be rationalized by rigorous mathematical models which account explicitly for the electrostatic dipole interactions between the adsorbates and the backspillover-formed effective double layer, as discussed in Chapter 6. 

Although natural selection is the only evolutionary agent that adapts organisms to their environments, the course of evolution has been profoundly influenced by major environmental changes, some of which had catastrophic effects. Some of these events resulted from Earth s internal processes, such as the activity of volcanoes and the shifting and colliding of continents. Others were the result of external events, such as collision of meteorites with Earth. 

The movement of Earth s crustal plates and the continents they contain - continental drift -has had enormous effects on climate, sea levels, and the distributions of organisms. Mass extinctions of organisms have usually accompanied major drops in sea levels. The collision of all the continents to form the gigantic landmass called Pangaea about 260 million years ago, triggered massive volcanic eruptions. The volcanoes... 

The occurrence of a compensation effect can be readily deduced from Eqs. (1.6) and (1.7). The physical basis of the compensation effect is similar to that of the Sabatier volcano curve. When reaction conditions or catalytic reactivity of a surface changes, the surface coverage of the catalyst is modified. This change in surface coverage changes the rate through change in the reaction order of a reaction. 

For the ascending branch of the volcano plot, the term (1/Z + 1) could serve by itself as an effective ORR activity predictor, whereas, for the descending branch, (1/Z + 1) becomes close to unity at 0.85 V, and the exponential factor exp(—A//, /R70, then determines the ORR rate based on the residual interaction of dioxygen with the (excessively) noble metal catalyst surface. 

The expression (1/Z+ 1)] exp[— AHl /RT] at 0.85 V, better reflects the reality of a partially oxidized Pt surface and the critical effect of active site availability on the rate of the ORR. Effects of site availability were not considered in the calculations in Nprskov et al. [2004] of ORR activity for various metals. The expression used to calculate activity defined the ordinate parameter in the ORR volcano plots presented. This parameter was defined in Nprskov et al. [2004] as kT min,- log(k,/ko). 

For the purpose of demonstrating the effects of surface coverage by Pd, 0pd, on the rate of electro-oxidation of formic acid and the ORR, Fig. 8.17 reveals that the i versus 0Pd relationship again has a volcano-like form, with the maximum catalytic activity being exhibited for 1 ML of Pd. The examples that we have given indicate that volcano relationships are the rule rather than the exception, emphasizing the importance of a systematic evaluation of the catalyst factors that control catalytic activity. A thorough... 

---