Electrocatalysts method

The change in the electronic properties of Ru particles upon modification with Se was investigated recently by electrochemical nuclear magnetic resonance (EC-NMR) and XPS [28]. In this work, it was established for the first time that Se, which is a p-type semiconductor in elemental form, becomes metallic when interacting with Ru, due to charge transfer from Ru to Se. On the basis of this and previous results, the authors emphasized that the combination of two or more elements to induce electronic alterations on a major catalytic component, as exemplified by Se addition on Ru, is quite a promising method to design stable and potent fuel cell electrocatalysts. 

Recently, rhodium and ruthenium-based carbon-supported sulfide electrocatalysts were synthesized by different established methods and evaluated as ODP cathodic catalysts in a chlorine-saturated hydrochloric acid environment with respect to both economic and industrial considerations [46]. In particular, patented E-TEK methods as well as a non-aqueous method were used to produce binary RhjcSy and Ru Sy in addition, some of the more popular Mo, Co, Rh, and Redoped RuxSy catalysts for acid electrolyte fuel cell ORR applications were also prepared. The roles of both crystallinity and morphology of the electrocatalysts were investigated. Their activity for ORR was compared to state-of-the-art Pt/C and Rh/C systems. The Rh Sy/C, CojcRuyS /C, and Ru Sy/C materials synthesized by the E-TEK methods exhibited appreciable stability and activity for ORR under these conditions. The Ru-based materials showed good depolarizing behavior. Considering that ruthenium is about seven times less expensive than rhodium, these Ru-based electrocatalysts may prove to be a viable low-cost alternative to Rh Sy systems for the ODC HCl electrolysis industry. 

Reaction products can also be identified by in situ infrared reflectance spectroscopy (Fourier transform infrared reflectance spectroscopy, FTIRS) used as single potential alteration infrared reflectance spectroscopy (SPAIRS). This method is suitable not only for obtaining information on adsorbed products (see below), but also for observing infrared (IR) absorption bands due to the products immediately after their formation in the vicinity of the electrode surface. It is thus easy to follow the production of CO2 versus the oxidation potential and to compare the behavior of different electrocatalysts. 

Finally, a simple method for a rapid evaluation of the activity of high surface area electrocatalysts is to observe the electrocatalytic response of a dispersion of carbon-supported catalyst in a thin layer of a recast proton exchange membrane.This type of electrode can be easily obtained from a solution of Nafion. As an example. Fig. 11 gives the comparative... 

Similarly, Pd, Ag, and Pd-Ag nanoclusters on alumina have been prepared by the polyol method [230]. Dend-rimer encapsulated metal nanoclusters can be obtained by the thermal degradation of the organic dendrimers [368]. If salts of different metals are reduced one after the other in the presence of a support, core-shell type metallic particles are produced. In this case the presence of the support is vital for the success of the preparation. For example, the stepwise reduction of Cu and Pt salts in the presence of a conductive carbon support (Vulcan XC 72) generates copper nanoparticles (6-8 nm) that are coated with smaller particles of Pt (1-2 nm). This system has been found to be a powerful electrocatalyst which exhibits improved CO tolerance combined with high electrocatalytic efficiency. For details see Section 3.7 [53,369]. 

The small metal particle size, large available surface area and homogeneous dispersion of the metal nanoclusters on the supports are key factors in improving the electrocatalytic activity and the anti-polarization ability of the Pt-based catalysts for fuel cells. The alkaline EG synthesis method proved to be of universal significance for preparing different electrocatalysts of supported metal and alloy nanoparticles with high metal loadings and excellent cell performances. 

Once we have developed our basic model and shown how it may be used to estab-hsh trends in electrochemical reactivity, we will take the further step of applying it to the identification of new bimetallic electrocatalysts. We will introduce simple procedures to rapidly screen bimetallic alloys for promising electrocatalytic properties, and we will demonstrate the importance of including estimates of the alloys stabihty in the screening procedure. Finally, we will give examples of successful apphcation of this method to specific problems in the area of electrocatalyst development. 

The above results demonstrate that computational screening is promising technique for use in electrocatalyst searches. The screening procedure can be viewed as a general, systematic, DFT-based method of incorporating both activity and stability criteria into the search for new metal alloy electrocatalysts. By suggesting plausible candidates for further experimental study, the method can, ultimately, result in faster and less expensive discovery of new catalysts for electrochemical processes. 

Fernandez JL, White JM, Sun YM, Tang WJ, Henkelman G, Bard AJ. 2006. Characterization and theory of electrocatalysts based on scanning electrochemical microscopy screening methods. Langmuir 22 10426-10431. 

PtRu nanoparticle electrocatalyst with bulk alloy properties prepared through a sono-chemical method Langmuir 22 10446-10450. 

Reddington E, Sapienza A, Gurau B, et al. 1998. Combinatorial electrochemistry A highly parallel, optical screening method for discovery of better electrocatalysts. Science 280 1735-1737. 

Basnayake R, Li Z, Katar S, Zhou W, Rivera H, Smotkin ES, Casadonte DJ, Korzeniewski C Jr (2006) PtRu nanoparticle electrocatalyst with bulk alloy properties prepared through a sonochemical method. Langmuir 22 10446-10450... 

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. 

Metal oxides, 31 78-79, 89, 102, 123, 157-158, 191, 32 199-121 see also Amorphous metal oxides Sulfate-supported metal oxides specific oxides adsorbed oxygen on, 27 196-198 binary, surface acidity, 27 136-138 catalytic etching, 41 390-396 coordination number, 27 136 electrocatalysts, 40 127-128 Fe3(CO)i2 reaction with, 38 311-314 Lewis acid-treated, 37 169-170 multiply-valent metals, electrocatalytic oxidations, 40 154-157 superacids by, 37 201-204 surface acidity, methods for determining, 27 121... 

A preparative method using a ferrous hyponitrite complex, [Fe(NO)2Cl] +, as an active electrocatalyst for selective cy-clodimerization has been investigated. The active catalyst Fe(NO)2 can be prepared... 

Direct metal deposition from metallic sources has been extensively used for model catalyst deposition for high-throughput and combinatorial studies. However, these methods are also increasingly used to deposit practical electrocatalyst materials. The best known approach is the one developed by 3M researchers have used physical vapor deposition to deposit Pt and Ft alloys onto nanostructured (NS) films composed of perylene red whiskers. The approach has been recently been reviewed by Debe. ... 

Wee, J. H., Lee, K. Y, and Kim, S. H. Fabrication methods for low-Pt-loading electrocatalysts in proton exchange membrane fuel cell systems. Journal of Power Sources 2007 165 667-677. 

XAS has been successfully employed in the characterization of a number of catalysts used in low temperature fuel cells. Analysis of the XANES region has enabled determination of the oxidation state of metal atoms in the catalyst or, in the case of Pt, the d band vacancy per atom, while analysis of the EXAFS has proved to be a valuable structural tool. However, the principal advantage of XAS is that it can be used in situ, in a flooded half-cell or true fuel cell environment. While the number of publications has been limited thus far, the increased availability of synchrotron radiation sources, improvements in beam lines brought about by the development of third generation sources, and the development of more readily used analysis software should increase the accessibility of the method. It is hoped that this review will enable the nonexpert to understand both the power and limitations of XAS in characterizing fuel cell electrocatalysts. 

Investigations of enzyme-catalyzed direct electron transfer introduce the basis for a future generation of electrocatalysts based on enzyme mimics. This avenue could offer new methods of synthesis for nonprecious metal electrocatalysts, based on nano-structured (for example, sol—gel-derived) molecular imprints from a biological catalyst (enzyme) with pronounced and, in some cases, unique electrocatalytic properties. Computational approaches to the study of transition state stabilization by biocatalysts has led to the concept of theozymes . " ... 

Pto.45Pdo.45Bio.n/C in 0.2 M NaOH + 0.1 M EC, at various potentials (each 100 mV) from 130 to 1030 mV/RHE (1) and chromatograms of the anodic outlet of a SAMEC working with a Pto.45 Pdo.45Bio.i/C anode without fuel recirculation (2). Electrocatalysts were prepared according to the water-in-oil microemulsion method. 

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