Volcano-type relationship

Support for the volcano-type relationship is also found in the gas-phase catalysis of the Haber process, namely the synthesis of NH3 from H2 and N2. On the other hand, the data given on the right-hand side of Figure 7.4, where the exchange-current density declines with increasing M-H bond strength, may be questioned, because the metals involved (from W to Ta in this figure) all have an oxide layer that is very... 

The magnitude of adsorption heat corresponds to the strength of adsorption bond, and so there should also be some relationship between adsorption and catalytic activity. The catal3dic activity is reversely proportional to adsorption strength when the surface coverage of reaction molecule reaches certain level, as indicated by Sabatier s theory of intermediate complex and experience. On the other hand, if adsorption is too weak, it is difficult to activate adsorbed molecules. The best activity can be obtained only in the case with suitable adsorption strength. This relationship is usually called as a volcano type curve, as shown in Fig. 2.4. 

It will be seen from above discussion that the activity of ammonia synthesis catalyst correlates not only with the chemical compositions, but also the crystal types and crystal structure of iron oxides. The relationships between the activity and the Fe +/Fe + ratio can be interpreted perfectly by the molecular ratio / of the iron oxides, which have the different crystal structures in their precursors. At the same time, it also gives the theoretical explanation for those results of the classical catalysts (Fig. 3.27). For example, for the classical volcano-type activity curve, when Fe +/Fe + = 0.5, then / = f (Eqs. 3.16 and 3.17), so the catalyst has the good activity both sides at Fe +/Fe + = 0.5, due to / < 1, so the activity of the catalyst decreases. 

Since the last century, it has been commonly believed that the catalyst has the best activity when its chemical composition and crystal structure of the precursor are most similar to those of magnetite. The relationship between the activity and the ratio (Fe +/Fe +) is a volcano type curve, which seems to be an unquestioned... 

This allows a direct influence of the alloying component on the electronic properties of these unique Pt near-surface formations from subsurface layers, which is the crucial difference in these materials. In addition, the electronic and geometric structures of skin and skeleton were found to be different for example, the skin surface is smoother and the band center position with respect to the metallic Fermi level is downshifted for skin surfaces (Fig. 8.12) [Stamenkovic et al., 2006a] owing to the higher content of non-Pt atoms in the second layer. On both types of surface, the relationship between the specific activity for the oxygen reduction reaction (ORR) and the tf-band center position exhibits a volcano-shape, with the maximum... 

Fig. 4 Depth-age relationship of the ice cores from Fiescherhom glacier [12] and Colle Gnifetti [13, 14], Besides annual layer counting and radiocarbon ( C) dating, two types of time markers were used Saharan dust events (labeled by the year only) and volcanic eruptions (labeled by year and name of volcano). Depth is given in water equivalent. This is the amount of water contained in the ice core which is calculated using fim and ice density, respectively, both increasing with depth...

We have summarized these developments in two recent papers the first addresses the topic of structure sensitivity in combination with BEP relationships (14) and the second addresses the Sabatier principle (27). Sabatier-type volcano relationships can be deduced for activity as a function of adsorption energy, and they can also be used to predict trends regarding deactivation of Fischer-Tropsch catalysts by C—C recombination reactions (28). We refer to these texts as background information to the material presented here. 

Recently there have appeared papers by other authors in which volcano-shaped curves have been obtained. Fahrenfort, van Reijen, and Sachtler (467) have carried out complex kinetic, IR spectroscopic, calorimetric, and mass spectrometric investigations on the decomposition of formic acid on various metals. The authors come to the conclusion that the reaction proceeds via the intermediate formation of an adsorption complex of the surface nickel formate type. By comparing the heat of formation of the formate of the corresponding metal with the temperature Tr at which a fixed depth of conversion r (log r = —0.8) is reached, the authors have obtained a broken line similar to the Balandin volcano-shaped curves (Fig. 63). The catalyst half-covered with the adsorption complex is the most active one. The reaction investigated by the authors differs from those investigated by us. It is characteristic, however, that in the case of oxides the selectivity is the same with respect to the decomposition of alcohols and of formic acid [Fig. 1 in Mars (468)). In their report at the Paris Congress on Catalysis Sachtler and Fahrenfort (469) give additional data on volcano-shaped curves for a number of reactions and point out that this relationship between the catalytic activity and the stability of the intermediate complex has been qualitatively predicted by Balandin. ... 

The relationship between thermodynamics and kinetics in chemical reactions is usually expressed by the Bronsted equation (eq. 3.52 in chapter 3.4) k = gKa, where k is the rate constant, K is the equilibrium constant of the elementary stage, and g and a (Polanyi parameter) are constant values for a serious of reactions. These constants are determined by parameters characterizing the elementary mechanism (composition and structure of the activated complexes, etc.) thus allowing for the existence of an optimum catalyst, on which the rate of catalytic reaction per unit of surface has a maximum value. Equations of the type (3.52) were used for the explanation of "volcano-curves", when catalytic activity as a function of thermodynamic characteristics follows a curve with a maximum. An example for a volcano curve in methanation of CO is given in Figure 7.6. 

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