Electrocatalytic Selectivity

Catalyst specificity to promote a certain reaction path is of immense importance for process design and economic evaluation. Selective catalysts 

The differences in selectivity between catalysts cannot be explained only in terms of the strength of reactant adsorption. A tentative explanation lies in the preference of platinum for concerted addition of protons to adsorbed alkenes with simultaneous electron transfer (25). The electronic structure of the surface intermediate of the concerted step appears to lead to halide cleavage. Palladium, on the other hand, can participate in insertion reactions (305) and promotes surface reaction between hydrogen atoms and adsorbed alkenes 4Sa. It is possible that palladium adsorbs vinyl halides on two different sites or at two different states, dependent on potential, one of which 

The selectivity of palladium and gold for alkene oxidation to aldehydes 28,29,170) was attributed initially to adsorption strength. However, electrooxidation in the presence of palladium ions indicates possible homogeneous alkene insertion, similar to the Wacker process 304). Homogeneous reaction is also involved in redox oxidations of hydrocarbons. In this case, the nature of the metal ions is expected to control selectivity. Indeed, toluene yields 20% benzaldehyde in electrolytes containing Ce salts, while oxidation proceeds to benzoic acid with Cr redox catalysts 311). In addition, the concentration of redox catalysts appears to affect yields in nonelectrochemical oxidation of ethylene large amounts of palladium chloride promote butene formation at the expense of acetaldehyde 312). Finally, the role of the electrolyte and solvent should not be ignored. For instance, electrooxidation of ethylene on carbon, in aqueous solution of acetic acid yields acetaldehyde 313) in the 

We should clarify here that the above cited studies are largely exploratory and the role of each parameter in reaction specificity is currently unclear. They show, however, the need for a fundamental understanding of molecular and electronic surface interactions that determine electrocatalytic as well as catalytic specificity. Thus, adsorption isotherms, surface states, molecular configurations, electronic distributions, dipole formation, and bond hybridization should be explored for well-characterized catalysts and model reactions in the presence and in the absence of an electric field. 

Selective surface poisoning may involve impurities or reaction intermediates, such as carbonaceous layers formed during hydrocarbon reactions. The order or disorder of this carbonaceous layer appears to affect selectivity, with demanding reactions favored by an ordered layer (575). Although alkene hydrogenation is assumed to occur on this layer (575), further characterization of its significance for catalyst selectivity is necessary. 

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The particular results of Figs. 34 and 35 and of Eqs. (121)—(128) can be extended to other values of kinetic parameters and to oxidation reactions as well (60-62). The qualitative information here, however, demonstrates the significance of transport processes for electrocatalytic selectivity control and of correctly identifying reaction products at several operating potentials. 

In the case of phenyldinitromethane [58[ the UPD-modified surfaces exhibit also remarkable electrocatalytic selectivity as regards the final reduction products under electrolysis conditions. From the two competitive reaction routes... 

Qi, J., Xin, L., Chadderdon, D.J., Qiu, Y., Jiang, Y., Benipal, N., Liang, C.H., and Li, W.Z. (2014) Electrocatalytic selective oxidation of glycerol to tartronate on Au/ C anode catalysts in anion exchange membrane fuel cells with electricity cogeneration. Applied Catalysis B Environmental, 154, 360-368. 

S.3.3 Electrocatalytic Modified Electrodes Often the desired redox reaction at the bare electrode involves slow electron-transfer kinetics and therefore occurs at an appreciable rate only at potentials substantially higher than its thermodynamic redox potential. Such reactions can be catalyzed by attaching to the surface a suitable electron transfer mediator (45,46). Knowledge of homogeneous solution kinetics is often used to select the surface-bound catalyst. The function of the mediator is to facilitate the charge transfer between the analyte and the electrode. In most cases the mediated reaction sequence (e.g., for a reduction process) can be described by... 

Table 3.1 lists some of the anodic reactions which have been studied so far in small cogenerative solid oxide fuel cells. A more detailed recent review has been written by Stoukides46 One simple and interesting rule which has emerged from these studies is that the selection of the anodic electrocatalyst for a selective electrocatalytic oxidation can be based on the heterogeneous catalytic literature for the corresponding selective catalytic oxidation. Thus the selectivity of Pt and Pt-Rh alloy electrocatalysts for the anodic NH3 oxidation to NO turns out to be comparable (>95%) with the... 

Silver films and Ag-CaO-SragOg cermets were chosen as the anodic electrocatalysts because of their high electrical conductivity, which is necessary for electrocatalytic operation, and also because of their high (>95%) selectivity to Cg hydrocarbons at very low (<2%) CH conversions [9]. 

Selecting a rigorous and convenient quantitahve parameter characterizing the catalyhc achvity, A, is of prime importance when studying electrocatalytic phenomena and processes. The parameter usually selected is the current density, i (in AJan ), at a specified value of electrode poteuhal, E. The current density is referred to the electrode s true working surface area [which can be measured by the Brunauer-Emmett-TeUer (BET) or other methods]. Closely related to this true current density is another parameter, known as the turnover number y (in s ), and indicating the number of elementary reachon acts performed or number of electrons transferred in unit time per surface atom (or catalytic surface site) of the catalyst. 

The values of electron work function (see Section 9.2.1) have been adduced most often when correlating electrocatalytic activities of given metals. They are situated between 3 and 5 eV. Two points were considered when selecting the electron work function as the parameter of comparison (1) it characterizes the energy of the electrons as basic, independent components of aU electrochemical reactions, and (2) it is closely related to many other parameters of metals. 

Special electrochemical sensors that operate on the principle of the voltammetric cell have been developed. The area of chemically modified solid electrodes (CMSEs) is a rapidly growing field, giving rise to the development of new electroanalytical methods with increased selectivity and sensitivity for the determination of a wide variety of analytes [490]. CMSEs are typically used to preconcentrate the electroactive target analyte(s) from the solution. The use of polymer coatings showing electrocatalytic activity to modify electrode surfaces constitutes an interesting approach to fabricate sensing surfaces useful for analytical purposes [491]. 

The selective and almost quantitative electrocatalytic formation of CO is obtained when [Ru(bpy)2(CO)2]2+ is used as electrocatalyst in aqueous acetonitrile (20 80) medium. In the absence of added water, formation of the [Ru(bpy)(CO)2]ra polymer is in competition with that of the hydride derivative [Ru(bpy)(CO)H]+, the latter being the active catalyst as demonstrated in a separate experiment using an authentic sample of this hydrido-complex.92 In those conditions HCOO" and H2 are also formed besides CO. 

The organic compounds were dissolved or dispersed in an aqueous solution of the catalyst, with or without an organic cosolvent, and the net oxidations were carried out at applied potentials causing the oxidation of Ru11 to RuIV complex (0.6-0.8 V vs. SCE). It has been demonstrated that this electrocatalytic system is capable of providing a general and selective method for the oxidation of alcohols, aldehydes, cyclic ketones, and C—11 bonds adjacent to alkeneic or aromatic groups. 

By using various polypyridyl oxo complexes a relationship between redox potentials ( 1/2) of the complexes and the efficiency and the selectivity of the electrocatalytic oxidation of alcohols and diols has been established.506 Higher 1/2 gives higher reactivity. The best results, from the point of view of synthesis, were obtained with the complex /ra ,v-[Ru (terpy)(0)2(0I I2)]2 which is characterized by a high redox potential and a relatively high stability. 

Techniques for attaching such ruthenium electrocatalysts to the electrode surface, and thereby realizing some of the advantages of the modified electrode devices, have been developed.512-521 The electrocatalytic activity of these films have been evaluated and some preparative scale experiments performed. The modified electrodes are active and selective catalysts for oxidation of alcohols.5 6-521 However, the kinetics of the catalysis is markedly slower with films compared to bulk solution. This is a consequence of the slowness of the access to highest oxidation states of the complex and of the chemical reactions coupled with the electron transfer in films. In compensation, the stability of catalysts is dramatically improved in films, especially with complexes sensitive to bpy ligand loss like [Ru(bpy)2(0)2]2 + 51, 519 521... 

J. Wang and H. Wu, Highly selective biosensing of glucose utilizing a glucose oxidase + rhodium + Nafion biocatalytic-electrocatalytic-permselective surface microstructure. J. Electroanal. Chem. 395, 287-291 (1995). 

Figure 15.14 illustrates a typical voltammetric result for the determination of dopamine in the presence of ascorbic acid with a CNT-modified electrode. The selective voltammetric detection of uric acid [82] or norepinephrine [83] in the presence of ascorbic acid has been demonstrated with a (3-cyclodextrin-modified electrodes incorporating CNTs. Ye et al. [84] have studied the electrocatalytic oxidation of uric acid and ascorbic acid at a well-aligned CNT electrode, which can be used for the selective determination of uric acid in the presence of ascorbic acid. The simultaneous determination of dopamine and serotonin on a CNT-modified GC electrode has also been described [85],... 

Figure 5.9 TEMPO DE is obtained by electrodeposition of a thin layer of orga-nosilica doped with TEMPO (2,2,6,6-tetramethylpiperidine-l-oxyl) upon application of — 1.1 V (v.v. Ag/AgCl) for 15 min to a solution of suitable organosilanes (left). The electrocatalytic film thereby obtained selectively converts benzyl alcohol dissolved in 0.2 M NaHC03 (right). 

The electrocatalytic activity of the nanostructured catalysts was investigated for electrocatalytic reduction of oxygen and oxidation of methanol. Several selected examples are discussed in this section. The results from electrochemical characterization of the oxygen reduction reaction (ORR) are first described. This description is followed by discussion of the results from electrochemical characterization of the methanol oxidation reaction (MOR). 

Electrocatalytic hydrogenation has the advantage of milder reaction conditions compared to catalytic hydrogenation. The development of various electrode materials (e.g., massive electrodes, powder cathodes, polymer film electrodes) and the optimization of reaction conditions have led to highly selective electrocatalytic hydrogenations. These are very suitable for the conversion of aliphatic and aromatic nitro compounds to amines and a, fi-unsaturated ketones to saturated ketones. The field is reviewed with 173 references in [158]. While the reduction of conjugated enones does not always proceed chemoselectively at a Hg cathode, the use of a carbon felt electrode coated with polyviologen/Pd particles provided saturated ketones exclusively (Fig. 34) [159]. 

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