Electrocatalysts heterogeneous

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... 

Many polypyridyl metallic complexes have been used successfully as electrocatalysts in homogeneous and heterogeneous systems and generally CO and 11 COO are the main products of reduction. Among these, the two complexes, [Re(bpy)(CO)3Cl] and [Ru(bpy)2(CO)X]" + (X = CO, Cl, H 11 2 or 1), have attracted much attention because of their characteristic... 

Catalysis is known as the science of accelerating chemical transformations. In general, various starting materials are converted to more complex molecules with versatile applications. Traditionally, catalysts are divided into homogeneous and heterogeneous catalysts, biocatalysts (enzymes), photocatalysts, and electrocatalysts, which are mainly used... 

In view of the complexity of heterogeneous systems, none of the above techniques will be able to supply, by itself, a complete atomic-level description of surface phenomena. A multi-technique approach has been perceived by many as most appropriate for fundamental studies in electrochemical surface science (30-2). Since none of the existing electrochemical laboratories are adequately equipped to perform a comprehensive experimental study, collaborative efforts between research groups of different expertise are burgeoning. Easier access to national or central facilities are also being contemplated for experiments which cannot be performed elsewhere. The judicious combination of the available methods in conjunction with the appropriate electrochemical measurements are permitting studies of electrocatalyst surface phenomena unparalleled in molecular detail. 

Dendrimer-Encapsulated Pt Nanoclusters as Heterogeneous Electrocatalysts for O2 Reduction... 

The chemistry of electrochemical reaction mechanisms is the most hampered and therefore most in need of catalytic acceleration. Therefore, we understand that electrochemical catalysis does not, in principle, differ much fundamentally and mechanistically from chemical catalysis. In addition, apart from the fact that charge-transfer rates and electrosorption equilibria do depend exponentially on electrode potential—a fact that has no comparable counterpart in chemical heterogeneous catalysis—in many cases electrocatalysis and catalysis of electrochemical and chemical oxidation or reduction processes follow very similar if not the same pathways. For instance as electrochemical hydrogen oxidation and generation is coupled to the chemical splitting of the H2 molecule or its formation from adsorbed hydrogen atoms, respectively, electrocatalysts for cathodic hydrogen evolution—... 

The problem of diffusion in electrocatalysts is analogous to that of diffusion in heterogeneous catalysis. The assumptions adopted in the model are as follows... 

Evaluating dendrimer templated nanoparticles in the absence of the dendrimer provides opportunities for insights into these new materials. In order to pursue these investigations, it is first necessary to immobilize DENs onto an appropriate substrate and to gently remove the dendrimer shell see Scheme 5. Opportunities for controlling nanoparticle size and composition make DENs potentially important precursors for heterogeneous catalysts and electrocatalysts, and DEN deposition and thermolysis are similarly critically important steps in pursuing these applications [45]. 

Because carbon black is the preferred support material for electrocatalysts, the methods of preparation of (bi)metallic nanoparticles are somewhat more restricted than with the oxide supports widely used in gas-phase heterogeneous catalysis. A further requirement imposed by the reduced mass-transport rates of the reactant molecules in the liquid phase versus the gas phase is that the metal loadings on the carbon support must be very high, e.g., at least lOwt.% versus 0.1-1 wt.% typically used in gas-phase catalysts. The relatively inert character of the carbon black surface plus the high metal loading means that widely practiced methods such as ion exchange [9] are not effective. The preferred methods are based on preparation of colloidal precursors, which are adsorbed onto the carbon black surface and then thermally decomposed or hydrogen-reduced to the (bi)metallic state. This method was pioneered by Petrow and Allen [10], and in the period from about 1970-1995 various colloidal methods are described essentially only in the patent literature. A useful survey of methods described in this literature can be found in the review by Stonehart [11]. Since about 1995, there has been more disclosure of colloidal methods in research journals, such as the papers by Boennemann and co-workers [12]. 

In the first group belong the techniques which are also used in heterogeneous catalysis for determining the surface area of catalysts. Two such techniques are widely used The Brunauer-Emett-Teller (BET) method, based on the physical adsorption of N2 or Ar at very low temperatures [8, 44] and the H2 or CO chemisorption method [8, 44], The first method leads to the total catalyst surface area, whereas the second leads to the specific (active metal) surface area. In the case of supported electrocatalysts (e.g., Pt/C electrocatalysts used as anodes in PEM fuel cells) the two techniques are complementary, as the former can lead to the total electrocatalyst surface... 

As in heterogeneous catalysis [44], small coverages of electropositive or electronegative adatoms, acting as promoters or poisons, can have very significant effects in the performance of electrocatalysts, as they can significantly modify the metal work function [10, 23, 44] and, thus, its chemisorptive propensity [10, 23, 44]. 

A positive BE shift implies a more negatively charged Pt atom, and thus CO chemisorption is weaker (better elec-trocatalytic activity) on such alloy electrocatalysts. This is consistent with the predominantly electron acceptor nature of CO adsorption on most metals [23] and with the recently established rules of electrochemical promotion [23, 99] and of classical promotion in heterogeneous catalysis [100] which predict that CO binding is weakened on high work function, that is, negatively charged surfaces. 

Scherson, Palenscar, Tolmachev and Stefan provide a critical review of transition metal macrocycles, in both intact and thermally activated forms, as electrocatalysts for dioxygen reduction in aqueous electrolytes. An introduction is provided to fundamental aspects of electrocatalysis, oxygen reduction, and transition metal macrocydes. Since the theoretical and experimental tools used for investigation of homogeneous and heterogeneous electrocatalysis are considerably different, these topics are given separate discussion. The influence of the electrode surface on adsorbed macrocydes, and their influence on mechanism and rates of 02 reduction is treated in detail. Issues related to pyrolyzed macrocydes are also described. 

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